Paper 1

Process Safety and Environmental Protection 150 (2021) 323–355
Contents lists available at ScienceDirect
Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep
Heavy metal removal from wastewater using nanomaterials-process

and engineering aspects
Samyuktha S. Kolluru a , Shreya Agarwal a , Sadamanti Sireesha a , I. Sreedhar a,∗ ,
Samir Ramdas Kale b
a
Department of Chemical Engineering, BITS Pilani Hyderabad Campus, Hyderabad, 500078, India
b
Department of Chemical Engineering, BITS Pilani Pilani Campus, Pilani, 333031, India
a r t i c l e i n f o a b s t r a c t
Article history: Nanomaterial adsorbents are highly favorable for heavy metal removal due to their large specific sur-
Received 22 January 2021 face areas with enhanced active sites for contaminant adsorption. This paper focuses on nanomaterial
Received in revised form 31 March 2021 adsorbents covering aspects like methods of synthesis, types of nanomaterials, kinetics, process opti-
Accepted 17 April 2021
mization, modelling and simulation and column studies besides citing future challenges. It has been
Available online 22 April 2021
found that among various synthesis protocols, Chemical Vapor Deposition was most effective in giving
desired attributes. Metallic composites and organic nanomaterials viz., nanocellulose, carbon nanotubes,
Keywords:
graphene complexes, magnetite forms etc exhibited highest metal removal capacities of 1989 mg/g for
Nanomaterials
Heavy metal adsorption
Hg (II) 1641 mg/g for Cd (II) at optimal process conditions. Eco-friendly nanomaterial adsorbents, their
Synthesis protocols properties and potential are also discussed in detail. This work also explores the performance of nano-
Eco-friendly materials in fixed bed columns where it showed its capability to be used as an effective adsorbent in
Regeneration continuous adsorption mode.
Dynamic adsorption © 2021 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Optimization
Simulation
Fixed bed columns
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
2. Synthesis techniques for adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
2.1. Effect of pH value of solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
2.2. Effect of amount of adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
2.3. Effect of initial metal ion concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
2.4. Effect of contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
2.5. Effect of available surface area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
3. Overview of different nanomaterials used in heavy metal removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
3.1. Metal nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
3.1.1. Zero-valent Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
3.1.2. Titanate nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
3.1.3. Iron oxide based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Abbreviations: AL, Adsorbent loading; ANFIS, Adaptive network based fuzzy inference system; ANN, Artificial Neural Network; APH, Adsorbent Packaging Height; BT,
Breakthrough Time; CA-LDH, Ca/Al layered double hydroxides; CD, Column Diameter; CS-CNT, chestnut shell-carbon Nanotubes; CTS-G-PA, chitosan-graft-polyacrylamide;
DHPCT, 3,4-dihydroxyphenethylcarbamodithioate; DMSA, Dimercaptosuccinic acid; EC, Exhaustion Capacity; FR, Flow rate; LAMMPS, Large-scale Atomic/Molecular Massively
Parallel Simulator; LDH/GO, Mg−Al-layered double hydroxide-supported graphene oxide; MGL composites, Magnetic composites consisting of magnetite (Fe3O4), graphene
oxide (GO), and Mg3Al−OH layered double hydroxide (LDH); MI, Metal Ion; MLP-ANN, Multi-layer perceptron; NC, Nanocomposites; NP, Nanoparticles; ORP, Oxidation –
Reduction Potential; RA, Reducing Agent; RBF-ANN, Radial basis Function; RO, Reverse Osmosis; SCMNP, Silica Coated Magnetic Nanoparticles; SOS, Symbiotic Organism
Search; ZnCr-LDH, Zn-Cr layered double hydroxide; ZVI, Zero Valent Iron.
∗ Corresponding author.
E-mail address: [email protected] (I. Sreedhar).
https://doi.org/10.1016/j.psep.2021.04.025
0957-5820/© 2021 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
S.S. Kolluru et al. Process Safety and Environmental Protection 150 (2021) 323–355
3.1.4. Zinc based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335

3.2.
Magnetic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.2.1. Magnetite (Fe3O4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.2.2. Other magnetic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.3. Carbon based nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.3.1. Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.3.2. Graphene based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3.3.3. Carbon nitride based (g-C3 N4 ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
3.3.4. Cyclodextrin based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
3.3.5. Sulphur impregnated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
3.4. Other nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
3.4.1. Agricultural waste materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
3.4.2. Zeolites and silica based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
3.4.3. Clay minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
3.5. Analysis of kinetic and equilibrium models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
3.6. Eco-friendly nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
4. Thermo-kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
4.1. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
4.2. Isotherms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .342
5. Desorption and Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
6. Continuous removal of metal ions and role of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
7. Modelling and simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
8. Process optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
9. Scale up and feasibility studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
10. Discussion and future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
11. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
1. Introduction (Gollavelli et al., 2013) and adsorption. Most of these methods

have limited industrial pollution as they are tedious, expensive and
Water pollution has become a serious problem all over the cause secondary pollution. Among the prevalent methods, adsorp-
world. Among the various water pollutants, heavy metals are an tion (Sreedhar et al., 2020) seems to be one of the most effective and
important environmental concern and the most hazardous as they broadly applied techniques due to the usage of commonly available
are highly toxic even at dilute concentration, non-biodegradable, by-products and low-cost alternatives such as fly ash, agricultural
and will accumulate through the food chain destroying aquatic life wastes, chitin, and chitosan (George et al., 2016).
and posing serious threats to human health. Heavy metals usually When used to remove heavy metals, presence of large surface
enter the food chain through plants and fish. Plants tend to take area is desired for contaminant detection, adsorption and immo-
up heavy metals dissolved in water, and those metals get accu- bilization and this is satisfied by the use of nanomaterials (Lu and
mulated at their roots and later get translocated to edible parts Astruc, 2018). Nanomaterial adsorbents have many unique prop-
like fruits & vegetables (Ahmad et al., 2020; Barakat, 2011). Major erties like nano size, large surface area, highly reactive, strong
heavy metals include cadmium, aluminum, cobalt, copper, iron and solution mobility, strong mechanical property, porosity characters,
lead. Although a minimum concentration is acceptable according hydrophilicity, dispersibility and hydrophobicity (Yaqoob et al.,
to regulatory limits, exceeding these limits can be hazardous to 2020). Several types of nanomaterials such as biosorbents(Journal,
humans. For example, cadmium can cause kidney damage and renal 2020), graphene, activated carbon and magnetic nanoparticle have
disorder. It mainly emanates from manufacturing of alloys, elec- been investigated as efficient adsorbents to remove heavy metal
troplating and smelting industries. Similarly, copper, which mainly ions from raw wastewater (Huang et al., 2018a; Zong et al., 2013).
comes from electronic industry and devise scraps can cause insom- Various researches have been conducted on use of nanoma-
nia, Wilson disease and liver damage. Nickel mainly originates terials aiming to improve its adsorption properties. This paper
from electroplating industries, mineral processing plant & battery compiles many nanomaterial based adsorbents where adsorption
manufacturing industries. It can cause chronic asthma, dermatitis capacities, process conditions and synthesis methods have been
and lung cancer. Lead comes mainly from metal plating indus- discussed along with the possibility of using these nanomaterials
tries, batteries industries, smelting of ores, fertilizers and pesticides for large scale applications and feasibility studies, with focus on
industries. It can cause brain damage, reproductive complications, eco-friendly adsorbents as these are the need of the hour. This paper
digestive problems and anemia(Ahmad et al., 2017; Barakat, 2011; also highlights the merits and demerits of each adsorbent to allow
Li et al., 2017b; Saha et al., 2019). Different detected metals and swift comparisons to be drawn and provides a complete analysis on
their concentration in the sample collected from the industry along nanomaterial modification and modelling techniques. This paper is
with WHO permissible limits are given in Table 1. unique for its vast yet concise coverage of the topic.
Various methods are being applied to treat wastewater and
eradicate the presence of heavy metals, such as chemical precip-
2. Synthesis techniques for adsorbents
itation and oxidation (Charerntanyarak, 1999), reduction, solvent
extraction, ion exchange (Wang et al., 2018a), membrane sepa-
There are various methods that are utilized to prepare adsor-
ration (Wang et al., 2017), coagulation (Charerntanyarak, 1999),
bents with nanomaterials. Fig. 1 gives an overview of the various
reverse osmosis (Volpin et al., 2018), solvent extraction (Hutton-
types of synthesis methods based on the adsorbent structure.
Ashkenny et al., 2015), ultrafiltration, remediation, electrodialysis
Few of the frequently used methods and their procedures, merits,
324
Table 1
Detected metals and their concentration in the sample collected from the industry.
Industry Iron Nickel Cadmium Lead Copper Zinc Chromium Arsenic Manganese Mercury References
Electroplating 127.5a 106.1 3.02 4.94 97.57 167.6 72.34 58.03 NDb ND (Bankole et al.,
2019)
Textile 0.39 0.13 ND 0.06 0.21 0.11 0.18 ND ND ND (Bhardwaj et al.,
2014)
Tannery ND ND 0.92 4.7 48.1 20.02 10,000 ND ND ND (Chowdhury et al.,
2015)
Smelting <0.1 ND 60 <1.0 <0.5 152 ND ND 170 ND (Xu et al., 2018b)
Automobile ND 2.04 6.09 2.91 14.50 19.38 0.46 ND 9.81 ND (Akpomie and
Dawodu, 2016)
Copper mining 292.6 ND 21.3 1.1 27.8 22.5 ND ND ND 7.5 (Fu et al., 2020)
WHO Permissible Limits 0.3 0.07 0.005 0.01 2 5 0.05 0.01 0.1 0.003 (Bankole et al.,
2019; Sayato,
1989)
a
All concentrations are in (mg/l).
b
ND = Not Detected.
Fig. 1. Dependence of Synthesis Protocols on structure of adsorbent.
demerits along with examples of adsorbent produced have been The influence of the pH of the solution, the amount of adsorbent,
summarized in the Table 2. the initial metal ion concentration, the contact time and surface
Widely categorized, there are two basic approaches for nanopar- area are factors that determine the efficiency of removal of metal
ticle synthesis: top-down approach and bottom-up approach ions (Grozdanov et al., 2018).
(shown in Fig. 2). Top-down approach involves the breakdown
of bulk material into small particles. These techniques are the 2.1. Effect of pH value of solution
extension of those that have been used to produce micron sized
particles. Top-down approaches are relatively simpler and depends The pH value of the solution is the most important factor gov-
on removal or division on bulk material to its desired properties. erning the adsorption process. Metal adsorption is sensitive to pH
A drawback of this approach is the imperfection of surface struc- and usually does not occur at low pH value. A study of the adsorp-
ture (Nizamuddin et al., 2018). For example, nanowires made by tion capacity of lead ions revealed that there was a sharp increase
lithography may contain many impurities and structural defects when pH increased from 1.0 to 5.0. The lower efficiency at acidic
on the surface. Some examples of synthesis techniques that use pH levels, can be justified by the adsorbent surface properties and
this approach are sol-gel synthesis (Epifani et al., 2000), electron conversion of functional groups due to protonation (Alam et al.,
beam lithography (Corbierre et al., 2005), atomic force manipula- 2020). For example, presence of positively charged groups can eas-
tion (Theil Hansen et al., 1998), gas-phase condensation (Liu et al., ily be protonated at lower pH, inducing an electrostatic repulsion
2020), etc. Bottom-up approach creates less waste and therefore to the heavy metal ions (Egodawatte et al., 2016; Li et al., 2014). For
is more economical than the top-down approach. This method some other adsorbents like phenanthrene, the effects of pH were
refers to synthesis techniques where build-up of the material less obvious. But studies still show that desirable range is 2.0 to 12.0
occurs from the bottom. It utilizes the concepts of molecular self- (Huang et al., 2019; Krishna Kumar et al., 2017; Plohl et al., 2019).
assembly and/or molecular recognition. The foremost advantage
of the bottom-up approach is that it can synthesize homogenous
nanostructures with perfect crystallographic and surface structures 2.2. Effect of amount of adsorbent
(Ali et al., 2019). Some examples are hydrothermal synthesis (Darr
et al., 2017), template assisted sol-gel (Anuradha, 2010), electrode- The amount of adsorbent is another vital factor to improve
position (Tonelli et al., 2019), etc. Among the two approaches, process efficiency. Generally, it was found that increasing the adsor-
bottom-up is preferred as it has many merits such as fewer surface bent dose provides greater surface area and availability of more
defects, better ordering and more homogenous chemical composi- active sites, thus leading to enhancement of metal ions uptake.
tion (Pareek et al., 2017; Prof et al., 1986). Studies conducted with biosorbents, perlite and graphene proved
the same (Bankole et al., 2019; Singh et al., 2017; Wadhawan et al.,
325
S.S. Kolluru et al.
Table 2
Synthesis Methods.
Sr No. Method Used Structure/ Examples of Process Summary Merits Demerits Remarks Reference
for Synthesis absorbents Produced
1. Microwave Iron Based Electromagnetic irradiation via Restricted agglomeration, low low yield due to To scale up synthesis, (Bilecka and
assisted Nanoparticles (NP)/ ionic and molecular conduction contamination low cost, rapid limitations in vessel use multimode Niederberger,
synthesis Nanocomposites (NC) heating with less energy size microwave 2010; Lidström
et al., 2001; Mondal
et al., 2020)
2. Hydrothermal Iron based NP/NC, Mixture of desired plant lower temperature to produce control thickness of Highly pure hematite (Byrappa and
Synthesis Nano zeolites extract and required metal salt crystals than calcination carbon coating by using leaf extract with Adschiri, 2007; Ji
molarity, from alkaline silica modifications double photolytic et al., 2018;
source activity Mondal et al.,
2020; Su, 2017)
3. Novel Magnetic Cellulose NC Cotton cellulose and NaOH, pH Works in any environmental – Iron NP spread evenly (Klemm et al.,
(Borohydride) 7, add FeCl2, KBH4, NH4, conditions, cellulose is widely through cellulose 2011; Siró and
Reduction separated with magnet available matrix. Plackett, 2010;
Zhou et al., 2014)
4. Sintering Cementous Composites Mixed with ball mixing Energy-saving, low cost, reuse of Fe Oxide to be prepared Add Fe Oxide NP to (Maiti et al., 2018;
(FA10C) machine, Fly Ash sintered with fly ash decreases carbon footprint by Hydrothermal diminish mullitization Wang et al., 2020a)
Fe Oxide NP synthesis first temperature
5. Adsorption Chitosan Magnetic Coprecipitation synthesized NP strong metal chelating tendency, pH reduced from high constant stirring and (Bhatia et al., 2017;
Nanocomposites Eg:- dissolved in de-ionized water, large surface area, rigid to low resulted in bubbling of N2 gas for Shalaby et al.,
Fe Oxide NP coated pH increased, chitosan solution membranes decrease in removal 30 min for completion 2014)
with chitosan added adsorbs on nanoparticle efficiency
surface.
326
6. Sol-gel Process Fe3O4 magnetic core SCMNPs dispersed using High Reusability (5 cycles), direct Optimum removal only Maximum removal (Bhatia et al., 2017;
shelled by mesoporous ultrasonic agitation, application to contaminated when pH is close to 98.8 %, 96.4 %, 95.7 % Egodawatte et al.,
silica, and productredispersed, refluxed, sites(non-toxic) 6.9(zero-point charge) for Hg (II), Pd (II) and 2016; Vojoudi
cetyltrimethylammo- collected magnetically Pb(II) ions et al., 2017; Zhang
nium bromide (CTAB) et al., 2013a)
as surfactant template
Chemical Vapor 3D Graphene based Carbon source decomposed on Nickel substrate formation of Copper substrate Plasma enhanced CVD- (Hiew et al., 2018;
7. Decomposition metal substrate; control
structures (foam, several layers increases stability breaks down during without sacrificial Xiao et al., 2019a)

(CVD) network, hydrogel, formed layers with handling template
aerogel, monolith, prefabricated metal framework
bead, sponge)
CNTs highest aspect ratio, lowest adsorption capacity of modified multi-walled (Chawla et al.,
integrated intensity ratio and CNTs grown on Al2O3 carbon nanotubes 2015; Park et al.,
diameter size distribution is superior increases adsorption 2016)
capacity
8. Freeze Drying 3D Graphene based Rapid freezing of aqueous Yields highly oriented Configuration synthesis depends on (Hiew et al., 2018;
structures dispersion of to construct 3D interconnected GO composite inconsistent the freezing Xiao et al., 2019b)
structure (ice template), GO layers throughout the temperature of
sheets between neighboring structure additive
ice crystals
9. Emulsion Magnetic Fe/C Dissolved in deionized water, High surface area, environmental Higher activity removal (Chen et al., 2018;
Synthesis (In crosslinked NP nanotube suspension added, stability, fast removal towards Cr Zhou et al.,
situ Oxidation) (MNZVI/CNTs-OH NP) ultrasonic vibrations, 2014)(Su, 2017)
magnetized by hot wind and
separated
S.S. Kolluru et al.
10. Bio Reduction Reduced GO/Iron NP Oxidized graphite powder with low cost, green method, rapid Higher removal of Pb, (Lu and Astruc,
H2SO4, KMnO4, heated, add removal, Single step, 1:2 ratio of solution to 2018; Saharan
H2O2 and filter, add eucalyptus leaf extract et al., 2014; Xiao
FeCl3.6H2O and eucalyptus et al., 2019a)
leaf extracts, vacuum filtered
11. Calcination Graphitic Carbon facile one-step calcination of low-cost, environmentally friendly, Rarely used till now in Surface ammonia (Dickie, 1929; Xiao
Nitride Nanosheets guanidine hydrochloride and efficient adsorbent for metals practical application groups active in et al., 2018; Zhao
adsorbing metal et al., 2015)
12. Co- Layered Double Coprecipitation of Mg and Al One step, simple process Potential is present, Used to remove Cu(II), (Anjum et al., 2019;
precipitation Hydroxides compounds under protection but yet to be used in Pb(II) and Cd(II) He et al., 2005; Li
of nitrogen practical application and Duan, 2005;
Zhang et al., 2020)
13. Modified Graphene Oxide (GO) Expandable graphite powder, Introduces many Trace of Ni ions concentration of GO at (Chawla et al.,
Hummers nanosheets sodium nitrate, sulphuric acid; oxygen-containing functional decrease gradually 70 mg removes all the 2015;
Method KMnO4 solution added; kept in groups on surface of nanosheet with increase in GO heavy metal ions Gopalakrishnan
reflux system, washed with which result in high-sorption of concentration. effectively et al., 2015)
repeated centrifugation heavy metal ions.
14. Facile one-pot Mesoporous Doping CP into silica Large pore volume, bimodal pore Low removal efficiency very efficient even at (El-Nahhal et al.,
327
method silica-calcium framework (Na2HPO4.12H2O, distribution at low pH low metal 2018; He et al.,
phosphate hybrid NP ethanol, ammonia; add concentration and 2018)
(MS-CP) C18TMS and TEOS, filter substantial amounts of
product), calcine to remove M(II) can be removed
template and obtain MS-CP. from aqueous
solutions.
15. Inverse Covalently bonded Modification of Fe3O4 Excellent mechanical stability and – One pot (Li-ping Jiang et al.,
suspension Fe3O4 nanoparticle/ nanoparticles, nanorods; reusability method-carried out in 2018a; Meouche

polymerization poly (acrylic acid-co- grafting, polymerization of the same oil phase and et al., 2012; Xu
process acrylamide)/attapulgite organic monomers in terms of consequently in the et al., 1998)
nanorod composite acrylic acid and acrylamide; same reactor
soft magnetic beadlike simplified into one-pot method
adsorbent
16. Electrospinning Fe3O4/o-MWCNTs/ electrospinning solution of superparamagnetic properties for Regeneration capacity (Bassyouni et al.,
polyamide 6 hybrid CFPA6 for fabrication its separation of four 2019; Huang et al.,
nanofibrous membrane nanofiber membrane adsorption-desorption 2003; Subbiah
composite composite cycles. et al., 2005)
Fig. 2. Top-down and Bottom-up approach of nanoparticle synthesis.
2020). Experiments studied the effect of the amount of the nano carbon nanotubes, graphene and magnetic nanocomposites can be
adsorbent on the removal of Hg(II), Pd(II) and Pb(II) metal ions were mainly used. Similarly, it was observed that in some cases nanorods
carried out at room temperature and at pH = 4 by varying amounts show better adsorption capacity in comparison to nanotubes, for
of the adsorbent (i.e. 20−100 mg) in 10 mL of 50 mg L-1 solution example in case of Zn+2 and Pb+2 removal but lower in case of
of each metal ions. The results showed that the removal efficiency Cu+2 . It was also observed that super-paramagnetic nanoparticle
increased from 46.31% to 91.63% for Hg(II), 56.75% to 92.75% for having faster and selective adsorption towards Hg+2 (Khan et al.,
Pd(II), and 69.57% to 96.63% for Pb(II) with the increase in dosage 2019; Li et al., 2018; Tang et al., 2014). Suitable adsorbents with
of adsorbent from 20 to 50 mg (Vojoudi et al., 2017). respect to the metal that they remove efficiently is shown in the
Table 3 .
2.3. Effect of initial metal ion concentration The growing concern about degradation of the environment has
significantly increased use of green methods in recent times. In
Another important factor that was studied is the effect of initial 2015, Carbon-based adsorbents were very widely researched and
metal ion concentration. Studies on the variation and effects on being used. Whereas nearing 2020s we see a shift of research inter-
percentage removal revealed that decreases with increase in initial est into green methods (Gan et al., 2020). Agglomeration is a huge
metal ion concentration (Grozdanov et al., 2018). For example, in drawback in chemical synthesis of NPs. Without proper storage,
a study of green synthesized silicon nanocomposites for enhanced adsorbents can lose their properties by agglomerating using the
Lead (II) removal, the adsorption capacities increased from 24.92 to moisture present in the environment. Although adding particles
197.93 mg/g as the initial concentration of Pb2+ ions increased from like cellulose, chitosan and GO, will decrease agglomeration; in
10 to 100 mg/g. These results suggested that the actual amount of green route synthesis, a main advantage is that nothing has to be
Pb2+ ions adsorbed per unit mass of the adsorbent increased with added manually as there are proteins already present that act as
metal ion concentration (Saini et al., 2020). stabilizers and coating agents. Green methods are advantageous as
the materials used such as microorganisms, plants, seeds, etc. can
2.4. Effect of contact time be acquired without difficulty. An additional advantage with the
use of cellulose based NP is that they can be used to increase effi-
Another crucial factor is contact time, which shows an increase ciency, as the cellulose matrix offers even spread of all iron NP (Liu
in biosorption with an increase in contact time (Alhan et al., 2019) et al., 2015, 2014a).
In the same study of green synthesized silicon nanocomposites, Another resourceful green methods is sintering. Fly ash is usu-
experiments were performed by varying contact time (10–60 min.) ally disposed into ash ponds. This ash can eventually leach toxic
and initial Pb2+ concentration (10–100 mg/L) keeping all other compounds into water bodies. Hence Cementous composite syn-
parameters constant. The percent removal increased from 63.43 thesis by sintering is one of the notable green methods as it reuses
% to 93.94 % with time (Saini et al., 2020). this fly ash.
These are yet to be scaled up and put into production, but there
2.5. Effect of available surface area is increasing scope for these methods to be made more efficient and
cost effective through intensive research. For instance, microwave
The last crucial factor for nanomaterial adsorbents is availability assisted synthesis faces difficulty in the scaling up process but using
of large surface areas to increase the number of active sites. For multimode microwaves can overcome this problem. This shows the
example, in case of Pb(ii) adsorption on etched Ti3AlC2 nanofibers scope of research being done to derive methods to assist in scaling
and nanosheets, the maximum value of adsorption was ascribed to up green processes successfully and efficiently.
higher surface area and the abundant oxygen-containing functional Bio reduction can also be used to synthesize graphene oxide
groups. Layered 2D etched Ti3AlC2 nanofibers and nanosheets with (GO) that can remove contaminants very rapidly, at low costs.
different morphologies had positive and high S 0 values of 74.6 Trading off cost for high efficiency, Chemical Vapor Decomposition
J/mol K and 48.8 J/mol K respectively, indicating feasibility and high (CVD) and freeze drying can be used. These give 3D graphene-
affinity towards Pb(ii) adsorption. based structures with interconnected GO composite layers. In CVD,
The type of adsorbent that should be utilized depends on the efficiency changes according to the substrate. Use of a plasma mem-
heavy metal that is targeted to be removed. For instance, iron brane is a very efficient way to perform CVD. From an economical
containing adsorbents have been proved to be very effective in viewpoint, magnetic separation of adsorbents is a successful tech-
the removal of arsenic (Xu et al., 2018a). Whereas GO effectively nology, as it is able to deal with huge amounts of effluents despite
removes Cr and Pb completely but traces of Ni decrease grad- successive regeneration (Abouzeid et al., 2019). However, separat-
ually with increase in concentration of GO. Further, studied at ing nanoparticles from the solution after the adsorption process
specified conditions, GO is able to remove all heavy metal ions involves a complex procedure. To ease the separation, a combina-
(Gopalakrishnan et al., 2015). For removal of Hg, Pb, Cr, and Cd, tion of magnetic particles and NP is used to form magneticnano
328
Table 3
S.S. Kolluru et al.

Performance of Various Materials Used.
S.NO. Material Used Metal Kinetics Best Equilibrium Adsorption Conditions Remarks Reference
Removed Capacity
1. H-TiO2 Arsenic Pseudo-first-order Langmuir model 24 to 46 mg/g pH - 4 to 9 Increasing total As (III) concentrations, (Jegadeesan et al.,
kinetics sorption behaviour increases (surface 2010)
saturation)
2. Zero-valent iron Cr(VI) Pseudo-first-order Langmuir 101 mg/g pH 3.0, contact assembled on magnetic (Lv et al., 2014)
kinetics time: 120 min Fe3O4/graphene nanocomposites
3. CuO Hg2+ Pseudo Langmuir model 825.21 mg/g pH 9, 278 K, High adsorption at high pH, decreasing (Fakhri, 2015)
second-order CuO dose -0.05 protonation, easier diffusion.
equation g
4. Zerovalent Iron Arsenic Pseudo Langmuir model 1.997 mg/g pH 7.5, ORP Loaded with activated C, useful for (Zhang, 2003)
(ZVI) second-order −300 V to aqueous phase
-500V
5. Fe2 O3 Pb(II) Pseudo-first-order – 93.9 mg/g pH below 7 cobalt or nickel doping enhances (Chen et al., 2019)
kinetics removal capacity
6. Al(OH)CO3 As(V) Pseudo-first-order Langmuir As(V) – 170 m/ 150C 5 mg Al(OH)CO3 nanospheres could (Cao et al., 2012)
Cr(VI) kinetics g Cr(VI) - 60 purify 6 kg As(V) contaminated water,
mg/g reducing the As(V) concentration from
100 ppb to less than 10 ppb
Cd(II) 123.205 mg/g, environmentally friendly and
g-C3 N4 Pseudo first Langmuir low-cost adsorbent, superior (Xiao et al.,
7. Pb(II) 136.571 mg/g pH 6 to 8
nanosheets order kinetics isotherm 2019a)
Cr(VI) 684.451 mg/g adsorption capacity (multiple
As(III) functional groups)
Pseudo second 0.72 mg/g High binding because of different (Parsons
8. MnFe2 O4 Langmuir pH: 2−6
As(V) order kinetics electron transfer from Mn or Fe et al., 2009)
2.13 mg/g
Sr(II)
Th(IV) 280.8 mg/g pH 3.0 for
Fungus Pseudo second Langmuir Th(IV) Fungus magnetite nanocomposites (Chen et al.,
9.
Magnetite 2014)
329
order kinetics isotherm eliminate radionuclides.

U(VI) 100.9 mg/g pH 5.0 for
223.9 mg/g Sr(II) and
Mn(II) U(VI) Metal cations as high-spin aqua
Freundlich 76.78 mg/g (Erdem
10. Zeolite – – complexes, hydrate ion diameter
adsorption et al., 2004)
same as diameter of aqua-complex
Zn(II)
133.85 mg/g ions
11. Graphene oxide Cr(II) Limiting pseudo Langmuir 45 mg/g pH 4, contact Inverse spinel nickel based ferrite (Lingamdinne et al.,
second order time: 120 min composite 2016)

12. Carbon Nanotubes Cr(VI) Pseudo second Langmuir 264.5 mg/g pH 2, contact Composite with activated alumina (Sankararamakrishnan
order kinetics Freundlich time: 240 min et al., 2014)
13. Silica Cd(II) Pseudo second Langmuir 14.61 mg/g pH<8, contact Functionalized with mono amino and (Machida et al., 2012)
order kinetics time: 1440 min mercapto groups
14. Nano bentonite Pb(II) – Langmuir 7.93 mg/g pH: 4.5, contact Crosslinked tubes were visualized by (Tirtom et al., 2012)
crosslinked time: 80 min SE
Chitosan
15. 3,4 – Hg(II) Pseudo second Langmuir and 52.1 mg/g pH: 9 Fe3O4 was capped by DHPCT ligand via (Venkateswarlu and
dihydroxyphenethyl- order kinetics Freundlich facile synthetic method Yoon, 2015)
carbamodithioate
16. Hematite Pb(II) Pseudo second Freundlich 100 % pH:8, Temp: – (Shipley et al., 2013)
order kinetics 45C
17. n-Al2 O3 Cr(VI) Non-linear pseudo Langmuir 5 *10-̂3 mg/L Temp: 30−60, g-alumina nanoparticles modified with (Almeida et al., 2019)
second order contact time: cetyl trimethyl ammonium
kinetics 0−1.5 hours bromide(CTAB)
18. ZnO Cd(II) Pseudo second Langmuir and 96.15 mg/g pH: 7 prepared with activated carbon (ratio (Alhan et al., 2019)
order kinetics Freundlich 9:1)
19. Nanochitin isolated Ag+ Pseudo second Langmuir 34.35 mg/g pH: 6.5 Both negative charge density and the (P. Liu et al., 2014a)
from bioresidues order kinetics absence of aggregation favoured
adsorption
20. NanoCellulose Hg(II) – Redlich–Peterson 926.3 mg/g – adsorption is an endothermic and (Zarei et al., 2018)
isotherm spontaneous
S.S. Kolluru et al.
Table 3 (Continued)
S.NO. Material Used Metal Kinetics Best Adsorption Conditions Remarks Reference
Removed Equilibrium Capacity
21. UiO-66-NH2 Hg(II) Pseudo second Langmuir and 1111.2 mg/g pH: 5 peroxidase-like activity, peroxidase (Li et al., 2017a)
order kinetics Freundlich substrate TMB can be catalytically
oxidized in the presence of H2O2
22. SiO2 /TiO2 -MoS2 Pb(II) First order kinetics Langmuir 740.4 mg/g 450C Affinity of Pb(II) to sulfur atoms from (Liu et al., 2012a)
MoS2
23. Fe3 O4 -Graphene U(VI) Pseudo second Langmuir 69.49 mg/g 293 K, pH: 5.5 simultaneous precipitation and (Zong et al., 2013)
Oxide order kinetics inner-sphere surface complexation
24. Magnetite-reduced As(III) Pseudo second Langmuir 13.10 mg/g pH: 5−7 iron nanoparticles uniformly dispersed (Zhou et al., 2014)
graphene oxide order kinetics in the cellulose matrix due to strong
interaction between cellulose and nZVI
25. Fe3 O4 @ Pb(II) Pseudo second Langmuir 238 mg/g pH: 5−6, 25C uniform core–shell structure, high (Zhang et al., 2013b)
SiO2 -NH2 -MNPs order rate equation loading of amino-functionality via
sol–gel process by conformal coating
Fe3O4 particles with SiO2 and –NH2
groups in one-pot sol–gel process
Cu(II)
Pb(II) 122.7 mg/g CA-LDH synthesized by facile
CA-LDH + Graphene Pseudo-second Langmuir and
26. pH: 5, 298 K hydrothermal method, characterized (Yao et al., 2017)
Oxide order kinetics Freundlich
Cr(VI) 221.2 mg/g by TEM, SEM, FT-IR, XRD and XPS
64.4 mg/g
As(III)
Iron doped nano Pseudo-second 15 mg/g pH 6.5−7.5 (Sharma et al.,
27. Langmuir Suspension Polymerization
carbon As(V) order kinetics 2010)
5 mg/g pH 5-5−6.5
28. CS-CNT Pb(II) – Langmuir 1641 mg/g pH: 5 Mono-layer adsorption (Yang et al., 2020)
29. EDTA Hg(II) Pseudo-second Langmuir 268.4 mg/g 298 K – (Cui et al., 2015)
functionalized order kinetics
330
magnetic GO
30. Alumina in As(V) Pseudo-second Langmuir 6.56 g/g pH: 7.2, 30C 0.05 M Sodium hydroxide – most (Saha and Sarkar, 2012)
CTS-G-PA Cupric order kinetics suitable desorption agent, almost 100
Oxide % recovery without deforming beads
As(III) Presence of sulphate and silicate
Pseudo-second 26.9 mg/g pH 6−10, (Martinson and
31. CuO Langmuir inhibits As(III) adsorption, no effect
As(V) order kinetics 21−25C Reddy, 2009)
22.6 mg/g on As(V)
32. ZnO-Gr Ni(II) Pseudo-second Langmuir and 29.80 mg/g pH: 8.2 At pH > 8.2, adsorption uptake (Hadadian et al., 2018)

order kinetics Freundlich decreases
33. Anatase Pb(II) Pseudo second Langmuir 31.25 mg/g pH: 6, Temp: Sol–gel method using (Özlem Kocabaş-Atakli
order kinetics model 25C, contact tetraisopropoxide and 2-propanol and Yürüm, 2013)
time: 750 min
34. 3- Hg(II) Pseudo second Freundlich 98.6 mg/g Surface area: Lipase catalysed thiolation process (Ram and Chauhan,
mercaptopropionic order kinetics isotherm 404.95 2018)
acid
35. Graphene oxide Cu(II) Pseudo-second Langmuir 390.34 mg/g pH: 2.0–6.0 PAA chains act as binder, modifier, and (Han et al., 2018)
(GO)/ polyacrylic order kinetics Model active sites provider. Synergistic effects
acid (PAA) of 3D porous structure
Zn(II) Higher pH increases dedoping of
Polyaniline 49.751 mg/g pH: 9, contact (Diab et al.,
36. – Langmuir Model protons from nitrogen centers,
Fibres time: 1 h gives more adsorption sites 2020)
accessible for metal ions for
Cr(VI) coordination interaction
42.735 mg/g
37. Titanium Pb(II) Pseudo second Freundlich 80 mg/g pH: 6, contact Sol-gel method, drying and annealing (Bhatia et al., 2017)
tetrapropoxide and order kinetics isotherm time: 1200 min at 100 and 400 C,
propanol
38. FeS Hg(II) Pseudo second 1989 mg/g pH range: 6−11 Stabilized by biomaterials like sodium (Sun et al., 2018)
order kinetics carboxymethyl cellulose (CMC), gelatin
and starch
S.S. Kolluru et al.
39. Polyaniline Cr(VI) Pseudo second Langmuir 186.6 mg/g pH: 5.2 Reduction activity of redox pair of = (Lei et al., 2020)
magnetic chitosan order kinetics model N-/-NH groups in material structures
nanomaterials facilitated in-situ chemical reduction
of Cr (VI) to Cr (III),
Monodispersed As(V)
Pseudo second Langmuir and 43.8 mg/g Monodispersed hierarchical (Zhang et al.,
40. Gamma-AlOOH / pH: Neutral (7)
Cr(VI) order kinetics Freundlich structures 2016a)
Fe(OH)3 13.1 mg/g
Cd(II) pH: 6, contact formation of mono-layer,
Thioglycolic acid/ Pseudo second 91.3 mg/g (Kenawy et al.,
41. Langmuir model time: 30, room homogeneous adsorption sites,
mesoporous silica Hg(II) order kinetics 2018)
42.8 mg/g temperature exothermic
42. LDH/GO U(VI) Pseudo second Langmuir 129.9 mg/g Temp: 298 K, Hydrothermal Treatment (Linghu et al., 2017)
order kinetics model pH: 4.5
43. MgAl-LDH/rGO Pb(II) Pseudo second Elovich Model 116.2 mg/g pH: 4.5, Temp: Co-precipitation (Varadwaj et al., 2017)
order kinetics 300K
44. Halloysite Cd(II) Pseudo second – 11.4 mg/g Contact time: magnetic sorption for (Amjadi et al., 2015)
nanotubes - Fe3 O4 order kinetics 45 min, Room preconcentration of cadmium(II)
Temp
Cu(II)
Ni(II) 21.05 mg/g (Chenab et al.,
Pseudo second Contact Time: 2 Signs of precipitation over long
45. Talc- Fe3 O4 Langmuir model 2020) (Kalantari
order kinetics min periods
Pb(II) 33.33 mg/g et al., 2015a)
74.62 mg/g
46. Chitosan/ Fe3 O4 Hg(II) Pseudo second Langmuir 10 mg/g pH: 3, room Binding via carbodiimide activation (Nasirimoghaddam
order kinetics isotherm temperature et al., 2015)
47. Magnetite GO/LDH Pb(II) Pseudo second Langmuir 192.3 mg/g contact time: Adsorption (Huang et al., 2018b)
331
order kinetics model 240 min,

unadjusted
initial solution
pH
48. Starch/SnO2 Hg(II) Pseudo second Freundlich 192 mg/g pH: 6, contact Endothermic adsorption (Naushad et al., 2016)
order kinetics isotherm time: 60 min
98 %
87 %
Pd(II)

Mesoporous Pseudo second Langmuir 90 % Contact time: adsorption mechanism limited (Fato et al.,
49.
Fe3 O4 order kinetics isotherm 30 min by monolayer coverage 2019)
Cd(II) 78 %
Cu(II) Ni(II)
(simultane-
ous)
50. MWCNT based PVA Pb(II) – Langmuir and 1000 microg/L pH: 2.9 Hydrogel used as substrate for (Abraham et al., 2012)
hydrogel Freundlich effective dispersion of CNT
51. Polypyrolle Hg(II) Pseudo second Elovich model 769 mg/g pH: 7, Temp: chemisorption as well as intra-particle (Zhou et al., 2017)
graphene oxide - order kinetics 300K diffusion
Fe3 O4
52. Carbon nanosphere Cr(VI) Pseudo second Langmuir- 200 mg/g Contact time: Synthesis by novel thermal (Ji et al., 2012)
– Fe2 O3 order kinetics Freundlich 720 min, pH: decomposition
model 5.3
Pb(II)
81.5 mg/g Contact time:
Bentonite- Cd(II) Pseudo second Langmuir Facile one-step solvothermal (Yan et al.,
53. 30 min., Temp:
Fe3 O4 order kinetics isotherm 21.7 mg/g method 2016)
Cu(II) 200C
S.S. Kolluru et al.
Table 3 (Continued)
S.NO. Material Used Metal Kinetics Best Adsorption Conditions Remarks Reference
Removed Equilibrium Capacity
19.6 mg/g
54. Carbon – Fe3 O4 As(III) Pseudo second – 29.4 mg/g Temp: 25C Magnetic separation (Wu et al., 2012)
order kinetics
Cu(II)
Ni(II) 70.92 mg/g
Montmorillonite Pseudo second Langmuir Contact Time: 2 (Kalantari et al.,
55. Response surface methodology
Fe3 O4 order kinetics isotherm min 2015b)
Pb(II) 65.78 mg/g
263.15 mg/g
98 mg/g
Cu(II)
106 mg/g
Pb(II)
Langmuir- 97 mg/g
Pseudo second pH: 5.5, Contact Synthesis by chemical (Lasheen et al.,
56. Kaolinite- Fe3 O4 Cd(II) Freundlich
order kinetics Time: 120 min co-precipitation method 2016)
model 100 mg/g
Cr(VI)
95.2 mg/g
Ni(II)
57. Hydroxyapatite- Pb(II) Pseudo second Langmuir- 598.98 mg/g pH: 2−7, Dissolution/precipitation and (Dong et al., 2010)
Fe3 O4 order kinetics Freundlich Temp: 25C surface complexation - mutually
332
model responsible for lead adsorption

58. MgO/Fe3O4 Cr (VI) Pseudo second Langmuir, 23.9 mg/g pH: 3, Contact Exothermic adsorption process, (Abshirini et al., 2019)
nanocomposite order kinetics Freundlich time: 30 min, negative Gibbs free energy
model Temp: 25C
Fe (II) Chitosan produced from shrimp
Chitosan NP extracted from shrimp Pseudo second 116.2 mg/g pH: 4.6–4.8,
59. Langmuir through 3 successive (Ali et al., 2018)
shells Mn (II) order kinetics Temp: 25C
74.1 mg/g methods-demineralization,
204 mg/g deproteinization, and DA
Pb (II)

208.3 mg/g
Magnetically MALA reusable after treatment
Pseudo second pH: 6, Temp: 25 (Abedi et al.,
60. modified aloe vera Cu (II) Langmuir model 204 mg/g ◦
with HCl solution (desorption
order kinetics C. 2016)
leaves ash studies)
Cr (II) 200 mg/g
Zn (II)
61. Chitosan/PVA Pb (II) Pseudo second Freundlich 14.24 mg/g pH: 5, Temp: Exothermic adsorption (Anitha et al., 2016)
blend order kinetics model 30C, Contact
Time: 40 min
Fe3O4 @ PDA Pb (II) Pseudo second 57.25 mg/g Ionic strength independent (Wang et al.,
62. Langmuir model Temp: 60C
(Polydopamine) Cu (II) order kinetics 86.35 mg/g adsorption process 2018b)
MNP grafted Cu Langmuir, 0.70 mg/mg, Nanoparticles were separated
Pseudo second (Almomani
63. hyperbranched Ni Freundlich 0.45 mg/mg, pH: 9.0 from wastewater using
order kinetics et al., 2020)
polyglycerol (HPG) model 0.79 mg/mg magnetic field in 35 s
S.S. Kolluru et al.
Al
64. Molybdenum Pb(II) Pseudo second Langmuir 333 mg/g pH: 2.0 Synthesized using two-step (Tong et al., 2018)
disulfide NP with order kinetics model hydrothermal reaction
ceriumoxide
(MoS2/CeO2)
nanohybrids
65. CoFe2O4@␥-Fe2O3 As(V) Elovich Kinetics Freundlich 46.9 mg/g pH: 6.4, Temp: Increasing ionic strength shows (de Oliveira et al., 2020)
model 23C positive effect on As(V) removal
66. CS/PVA/CuO beads Pb (II) Pseudo second Langmuir 116.84 mg/g pH: 5, Temp: Spontaneous, endothermic (Jiao et al., 2017)
order kinetics model 49C adsorption
67. CuH2ASO4+ As(V) Biphasic Langmuir 9.72 mg/g pH: 5.5 As adsorption decreased in (Darezereshki et al.,
first-order, pseudo- model presence of Fe3+ and Al3+ at pH 2.5 2018)
second-order
68. Epichlorohydrin Pb(II) Pseudo second Langmuir 86.20 mg/g pH: 4.0, Precipitation/complexation (Yan et al., 2018)
crosslinked order kinetics model Equilibrium dominated sorption process
chitosan schiff’s time: 105 min
base@Fe3O4
69. Fe3O4 NP coated Cd Pseudo second Freundlich 24.4 mg/g pH: 6, Contact Cd removal decreased with (Jorfi et al., 2020)
with natural order kinetics model time: 60 min enhancement of initial Cd
clinoptilolite concentrations
333
zeolite
70. nFe (green As (V) Pseudo second Langmuir 21.59 mg/g pH: 5.0, Temp: Adsorption mainly via an Fe-O-As (Wu et al., 2019)
synthesized iron order kinetics model 25C bond
nanoparticles)
Cu (II) Temp: 45C, Nanofibres can be prepared by
Chitosan/TiO2 Pseudo first order Redlich– 710.3 mg/g (Razzaz et al.,
71. Equilibrium 2 ways: Coating and entrapped
composite Pb(II) kinetics Peterson Model 2016)
579.1 mg/g time: 30 min method
72. Fe3O4@SiO2@NH2@SH Pb (II) Pseudo second Langmuir 23.92 mg/g pH: 6, Contact Bi-functional nano adsorbent for (Izanloo et al., 2019)

order kinetics model time: 40 min simultaneous adsorption of
pesticides
73. Thioureafunctionalized Pb (II) Pseudo second Freundlich 554.4 mg/g pH: 6.5, Endothermic and spontaneous (Alipour et al., 2020)
magnetic order kinetics model Contact time: sorption
ZnO/nanocellulose 14.5 min
composite
74. Chitosan- As (III) Pseudo second Langmuir 45 mg/g pH: 7.3 Separation and recovery of (Sherlala et al., 2019)
magnetic-graphene order kinetics model nanoparticles using an external
oxide magnetic field
75. Magnetite based Ni Pseudo second Langmuir 46.513 mg/g pH: 8, Contact Synthesis using co-precipitation (Baseri and Tizro, 2017)
nanocomposites order kinetics model time: 50 min, method
Temp: 40C
Fig. 3. Classification of Nanoparticle Materials.
particles (MNPs). Paramagnetic nature of MNPs result in easy sep- favorable characteristics like high adsorption capacity, large sur-
aration of contaminants from water (Gómez-Pastora et al., 2014). face area to volume ratio, well-structured pores, large surface area
The cost efficiency of the adsorbent is extremely paramount. etc. Various metals such as Fe, Au, Ag, Tl, Sn, Cu can be used for
Favorable factors of an adsorbent are that the processes should be heavy metal removal by a two-step process, first swift adherence
efficient, but the cost should also be low. In particular adsorbents, of the metal ions on the outer surface of the adsorbent followed
further research has been done and materials have been modified to by penetration inside the porous walls of the particle by nanoscale
lower the cost of production. For example, in the case of nanocom- matching. Their ease of modification, combined with adsorption
posite soft magnetic beadlike microgels. The cost of raw materials factors like energy of interaction, high number of reactive sites,
is reduced by using the inexpensive inorganic materials instead oxidation state, metal ion radius disparity with major pollutants
of organic cross-linking agents and by increasing the utilization present in water increase their suitability to be used in heavy metal
of KH-570; the process cost is remarkably lowered by simplifying removal (Abdelbasir and Shalan, 2019).
the synthesis procedure; the after-treatment cost is also decreased
since an alternative approach for the separation is provided; and 3.1.1. Zero-valent Iron
the long-term application cost is reduced without compromising its Zero valent Iron started becoming popular around the 1980s,
long service life resulting from the excellent mechanical strength when it was first utilized for groundwater remediation in per-
and regeneration properties (Jiang et al., 2018a). Modifications meable reactive barrier systems to get rid of pollutants like
like using ion exchange mechanism involving carbonate groups perchlorates, chlorinated hydrocarbons and nitroaromatics (Li
rather than using hydroxyl groups also increases efficiency (Cao et al., 2006). Ever since then, it has been a powerful remediation
et al., 2012). Modified graphene is another viable option. Here too, substance as it is non-toxic, easily available (Fe being the fourth
modification helps in increasing the removal efficiency. Therefore, most abundant element) and has a standard reduction potential of
according to the various properties and requirements, advantages about −0.44 V (acts as a moderate RA). It typically consists of a core-
and disadvantages of different adsorbents can be analyzed, and the shell structure. The metallic iron (zero-valent) constitutes the core,
best one can be selected. and the outer shell is formed as a result of oxidation (mixed-valent:
Fe2+ and Fe3+).
3. Overview of different nanomaterials used in heavy metal
Fe0 +2H+ +O2 → Fe2+ +H2 O2 (1)
removal
0 + 2+
Fe +H2 O2 +2H → Fe +2H2 O (2)
A large number of nanomaterials and their composites have
gained significant importance in the removal of toxic metal ions Fe2+ +H2 O2 → Fe3+ +OH− +OH∗ (3)
and organic pollutants from water and wastewater (Singh et al., However, limitations to target contaminant source area and
2013). Nanoparticles like metals and their oxides, carbon deriva- huge construction costs was a major drawback with typical zero-
tives like fullerenes and nanotubes, polymers, ceramics etc. possess valent iron. In the last few decades, the development of nanoscale
a unique blend of physical and chemical properties due to their zero-valent has aided to facilitate the process. Owing to their small
high surface area to particle size ratio, large number of adsorption size, they can be easily injected to the contaminant area by gravita-
sites and enhanced optical, electrical and magnetic properties as tional flow or pressure and under ambient conditions, they remain
compared to those of macroscopic particles of the same composi- in suspension, thereby cleaning water over extended periods and
tion (Theodore and Kunz, 2005). An ideal adsorbent for removal of yielding higher reactivity due to larger surface area (Fu et al., 2014).
heavy metals from water should be: (i) environmentally benign (ii) Many studies have even corroborated that bivalent iron-based
recyclable (iii) should exhibit high sorption capacity and selectivity nanoparticles (consisting of Ni, Pd, Pt) give benefits of synergy and
even at low concentration (iv) adsorbed pollutant should be easily facilitate further in the degradation of contaminants. A thin layer
removable from surface (Sadegh et al., 2017). A brief overview is of these noble metals on the surface of iron catalyzes the reac-
shown in Fig. 3. tion. It slows down deposition of corrosion products and fastens
the reaction kinetics.
3.1. Metal nanoparticles Amongst the bivalent nanoparticles, Iron-Palladium system has
high efficiency to remove polychlorinated biphenyl contaminants.
Nano-sized metal oxides and metals have recently gained signif- The enhanced degradation is due to change in debromination step
icant importance in the field of heavy metal removal, due to their owing to the presence of Palladium (Dave and Chopda, 2014).
334
spinel nickel ferrite (NiFe2O4), which acts as an effective adsorbent

owing to origination of strong momentum in ferromagnetic state by
antiparallel rotation between iron and nickel in the specific tetra-
hedral and octahedral structure (Nizamuddin et al., 2018).
As the industrial world is taking a step ahead towards
environment-friendly operations, processes like advanced oxida-
tion process (AOPs) with semiconductor photocatalysis has gained
significant importance. The traditional photocatalysts like Zinc
oxide, titanium oxide, zirconium oxide etc. could only exploit 5%
of the available solar energy (Santhosh et al., 2018). To resolve
this problem of underutilization, researchers explored photocata-
lysts with grater light absorbing capacity. Iron oxide in the form
of hematite (alpha-Fe2O3) is one such compound which has an
absorption capacity of around 43 % of the incident light in the
visible region (Malathi et al., 2018). Its photocatalytic activity can
further be enhanced using methodologies like doping with metal-
lic or nonmetallic elements, synthesis controlled by morphology,
Fig. 4. Steps in the formation of Emulsion.
composite formation etc. For instance, (Zheng et al., 2016) syn-
thesized BiOBr/Hametite composite by hydrothermal method and
Another iron-based nanomaterial gaining momentum is emul- used the composite to target the decomposition of organic pol-
sified zero-valent iron. It reduces the degradation of Nano lutant Rhodamine B. It showed remarkable improvement in the
zero-valent iron and facilitates easy transportation in oil-water degradation as a result of the synergy of formation of p-n hetero-
emulsion systems. They form a membrane of droplets around the junction between BiOBr and hametite.
zero-valent iron to degrade chlorinated hydrocarbons and are sur-
factant stabilized (Galdames et al., 2020). Fig. 4 depicts the steps 3.1.4. Zinc based
involved in the formation of a nano-emulsion gel. Zinc oxide is naturally found in the rare mineral zincite, and
it crystallizes in 3 structures – zincblende, rock salt and wurtzite
3.1.2. Titanate nanomaterials (Baruah et al., 2013). ZnO follows a four step heterogenous catalysis
Thallium, a toxic and non-essential trace metal poses high res- for removal of organic contaminants:
piratory and gastrointestinal health hazards. It has been declared
as a top priority water pollutant by many governments as it is toxic 1 Charge-carrier generation
in even acute amounts. Based on recent incidents in developing 2 Charge-carrier trapping
countries like China, there is urgent need to deal with this pol- 3 Charge-carrier recombination
lutant. Thallium can effectively be removed by tubular/ wire like 4 Photocatalytic degradation of organic pollutants (Lam et al.,
Titanium nanomaterials. 2012)
Besides Thallium, it can effectively be used for various other
metal removals. The order of adsorption preference for titanium is: The mechanism of photocatalysis as studied by (Gunti et al.,
Lead > Thallium > Copper > Cadmium > Zinc. 2018) is:
Surface complexion models studies suggest that Titanium based
monodentate surface complexes are more effective than bidentate Photocatalyst + h → e− +h+
surface complexes over broad range of pH for adsorption of Arsenic
(Lata and Samadder, 2016). Titanate nanoflowers that are manu- H2 O → H+ +OH−
factured by treatment of sodium hydroxide and nano-anatase in
hydrothermal conditions exhibit high stability in their framework, e− +O2 → O2−
which results in great reusability application of the adsorbent. They
don’t deviate much even under the effect of interfering cations like
h+ +OH- → OH∗
calcium and magnesium (Vikrant and Kim, 2019). However, a major
disadvantage is the large dependency on morphology and crystal
state of these nanomaterials developed by hydrothermal treatment h+ +OH− → OH
of Titanate Oxide and alkalis. They possess similar types of adsorp-
tion sites but differ in functional group location along the chain. OH ∗ +R(pollutant) → OH− +R ∗ (oxidized)
(Wang et al., 2020c)
O2 − +R → O2 +R ∗ ∗(reduced)
3.1.3. Iron oxide based
Iron being one of the most abundant metals in the earth, is R ∗ (oxidized)orR ∗ ∗(reduced) → (finalproducts) → CO2 +H2 O
found in various forms such as hematite (alpha - Fe2O3), mag-
netite (Fe3O4) and maghemite (gamma Fe2O3) (Paterson, 1999). For efficient photo splitting of water, an optimum temperature
In recent times, it has displayed amazing sorption capacities owing of nearly 600C is usually suggested. This can be attributed to the
to its large surface area, highly porous nature and strong magnetic higher optical absorption and reduced electric al resistivity of the
properties. It is being widely used for removal of dyes, heavy met- sample at these temperatures (Gupta et al., 2009). Depending on
als, inorganic and organic compounds. Its magnetic properties can the wavelength of irradiation, these photocatalysts have different
be controlled and managed by factors like size, surface defects and excited states, which give different reaction pathways for different
most importantly the appropriate ratio of ferromagnetic and anti- pollutants. An added benefit of this process is that it doesn’t need
ferromagnetic particles bring about a very stabilized morphology any secondary disposal method, is environment friendly, uses sus-
(Lu et al., 2007). Like most other metal oxides, it has the tendency to tainable technology and leaves no traces of any pollutants (Lee et al.,
form a composite, one such highly effective composite is inverse- 2016).
335
3.2. Magnetic nanoparticles mum separation was achieved by using Polyacrylonitrile as a binder
(Sheha, 2012).
Magnetic nanomaterials, characterized by their unique shape,
size and morphology possess high advantages in water treatment. 3.3. Carbon based nanomaterials
They outweigh the conventional substitutes and indicate advanced
benefits as they combine advantages of both nontechnology and 3.3.1. Carbon nanotubes
magnetic separation. They are biocompatible, chemically inert, eas- Carbon Nanotubes are long cylinder-shaped nanostructures that
ily dispersible and have minimal toxicity. However, their tendency are formed by sp2 hybridized rolled graphite sheet carbon atoms.
to form conglomerates easily in aqueous solutions and high oxi- Owing to their high chemical stability, favorable mechanical and
dation tendency make them practically less feasible. However, electrical characteristics, their highly dense mesopores, large sur-
surface modifications like ligand addition, complex formation and face area and high adsorption, carbon nanotubes are one of the most
functionalization with poly vinyl pyrollidine or poly vinyl alco- widely used materials for heavy metal removal. They can be used
hol enhance their oxidation stability and increases their adsorptive for removal of nonpolar compounds due to their hydrophobicity,
power (Wadhawan et al., 2020). and with ionic and polar compounds due to their high porosity (Lal
et al., 2020). They can mainly be categorized into single wall and
3.2.1. Magnetite (Fe3O4) multi wall nanotubes. While multiwalled nanotubes have nested
It is a form of iron ore that contains both ferrous and ferric ions, graphite cylinders in the range of 2−25 nm diameter, single walled
unlike most other oxides of iron. It has an energy gap of around 0.12 have a rolling sheet of nearly 1−2 nm diameter (Ghorbani et al.,
eV and exhibits both n-type and p-type semiconductor properties. 2020). Further modification in their chemical structure, like making
It has seen widespread applications in removal of radionuclide due them functionalized with a 3:1 vol ratio of nitric acid and potas-
to its highly enhanced properties. Studies have proven that Schiff sium permanganate, yields around 2.517 mg/g adsorption capacity
based complex of nanorod-decorated Silicon can be suitably used as compared to 2.49 mg/g for non-functionalized ones (Monthioux
for the removal of Lead(II) and Uranium(VI) from polluted water. et al., 2017). Although carbon nanotubes are extensively used for
(Abdel Maksoud et al., 2020) Pb (II) removal, low selectivity is a limitation of these environment
Superparamagnetic iron oxide (Fe3O4) nanomaterials can also friendly adsorbents. However, methods like microwave heating
be used as highly efficient adsorbents to treat toxic materials like accelerate the reaction kinetics and yield as high as 95 % removal
mercury, lead, cadmium etc by surface functionalization of DMSA. efficiency at optimum temperature and pressure conditions with a
It binds to the DMSA ligands for these heavy metals whereas in case pH between 7.5 and 8.5 (Renu et al., 2017).
of Arsenic, binding with iron oxide lattices is observed. Fig. 5 gives
a schematic representation of this process. A 1.2 T magnet can be 3.3.2. Graphene based
used to separate (Ahmaruzzaman, 2019) them from the solution. Graphene oxide, a composite of carboxylic, hydroxyl and epox-
A 1.2 T magnet can be used to separate (Ahmaruzzaman, 2019) ide functional groups shows high adsorption for heavy metal ions
them from the solution. Besides, they exhibit high functionality, due to its large surface area available for adsorption and numerous
of the order 1.85 mmol thiols/g for a surface area of nearly 120 functional groups present. It is highly effective in aqueous medium
m2/g. Ferromagnetic nanomaterials at low temperature have been as it has a tendency to aggregate quickly owing to its inert surface
proven effective for dye removal (containing hydroxyl group). chemistry and pi-pi interaction (Lam et al., 2006), which hinders its
contact with the pollutants and thus limits environmental degra-
3.2.2. Other magnetic materials dation. In order to improve their functionality, stabilizers to graft
Magnetic nanocomposites can broadly be classified into 3 types: functional groups are attached on their surface (Liu et al., 2019).
Industrially used stabilizers include soluble polymers or surfactants
(i) organic-inorganic nanocomposites: isolated nanoparticles are which bind to the surface by non-covalent forces. Functionalized
finely dispersed in a polymer (Wang et al., 2009) graphene oxides like octadecyl amine and tetrazolyl derivatives
(ii) core-shell inorganic nanocomposites: combination of two effectively co-adsorb even ultralow concentrations of primary-
nanoscale entities into a single hybrid composite ternary-quaternary mixture of heavy metal pollutants (Khaligh and
(iii) self-assembled colloidal nanocomposites: self-assembly of Johan, 2018).
small building blocks into ordered macroscopic superstruc- Graphene based Nano-spinel ferrites are mostly combined with
tures (Kalia et al., 2014) ferrites of cobalt or bismuth to form adsorptive NC which have
highly effective pores and low energy requirement (Kyzas and
In a study by Fan et al., 2013, magnetic nanocomposites of chi- Matis, 2015). Pi-pi stacking, complexation of inner surface and
tosan and graphene oxide particles were used to adsorb Pb2+ ions electrostatic interactions are responsible determine the adsorp-
with a adsorption capacity of 76.94 mg/g. Researches have indi- tive capacity of these complexes. (Reddy and Yun, 2016). This
cated that magnetic charcoal, magnetic chitosan gel particle and is due to the surface functional groups getting actively proto-
magnetite bearing covalently immobilized copper phthalocyanine nated and deprotonated over wide ranges of pH. X-ray photon
dye are efficient in the removal of polycyclic dyes, malachite green electroscopy analysis clearly suggest the exchange of protonated
and organic dyes from contaminated water (Khin et al., 2012). hydroxyl groups on surface of Arsenic (III) and Arsenic (V) by
Oil can be removed from contaminated water using polymethyl graphene – CuFe2O4 composites at pH below point of zero charge.
acrylate (PMA) which is a functionalized magnetite nano substance. The pH determines the surface charge of these composites and
It has extraordinary ability to absorb oil and exhibits high ferro- actively controls the adsorption process as it effects the chemi-
magnetism, recovery can be done by superconducting magnetic cal speciation of the graphene based nano-spinel composites (Sun
separation (Liu et al., 2012b). Organic pollutant crystal violet dye et al., 2015). Another major aspect of Graphene based nano-spinel
was removed by magnetic nanocomposite Fe3O4@SiO2 starch graft composites is their ability to remove organic contaminants via pho-
polyacrylic acid in a study by (Pourjavadi et al., 2013). 85 % degra- tocatalytic degradation because of their high chemical stability over
dation of the dye was achieved, primarily because of high magnetic wide range of temperature and pressure conditions (Anjum et al.,
sensitivity of the hydrogels. Magnetic hexacyanoferrate polymers 2019).
are used extensively to remove Cesium from low level radioactive Due to their low cost and easy recovery by applying external
wastes. With a contact time of 2 h, and independent of pH, maxi- magnetic field, they can be used as efficient budget-friendly alter-
336
Fig. 5. (Bertorelle et al., 2006): Schematic of surface modification of MNPs via the ligand absorption process with DMSA and fluorescent dye.
natives to the old conventional adsorbents. For upscaling the use of as compared to activated carbons and zeolites that work in parts
any adsorbent, its projected cost and potential for reuse/recycle per million level (Kumari et al., 2020).
plays an important role. Besides, magnetic separation at non-
sensitive environmental conditions, desorption with HCl and HNO3
can also be used for its recovery (Park et al., 2019). 3.3.5. Sulphur impregnated carbon
Mercury emission is a major environmental concern as it is con-
sidered to be one of the most toxic and hazardous elements found in
3.3.3. Carbon nitride based (g-C3 N4 ) the environment. Mercury removal is a big challenge in itself due to
Over the past few years, significant progress has been made on its highly volatility nature and relatively inert chemical behavior. At
the processes and mechanisms of using carbon nitride-based nano- present, many methods such as photo-chemical oxidation and irre-
materials in heavy ion removal owing to their diversified structure versible adsorption are implemented for mercury removal. With
and high sorption capacities. They are mainly prepared by hard increasing awareness and recent advances in technology, sulfur
template method which increases the density of active sites on impregnated carbons are being highly utilized for mercury dis-
the surface (Gautam et al., 2019). Doping is another way of surface posal in all forms such as elemental (Hg0), particulate (Hg(p)) and
modification used extensively in these nanomaterials to tune the oxidized (HgCl2 or HgO). The critical factors for proper impreg-
physical properties like outer electron density, specific surface area nation are sulfur to carbon ratio and impregnation temperature,
available for electron exchange and solubility in aqueous mediums with impregnation temperature being the more critical factor. At
(Wang et al., 2020d). Lewis acid-base is often used to justify the for- higher temperatures, small and short chain molecules become pre-
mation of powerful complexes between carbon nitride and metal dominant and being more mobile, they migrate through the porous
ions. Modifications like polymer coatings with polydopamine (PDA) carbon structure resulting in uniform distribution of sulfur ion the
(Mauter and Elimelech, 2008), melamine based dendrimer amine carbon matrix. At lower temperature ranges, the sulfur molecules
and polyethyleneimine (PEI) are used to resist layered aggrega- exist dominantly in ring form or as long linear chains. These chains
tion by electric stabilization and electrostatic repulsion (Anbia and or ring structures tend to block the pores owing to steric hindrance
Haqshenas, 2015). and sometimes combine together to form multilayer structures,
further decreasing the exposed area (Suresh Kumar Reddy et al.,
3.3.4. Cyclodextrin based 2014a). In a comparative study of adsorption capacities between
Recently, cyclodextrins have been gaining significant impor- sulfur Impregnated Carbon (SIC), UOP, Sulphonated Carbon (SC-
tance by researchers to improve the structural and functional 300/SC-600) and Norit, it was observed that Sulphonated Carbon
aspects of carbon nanomaterials. Cyclodextrin modified graphene had significantly high adsorption capacity (nearly 5501 micro g/g
oxide nanostructures has made significant contribution in not only at 50C). SO3H functional group attached to highly dense acid sites
water remediation but also fields like plant growth regulation, in graphitized rings were the driving factor for this high adsorption
drug delivery etc. (Li et al., 2014). These hybrid complexes are capacity. For temperatures exceeding 70C, the adsorption capac-
highly stable towards acids and thus exhibit better potential in ity faced a sharp decline owing to the removal of the SO3H group
removal of contaminants from water. It was used for the adsorp- (Kumar Reddy et al., 2016). At temperatures beyond 140C, the
tion of Rhodamine dye prepared in deionized water (Liu et al., decrease in adsorption capacity can be attributed to agglomer-
2014b). The reusability was examined for six reusability cycles ation of sulfur in the porous matrix of carbon. More than the
using the absorption-desorption method, and it was observed that amount of sulfur in the porous carbon matrix, its distribution and
the removal capacity was nearly 90 % after six cycles. bondage with functional groups at atomic levels played an impor-
(Karoyo and Wilson, 2015) reviewed CDMIPs – cyclodextrin tant role in determining the adsorption capacities (Suresh Kumar
based imprinted polymers adsorbents for perflourinated com- Reddy et al., 2014b). Copper sulfide impregnated adsorbents pos-
pounds and found them beneficial owing to their morphology, sess higher sorption capacity as compared to zinc sulfide or iron
tunability of surface and large number of binding sites. By decreas- sulfide based adsorbents because of lower diffusional resistance
ing the ratio of cross-linking agents and increasing the degree of for mercury and better dispersion of active copper sulfide phase
polymerization, insoluble cyclodextrin polymers can be obtained (Reddy et al., 2018).
which are particularly useful for water remediation (Krause et al., In a research conducted by (Rashid et al., 2013), the process of
2010). Various studies and researches have confirmed that these sulfur impregnation on to virgin commercial carbon was studied
polymers work in parts per trillion level for contaminants removal to maximize the adsorption of mercuric chloride. It was concluded
337
that RSM model (Response Surface Methodology) is a good tech- valent iron owing to characteristics like higher stability, lower
nique of optimizing the impregnation process as the experiment aggregation capacity etc (Deshpande et al., 2020).
validated the closeness between the predicted value (85.34 mg/g
mercuric chloride uptake) and experimental value (83.19 mg/g 3.5. Analysis of kinetic and equilibrium models
mercuric chloride uptake). However, sulfur impregnation suffers
from a major drawback of sulfur leaching due to condensation of Isotherm is a mathematical equation that portrays the relation
light weighted hydrocarbons in the porous carbon matrix. Large between the quantity of adsorbed sorbate and its concentration in
variability is observed in the sulfur leaching proportions based on the bulk at equilibrium conditions. The solid-liquid sorption sys-
the source of impregnation of sulfur. For example, HGR porous tems can be described using various models such as Freundlich,
impregnated carbon has sulfur content of nearly 5.2 % and leaching Langmuir, Redlich-Peterson, Temkin, Sips isotherms etc. These
of 76.8 %, whereas FeS-C having similar 5.0 % sulfur leads to only 0.1 models and their parameters give a deep insight into the mech-
% sulfur leaching (Kumar Reddy et al., 2015). This clearly indicates anism of the adsorption process, the surface properties of the
that the impregnation process is a much more effective parameter adsorbent involved, its affinity, quantitative distribution of adsor-
than the amount of sulfur loaded in the porous carbon matrix. bate etc. Some of the most commonly employed isotherms are
Freundlich and Langmuir isotherm (as in Table 2).
The linearized form of the Freundlich isotherm is: ln Qe = ln KF
3.4. Other nanoparticles + 1/n (ln Ce )
where KF indicates the extent of adsorption and is termed as
3.4.1. Agricultural waste materials the Freundlich adsorption constant (L/mg) KF is the slope of linear
Low cost abundantly available biodegradable materials and plot of ln Qe against ln Ce and it indicates the degree of monolin-
decomposable wastes, such as coffee remains, coconut husks, tea earity. 1/n is the intercept of linear plot of ln Qe against ln Ce . This
leaves, sunflower stalk, cotton and wool etc have recently been used model is employed to describe the correlation between non ideal
in removal of heavy metal ions. To investigate the mechanism of and reversible sorption in diverse systems, which is applicable in
how the metal binds to the biomass, a deep understanding of the understanding the multilayer sorption process (Singh et al., 2016a).
functional groups that are responsible for the binding is essential. On the other hand, widely used Langmuir model effectively pre-
In most cases, they are found in the plant cell walls whose major dicts the sorbate’s monolayer spread on the surface. The linearised
constituent is cellulose. It’s performance as a stratum is highly form of Langmuir isotherm, which assumes finite number of iden-
dependent on the degree of polymerization, the specific surface tical sites and no subsequent interaction between molecules on
area available and structural properties such as crystallinity. The adjacent sides is (Jiang et al., 2018b): Ce / Qe = 1 / bQm + Ce / Qm
relative composition of amorphous and crystalline portion varies Where, Qm is monolayer adsorption capacity in mg/g, B is Lang-
according to the sample and measurement mode. For example, muir constant, Ce and Qe are equilibrium sorbate and solid phase
wood cellulose is more amorphous than cotton cellulose. sorbate concentrations respectively (in mg/L).
Cellulose-polyacrylonitrile and cellulose- Another isotherm employed, though less popular than Langmuir
polymethacrylonitrile, called the cellulosic graft copolymers and Freundlich models is Redlich-Peterson model. It is commonly
are by combining acrylonitrile and methacrylonitrile monomers in understood as the intermediate system between Langmuir and Fre-
aqueous media with hibiscus cannabinus fibers in presence of ceric undlich as it explains sorption process on heterogenous surface
ion-toulene redox pair to remove Zinc and Chromium. At around systems. It can be defined by the mathematical expression: qe =
29.85C, zinc ions adsorbed 1.80 times more than chromium ions ACe / 1 + BCe ˇ
at the same environmental conditions (Demirbas, 2008). where A and B are Redlich-Peterson constants in L/g and L/mg
respectively, ˇ ranges between 0 to 1. The model can be understood
3.4.2. Zeolites and silica based as analogous to Freundlich and Langmuir models as:
Mesoporous silica are beneficial adsorbents for gas phase con- When ˇ equals 1, the model reduces to Langmuir isotherm with
taminants, owing to their tunable pore diameter and large surface b = ˇ (L/mg), and with A/B = KF and 1-ˇ = 1/n it resembles Freundlich
area. Surface modifications like presence of hydroxyl group aid in isotherm model (Azzam et al., 2016).
adsorption and boost reactions like wetting. A renowned strategy to To determine the most suitable isotherm, the linear regression
modify and enhance the performance of these adsorbents is to graft correlation coefficient values (R2 ) of all the models are evaluated
the functional groups on the walls of pore (Egodawatte et al., 2016). and compared. Table 3 displays Langmuir isotherm for most cases,
This surface modification opens up design for catalysts and new indicating that the sorption process was mostly monolayer type.
adsorbents. The presence of amine groups on silica surfaces max- Adsorption kinetics forms an integral part of the adsorption
imizes the removal efficiencies for carbon dioxide and hydrogen kinetics study as it provides useful information about the rate at
sulphide to as much as 80 % removal (Guerra et al., 2018). which pollutants are eliminated and for understanding the reac-
Zeolites are highly efficient materials for dealing with organic tion mechanics. It also gives a brief outlook about the reaction time
contaminants. Zeolite based membranes, like those covered with as it indicates the rate of uptake of solute. Some of the vital steps
thin films of polyamide, are effective for RO owing to their high that can be used to predict the rate law are as follows:
water permeability and ability to reject salt. Application of NAP1
zeolites has shown promising results for removal of metals like (i) Transport of sorbate from solution bulk to liquid film surround-
Chromium, Nickel, Copper, Zinc and Cadmium (Amin et al., 2014). ing the solid sorbent
(ii) Sorbent diffusion across liquid film surrounding the bare solid
particles
3.4.3. Clay minerals (iii) Diffusion of sorbate into the solid pores from liquid film
Besides materials like modifiers, stabilizers and inorganic clays, (iv) Surface reaction for sorption of sorbate on surface
composites like calcium polysulphides, kaolite, rectorites etc. are (v) Sorbate desorption from solid surface in case of reversible sorp-
gaining increasing importance in removing environmental contam- tion (Aigbe and Osibote, 2020)
inants. They help in prevention of accumulation and migration of
the contaminants. Various studies have indicated that zero valent The slowest of the above steps is the rate determining step which
iron supported inorganic clays are more efficient than bare zero guides the complete rate of the sorption process. To develop an
338
Fig. 6. (Shah et al., 2015): Biological synthesis of nanoparticles using plant extracts.
understanding of the reaction kinetics, pseudo-first-order, pseudo- As observed from Table 3, pseudo second order kinetic model
second-order, Elovich and intraparticle diffusion equations are is the most followed model, which indicates that the rate limiting
employed. step is the chemisorption aided sorption step which occurs when
Pseudo first order kinetic reaction rate is directly proportional active surface sites are effective. This is just a brief discussion to gain
to change in concentration and amount adsorbed with time. In this better understanding about the kinetic and equilibrium trends of
model, the sorption is preceded by diffusion across a boundary. It’s the table, a detailed discussion is presented in section 4.
mathematical equation can be represented as (Bandar et al., 2021):
In (qe−qt)= In qe−K1t 3.6. Eco-friendly nanomaterials
Where qt and qe are the the amount sorbed (in mg/g) on the
sorbent at the time (t) and equilibrium, K1 is the pseudo-first- Nanobiotechnology is gaining significant importance in devel-
order rate constant (1/min). On the contrary, pseudo second order opment of sustainable technologies for the future owing to their
kinetic reaction rate is dependent on the mass of the metal ion on unique ability of synthesizing metal composites into their nan par-
the sorbent surface and quantity sorbed at equilibrium. This model ticle size. This modulation and transformation considerably variate
is widely employed for study of chemisorption kinetics from liq- the chemical, physical and optical properties. However, most of
uid solution systems (Ahmadi et al., 2017). This model works on the existing technologies are either too costly, harmful to the
the underlying assumption that the metal ion gets sorbed to the environment or unsuitable with respect to energy and material
two polar available sorption sites. Its governing equation can be considerations. Therefore, to bridge the gap and fill the void, biolog-
represented as: t / qt = 1 / K2 qe 2 + t / qe ical approaches are being developed and this section highlights the
where K2 is the rate-constant of pseudo-second-order adsorp- different methodologies and parameters that affect the synthesis of
tion (g.mg-1.min), nanoparticles by green nanobiotechnology, and the various tech-
qe and qt are sorption capacities at equilibrium (mg/g) and niques used for characterizing the nanoparticles for their potential
quantity of adsorbate retained at time (t) (mg/g). use in remedial and environmental applications. The method used
Another model commonly employed for sorption of gas to solid for synthesis, particle size, pH, temperature etc. greatly determine
surface is Elovich model, which can be expressed by the linearized the characteristics, quality and application of the synthesized nano-
equation: qt = (1/)* ln(˛ˇ) + (1/ˇ)* ln t materials.
where ˛ is the initial sorption rate (mg/gmim), ˇ is the des- Plant extracts are often reviewed as an environment friendly
orption constant related to surface coverage (g/mg), ˛ and ˇ are route for detoxification and remediation purposes as they have
derived from slope and intercept of qt vs ln(t) plot. great potential to reduce metallic ions and hyper accumulate.
339
Active molecules like phenolic acids, polyphenols, terpenoids, alka- mulation approach as the later involves live organisms and thus
loids and proteins vary in composition and concentration, which added cost of nutrient supply. Besides, factors like bioavailability of
leads to their successful interaction with the aqueous metal ions the metal to microbe, environmental conditions like osmotic pres-
(Castro et al., 2011). The first step is the reduction of metallic ion sure, pH, oxygen, concentration of pollutants etc. play a major role
followed by stabilisation as illustrated in the figure. The process in the remediation capacity (Mani and Kumar, 2014). Besides, fac-
is initiated by straight-forward mixing of the plant extract sample tors such as cation exchange capacity, buffering load, clay content
with the metal salt. The formation of nanoparticles and initiation of etc. determine the bioavailability of each metal (Brar et al., 2006).
reduction is a spontaneous process, identified with colour change “Phytoremediation refers to the process of using plants and
in the mixture (Mittal et al., 2013). This has been pictorially repre- associated soil microbes to reduce concentrations or toxic effects
sented in Fig. 6. With the progress and growth, and variation in the of contaminants in the environments” (Ali et al., 2013). It is
concentration, reaction time, pH etc. the nanoparticles aggregate widespread application in the removal of toxic heavy metals,
and take different size, quality and morphologies. radionuclides and organic pollutants. This recent technology devel-
Biomass wastes, besides being valuable sources of energy, can oped in the last 2 decades has threefold advantage (Vangronsveld
also be used in the fabrication of Carbon Nanomaterials. For exam- et al., 2009):
ple, Coconut shell (which is a kind of biomass waste) has been
used in the synthesis of porous graphene nanosheets. Almost 3 g of
coconut shell along with 9 g of ZnCl2 as an activating agent were (1) phytoextraction of market valued metals (Nickel, Silver etc.)
mixed with 3 M, 50 mL FeCL3 solution for the fabrication (Sun et al., (2) risk containment (by photo stabilization)
2013). In another research, chitosan that was extracted from crus- (3) durable management.
tacean skin was treated and converted into N-doper graphene by
catalyst free synthesis (Primo et al., 2012). Turbostratic carbon is
The extent of phytoextraction is governed by factors such as
recovered by pyrolysis of dead neem leaves, is thereafter purified
bioavailability of metals, plant species concerned etc. Preferred
and dispersed in H2SO4-HNO3 solution (3:1) to obtain graphene
characteristics for plants suitable for phytoextraction are:
quantum dots (Suryawanshi et al., 2014).
As alternatives to the conventional methods, bioremediation
of heavy metals at low concentration using microorganisms is (1) Ease of translocation of accumulated heavy metal from roots to
being widely applied owing to their cost efficiency and environ- shoots
ment friendliness. Microorganisms like microalgae consume five (2) Accumulation capacity of target heavy metals from water
non-threshold toxic heavy metals, namely lead, mercury, cad- (3) Tolerance to the toxic effects of the target metal
mium, chromium and arsenic (Rahman and Singh, 2019). They (4) High distribution/ branching of root system and high growth
have various self-protection techniques in wastewater to fight rate.
against the toxic heavy metals, such as chelate formation, immo-
bilizing of heavy metal ions, exclusion and gene regulation. They
form a defensive layer by synthesizing antioxidant enzymes like (Adesodun et al., 2010; Sakakibara et al., 2011; Shabani and
SOD (superoxide dismutase), peroxidase along with non-enzymatic Sayadi, 2012)
antioxidants like GSH (glutathione), ASC (ascorbic acid) etc (Singh Studies are continuously being done to screen native plants
et al., 2016b). GSH and ASC have been proven highly efficient corresponding target heavy metals and to assess and monitor the
in the reduction of free radicals and the reactive oxygen species effect of different parameters on the phytoremediation efficiency.
(Devars et al., 2000). Cyanobacterial species such as spirogyra, Research is in progress to genetically mutate suitable plants and
anabaena etc. simulate the growth of microalgae due to hormesis characterize the different proteins involved in cross-membrane
phenomenon and their tolerance towards heavy metal stress (Balaji transport and vacuole sequestration of heavy metals. Progress and
et al., 2016). For determination of functional groups that are respon- development in this domain of molecular studies will aid in gaining
sible for complex formation with heavy metals and to study the better outlook and understanding about the involved mechanisms
behaviour and interaction, FITR (Fourier-transform infrared) and and enhancing the efficiency of phytoremediation.
NMR (nuclear magnetic resonance) spectroscopy can be performed. Chitosan is a non-toxic, eco-friendly and biocompatible natu-
Bioremediation has been effectively employed for the removal ral polymer, whose nanomaterials exhibit high stability, sorption
and recovery of heavy metals from wastewater. The microorgan- capacity and chelating activity. Chitosan based composites can be
isms either naturally detoxify or may be improvised by adding efficiently used for removal of heavy metals like lead, cadmium,
electron acceptors and nutrients (Dixit et al., 2015). The metabolic chromium iron etc and photo-oxidation of organic pollutants
process of the microorganisms helps to transform the pollutants in (Mansur et al., 2014). Chitosan based thin films have been be
the environment. Metals with different valence states show vari- developed with Ag-nanoparticles and found highly efficient for
able toxicity. Valence transformation mechanism can be employed photodegradation of organic contaminants under irradiation by
for detoxification in such cases. As an example, mercury resistant sunlight and in deficiency of oxygen (Al-Sherbini et al., 2019).
bacteria decreases the toxicity of methyl mercury hundred fold by Recent developments in the synthesis and stabilisation of mag-
converting it into Hg2+ using organomercurial lyase (Wu et al., netic nanomaterial composites have emphasized on the utilization
2010). Similarly, the toxicity of Cr(VI) can be reduced by converting of non-toxic synthetic bio-compatible materials. It has been discov-
it into Cr(III) using valence transformation (Siddiquee et al., 2015). ered that magnetite nanoparticles can be conveniently synthesized
Besides, mechanisms like metal binding, volatilization and vacuole by redox based hydrothermal method with starting materials as
compartmentalization can also be used to accomplish detoxifica- urea and ferric chloride. In another study, water soluble starch was
tion. used for stabilisation of bimetallic Iron-Palladium nanomaterials
The selection of microorganism depends on the extent of resis- (Saif et al., 2016). Iron nanomaterials, such as metallic iron and iron
tance developed by the organism when it comes in contact with the oxides can be produced via a feasible greener route, and this will
heavy metal pollutant to attain remediation. Few of the techniques mark a great step in the sustainable development and production
employed by microorganisms include biosorption, bioaccumula- of nanomaterials. Some of the biocompatible green methods with
tion, biotransformation, and biomineralization (Gadd, 2000). Dead their biogenic approaches and size – morphology considerations
biomass is more feasible on large scale application than bioaccu- are discussed in the Table 4.
340
Table 4
Iron Nanoparticles synthesized by biocompatible green reagents.
Nanoparticle Biochemical Agent Size Morphology Reference
Fe3O4 D-glucose gluconic acid 12.5 nm Spherical crystalline (Lu et al., 2010)
Fe3O4 Gluconic Acid and glucose 4 – 16 nm Crystalline (Sun et al., 2009)
Fe3O4 Sodium Alginate 27.2 nm Spherical (Kalantari et al., 2015a)
Fe NPs Myoglobin and haemoglobin 2−5 nm Aggregates (Gao et al., 2008)
Fe-core shell Chitosan – Gallic acid 11 nm Cubic (Dorniani et al., 2012)
Iron Oxide Tannic acid < 10nm Cubic (Herrera-Becerra et al., 2010)
nZVI Glutamine, arginine and cysteine – – (Siskova et al., 2013)
nZVI Ascorbic Acid 20 – 75 nm Spherical (Savasari et al., 2015)
Bimetallic Fe/Pd nanoparticles Starch 14.1 nm Discrete wall dispersed (He and Zhao, 2005)
Sugar (derived from 100−150 nm Nano-sphere (Yan et al.,
Carbon Encapsulated
wood) 10−25 nm Iron-core 2015)
Fe nano shell Ascorbic Acid < 100 nm Cubic (Nadagouda and Varma, 2007)
√
4. Thermo-kinetics qt =kid t+C (8)
1 1
4.1. Kinetics qt = ln ˛ˇ + ln(t) (9)
ˇ ˇ
Study of adsorption kinetics is vital before choosing the suitable The pseudo first order assumes that the rate of adsorption is
adsorbent for the practical use. It helps determine characteris- directly proportional to the number of available vacant sites. In
tics such as residence time, reactor design and other optimum the cases that fit this model, physisorption is the leading mech-
parameters(Do, 1998; Qiu et al., 2018). Furthermore, kinetics can anism of the process(Corbett, 1972; Lee et al., 2011). This is not
tell us about the rate controlling steps such as mass transport or common in adsorption using nanomaterials. But still, for a few
chemical reaction processes (Azizian, 2004; Kyzas and Matis, 2015). mechanisms, pseudo first order is the best fit. For example, cal-
For example, when the diffusion mechanisms were not taken into cium alginate biosorbent for the capture of Ni shows a very good
consideration, adsorption by layered double hydroxide followed correlation coefficient to the pseudo first order model.
the pseudo second order model, but this changed when diffusion Second order model assumes that rate depends both on the
was considered. This shows that diffusion was the only rate deter- number of sites available for adsorption and the concentration of
mining step in the adsorption process (Zhang et al., 2020). metal ions in the solution (Vijayaraghavan et al., 2017). Chemisorp-
Generally, in order to determine the best-fit kinetic model from tion is the rate limiting step in the cases that fit this model (Fang
the available models, batch experiments are carried out by vary- et al., 2020). It shows that the removal process is possibly related
ing the values of different parameters such as adsorbent dosage, to the strong complexation between metal ions. Among all the
pH, initial metal ion concentration, temperature, etc. followed by kinetic studies performed on adsorption by nanomaterials, pseudo
linear regression to ascertain the best-fitting kinetic model (Lei second order is the best-fit model for a majority of them. For exam-
Zhang et al., 2016). For determining these parameters, sophisti- ple, efficient Pb(ii) adsorption on etched Ti3AlC2 nanofibers and
cated scientific instruments are used. For example, in removal of Pb nanosheets follow pseudo second order(Gu et al., 2018).For the
from contaminated water, the concentration of the filtrate is deter- removal of copper using goethite and hematite, batch adsorption
mined using a flame atomic absorption spectrophotometer. (Zhang experiments revealed that it is well fitted to pseudo first order and
et al., 2020). Thermodynamic parameters such as enthalpy, entropy pseudo second order kinetics but suits the second order more. It
and free energy also provide a great deal of information concern- also shows negative free energy and is time dependent therefore
ing the type and mechanism of the process (Milonjić, 2007). These adsorption capacity increases with time(Chen and Li, 2010; Gerente
parameters are determined using the following equations: et al., 2007).
Kc = qe /Ce (1) In pseudo first order and pseudo second order models, surface
adsorption is the dominating factor (Simonin, 2016). In adsorbents
0
G = −RT lnKc (2) made of porous material, these models cannot fit the data in the
best way. Hence the intraparticle diffusion model is used in these
H 0 1
lnKc = − + S 0 /R (3) cases. A value of C, a constant relative corresponding to film thick-
R T
ness, near to zero indicates that diffusion is the individual rate
H 0 and S 0 can be obtained from the slope and intercept controlling step in the adsorption process (Neeli et al., 2020; Wang
√
of Van’Hoff plots of ln Kc vs 1/T (Romero-González et al., 2005). et al., 2020e). This implies that the plot of qt vs is a straight line.
In order to understand a process better, specific enthalpies and When the plot is not linear over time, it indicates that mechanism
entropies can be calculated for particular temperature intervals is controlled by more than one mode of adsorption. For exam-
using the following equations: ple, in the case of WS2 microcrystals fits this model (Wang et al.,
2020b). It also shows two different linear zones, indicating that
lnKc2 /Kc1 = H 0 (T2 − T1 )/RT2 T1 (4) multiple steps are involved in the adsorption. Firstly, metal anion
0
G = H − TS 0 0
(5) species moved towards the surface and secondly, there is interac-
tion between metal anions and functional groups. The plots do not
The most celebrated models that are used to fit experimental pass through the origin implying that the adsorption process can
data obtained from heavy metal adsorption onto nano adsorbents be dominated by intra-particle and external diffusion (Mahlangu
are pseudo first order (Eq. 6), pseudo second order (Eq. 7), intra- et al., 2019; Mahmoud et al., 2020). The combination of pseudo sec-
particle diffusion (Eq. 8) and Elovich model (Eq. 9). ond order rate equation and intraparticle diffusion model is able
qt = qe (1 − e−kt ) (6) to explain the experimental data of ultrasound-assisted simulta-
neous removal of Pb2+ and MG at optimum condition (Dil et al.,
t 1 t 2016; Jung et al., 2019; Wang et al., 2020e). In the study of super-
= + (7)
qt k2 q2e qe paramagnetic nanocomposites, the plot shows experimental data
341
1 indicates linear adsorption leading to identical adsorption ener-

gies for all sites. For a value of n less than one, cellulose and other
bio-based sorbents fit into a concave isotherm, also called solvent-
affinity isotherm. This isotherm shows marginal sorption energy
increase with increase in surface concentration. If the parameter n
is less than one, isotherm gives a concave shape. These irregular pat-
ters might be caused by the complex structure of the sorbents and
its multiple active sites. The parameter n also expresses the method
in which interaction between sorbent and heavy metal takes place
(Singh et al., 2016a). Adsorption capacities and adsorption intensity
of adsorbents is obtained from Freundlich KF parameter. Freundlich
Isotherm goes to extremes at high conditions and therefore cannot
be used to express results at these concentrations. But this is gener-
ally not a problem as researchers use moderate conditions for their
studies.
1
Qe = KF Cen (10)
Fig. 7. (Shivaprasad et al., 2020) Intraparticle diffusion plot.
Langmuir equation relates molecules on a solid surface to
concentration of a medium above the solid surface at a fixed
points corresponding to three linear portions. The initial steep por- temperature. This model assumes that adsorption is limited to
tions correspond to film diffusion. The second linear portion is the monolayer, all surface sites are alike and only can accommodate
intraparticle diffusion region, followed by adsorption where the one adsorbed atom and the ability of a molecule to be adsorbed
saturation occurs (Shivaprasad et al., 2020). This is shown in the on a given site is independent of its neighboring sites occupancy.
Fig. 7. Using these, a kinetic principle can be formed (Eq. 11). The Lang-
Despite being a very successful model, pseudo second order muir constant KL is related to the energy of binding sites as well
suffer from a disadvantage of being a pseudo-kinetic model and as the affinity of adsorption (Liu et al., 2017a). Therefore, a process
hence, for every change in system variable, a different rate constant following Langmuir Isotherm suggests that adsorption occurred at
is obtained which makes it necessary to form an equation which a homogenous site (Fang et al., 2020). The decrease in the value
correlates the pseudo rate constant with each variable (Gerente of Langmuir constant, with increase in temperature indicates the
et al., 2007). Therefore, in a few cases, the experimental data of exothermicity. The opposite trend indicates the supply of ther-
a process is a best fit of other models. Elovich model is also a mal energy(endothermicity), leading to chemisorption. Integrated
useful model for modeling kinetics at heterogeneous energy solid Van’t Hoffequation relates Langmuir constant with temperature
adsorbent surfaces. Along with pseudo first order and pseudo sec- (Eq. 12) (Febrianto et al., 2009).
ond order, graphitic carbon nitride nanosheets follow the Elovich
kinetic Model possibly because of the increase in adsorption pro- Q m K L Ce
Qe = (11)
cess time with increase in metal ion concentration (Xiao et al., 1 + K L Ce
2018). Graphitic carbon nanosheets also follow this model.
Ea
Table 3 provides information about the kinetic models followed KL = K0 exp (12)
by various nano adsorbents. RT
RL is a dimensionless parameter used to foresee the nature of

4.2. Isotherms the process and shape of the graph (Ihsanullah et al., 2020). The RL
value demonstrates the adsorption nature to be either undesired
For proper analysis and design of the optimal (RL > 1), linear (RL = 1), desired (0< RL < 1), or irreversible (RL = 0)
adsorption/biosorption process, knowing the relevant adsorp- (Sadeghi et al., 2020).
tion/biosorption equilibria is one of the vital information. At From correlation coefficients, the isotherm that fits the data
equilibrium, there is a certain relationship between solute con- best is obtained. To be the best-fit, the coefficient is usually 0.99.
centration in solution and adsorbed state (i.e., the amount of Therefore, adsorbents that undergo monolayer adsorption have
solute adsorbed per unit mass of adsorbent). Concentrations regression coefficients of 0.99 for Langmuir isotherm. For example,
at equilibrium depend on temperature. Hence, the adsorption micro/nanoflowers adsorbent having 0.99 for Langmuir isotherm
equilibrium relationship at a given temperature is referred as but only 0.90−0.92 for Freundlich isotherm (Zhang et al., 2016b).
adsorption isotherm. Therefore, the kinetics of adsorption also Whereas, in the case of nano alginate-based biosorbents, the best
describe the solute uptake rate governing the residence time of the fit of the equilibrium data is Freundlich adsorption isotherm model
adsorption reaction. In kinetic modelling, Langmuir and Freundlich which confirms the heterogeneity of the adsorption sites. This is
models are the most common isotherms for fitting experimental due to regression coefficient of 0.97 for Langmuir and 0.998 for
data obtained from heavy metal ions adsorption, but other models Freundlich (Geetha et al., 2015).
have also been accepted such as Redlich-Peterson, Khan models. Another example is biochar-based carbon nanotubes. R2 val-
(Febrianto et al., 2009). The intercept and the slope of each linear ues are higher for Langmuir model. This means that the Langmuir
plot are used to calculate Freundlich and Langmuir parameters isotherm model is a better fit than the Freundlich isotherm model,
(Sadeghi et al., 2020). suggesting that the interactions might be mainly related to mono-
Freundlich isotherm is an empirical equation (Eq. 10). It has layer adsorption; this might be because of the homogeneous
the ability to fit experimental data of a wide variety of adsorbents distribution of active sites on the biochar sample surfaces (Zhang
including bio sorbents and highly heterogeneous sorbent systems. et al., 2020). Layered double hydroxide, on the other hand, shows
Generally, favorable Freundlich isotherms have a n value between correlation coefficient of only 0.95 with Langmuir Isotherm. Along
1 and 10. Larger n is preferred as it implies stronger interaction with fitting into Freundlich and Langmuir models, DNA functional-
between biosorbent and heavy metal. Whereas a 1/n value nearing ized graphene it also fits into the Henry Model (Eq. 13). Graphitic
342
carbon nitride nanosheets follows Langmuir, Freundlich, Redlich-

Peterson (R-P)(Eq. 14), and Khan models(Eq. 15) (Liu et al., 2017b).
Qe = KHE Ce (13)
K R Ce
Qe = g (14)
1 + aR Ce
Qs bK Ce
Qe = (15)
(1 + bK Ce )aK
Sips isotherm is also a very accurate model (Eq. 16). The model’s
accuracy is justified by its use of three parameters, instead of two-
parameter models like Langmuir and Freundlich. Therefore, Sips
isotherm has the aptitude to fit wide ranges of adsorbate concen-
tration (Ihsanullah et al., 2020).
KS Ce ˇs
Qe = (16)
ˇ
1 + aS Ce s
To evaluate heat of adsorption of adsorbate molecules (B) with
the extent of coverage over the surface of adsorbent particles, the
adsorption data is analyzed through linear form of Temkin isother-
mal model (Eq. 17).
RT
Qe = ln(AT Ce ) (17)
bT
Another adsorption isotherm Dubinin–Radushkevich (D–R
model) is generally applied to express the adsorption mechanism
supported by a Gaussian energy distribution onto a heterogeneous
surface (Jakubov and Mainwaring, 2002; Nguyen and Do, 2001).
Thus, this isotherm fits well for the particles or structures having a
high degree of heterogeneity. It is governed by Eq. 18.
Qe = Qs e−kDR ε2 (18)
Isotherm constant (BDR), calculated from slope of the Dubinine-

Radushkevich isotherm can be used to calculate mean free energy
(E) of the adsorption process. For example, Cr(VI) by Ni2O3 coral
like nanostructure follow this isotherm (A.O, 2012; Dey et al.,
Fig. 8. (Krishna Kumar et al., 2017): Regenerative properties of Magnetic Fe3O4
2018). Hence, it can be applied to estimate the porosity, apparent nanoparticles for Cr adsorption.
free energy and the characteristics of adsorption. Table 3 provides
information on the isotherm models followed by various nano
where q0 and qr are respective adsorption capacities before and
adsorbents.
after regeneration.
Regeneration capacity also depends on the strength of the
5. Desorption and Regeneration
reaction between adsorbent and adsorbate. For example, in
physisorption molecules are weakly bound via van der Waals or
The regenerative property of an adsorbent is as important as its
electrostatic forces. Thus, regeneration is easier when compared
adsorption properties. It makes the adsorbent available for reuse,
to chemisorption where the adsorbate has a chemical interaction
reduces secondary pollution and also reduces cost of production
with the adsorbent surface through strong ionic or covalent bonds.
as it allows use of one adsorbent for multiple cycles (Kyzas et al.,
Therefore, in chemisorption processes the adsorbent is treated with
2014).
drastic procedures like thermal regeneration. For example, mix-
For industrial applications, it is crucial for adsorbents to be capa-
tures of iron oxide NPs use surface complexation and ion exchange
ble of maintaining their adsorptive properties throughout multiple
as their binding pattern so their efficiency decreases around 11
adsorption desorption cycles. Although an adsorbent is required
percent in six adsorption/regeneration cycles (Trujillo-Reyes et al.,
to have both good adsorption and desorption properties, this is
2014).Fig. 8 shows the regenerative properties (A) and change
difficult as both processes are opposites. Larger the adsorption
in efficiency through number of cycles (B) of magnetic Fe3O4
capacity, larger the affinity of molecules to the adsorbent which
nanoparticles used for the adsorption of chromium.
means smaller the desorption capacity. Although the regeneration
The selection of a suitable eluent depends on adsorbent and
process is very crucial for choosing the best adsorbent for a process,
adsorbate as well as process variables such as pH, temperature
only few papers have highlighted the specifics of this area and much
and contact time between the solid and liquid phases. Insight into
research is still yet to be done about the desorption of nanomaterial
the efficacy of regeneration process can be gained by observing
adsorbents(Kulkarni and Kaware, 2014; Lata et al., 2015).
the adsorption mechanism. Generally, it is easier to desorb metal
A loaded adsorbent can be regenerated to its original state to be
ions from adsorbent that follow Freundlich adsorption model when
reused again by using chemical, thermal or biological processes. In
compared to those following Langmuir adsorption model. This is
general, the capacity of adsorbent gradually decreases with each
due to the monolayer adsorption mechanism assumed by Langmuir
cycle. Regeneration efficiency can be calculated as shown in Eq. 19.
isotherm results in strong bond between adsorbate and adsorbent
qr whereas Freundlich model assumes multilayer adsorption of metal
RE% = × 100 (19)
q0 ions on heterogenous surface thus leading to formation of weaker
343
bonds (Plohl et al., 2019). The desorption of heavy metal ions from works in large scale industries. Among the various possible setups
adsorbents has been performed using different solutions, picked like pulse bed column, continuous moving bed column, fixed bed
according to the influence of pH value. column and continuous fluidized bed column, fixed bed column
Aqueous solutions of sodium hydroxide and strong acids are is the most popular setup used for dynamic mode of heavy metal
often used as regeneration solutions to elute heavy metals from adsorption on large scale as it is easy to operate as well as low cost
MNPs. In many studies, it has been concluded that desorption pro- (low cost since adsorbent regeneration is possible in this setup)
cess is heavily dependent on pH factor. So, the desorption stage is (Patel, 2019). A continuous fixed bed column setup is presented in
usually carried out by controlling the pH of eluent. Metal anions are Fig. 8. The effluent contaminated with metal ions is pumped to the
usually desorbed using basic solutions like NaOH whereas regen- top of the adsorption column. Initially, as the effluent flows through
eration of MNPs loaded with cations is carried out using acidic the bed, the top few layers of the adsorbent inside the bed adsorbs
solutions. Stronger acids like HNO3 and HCl are also used due to most of the metal ions that had been pumped with the effluent and
their high adsorption efficacy as ions are completely desorbed in almost metal free effluent flows through the rest of the adsorbent
one minute and no differences in adsorption capacities even after layers in the bed. The metal free effluent then exits the bed and is
15 cycles of adsorption. However, strong acids promote the disso- stored in another tank for further treatment or is discharged. The
lution of magnetic core and therefore are used limitedly. To get rid zone inside the bed, where most of the metal ions get adsorbed,
of this problem, EDTA is used as it shows efficacy similar to strong is called the mass transfer zone (MTZ). After some time of contin-
acids but does not degrade the adsorbent (Gómez-Pastora et al., uous effluent flow through the bed, the top layers get saturated
2014; Nizamuddin et al., 2018). with the metal ions and hence middle layers adsorb most of the
While alkalis were observed to be the best desorbing agents metal ions resulting into metal free effluent flow through the sub-
for chemical adsorbents, NaOH was found as the most effective sequent lower layers of the bed. Eventually, middle layers also get
desorbing agent for nanomaterial adsorbents. saturated with the metal ions and MTZ shifts to the last lower lay-
Nanocellulose as an adsorbent is also very favorable as it has ers of the bed. Finally, the whole bed gets saturated with the metal
a very efficient desorption capacity. This is attained by using the ions which results into higher exit concentration of metal ions from
nanocellulose in different desired shapes of solid aerogel form. This the bed (Upadhyay et al., 2020). At the outlet, the concentration
form allows recovery of adsorbent by simple filtration thus there of exit metal ions is continuously monitored using chemical opti-
is also no risk of aggregation (Mahfoudhi and Boufi, 2017). These cal sensors like surface plasmon resonance sensors unlike using
are all the frequently used desorption methods summarized which atomic absorption spectroscopy, which is only successful for lab
provide a good overview of regeneration process for nanomaterial setups where constant monitoring of metal ion concentration is
adsorbents. not required (Song et al., 2019). Once the exit concentration of
the metal ions from the bed exceed the permissible levels, the
flow of effluent is diverted to another bed (or the flow may also
6. Continuous removal of metal ions and role of be paused), while the saturated bed is treated with a regenerat-
nanomaterials ing agent (which mostly an acid, base or complexing agent). As the
regenerating agent flows through the bed, it desorbs the metal ions
Over the years, researchers have synthesized innumerous from the surface of adsorbent particles and makes the bed suitable
nanoscale adsorbents in the lab and have tested their performance for another cycle of effluent treatment. To achieve adsorption at low
for metal adsorption. However, most of this testing has been done cost, the adsorbent packaging inside the bed must be able to with-
in the batch mode of adsorption. Batch studies are important in stand several cycles of regeneration (Salvador et al., 2015; Vakili
order to obtain a value for maximum adsorption capacity of the et al., 2019). The regenerating stream collected during the regen-
adsorbent, understand the mechanism and kinetics of the adsorp- eration process is stored in the tank and might be taken for metal
tion process and to understand the effect of various parameters recovery processes. Unlike the case shown in Fig. 9, many setups
(like pH, Temperature, co-existing ions, etc.) onto the performance also use peristaltic pump to transport the effluent bottom to top as
of the adsorbent(Agarwal et al., 2020; Shahrokhi-Shahraki et al., it reduces the possibility of channeling that might occur inside the
2021). However, limiting the experiments only to batch experi- column (Leudjo Taka et al., 2020).
ments, in some cases, can be seen as something similar to leaving Keeping in mind that the adsorbent is generally supposed to be
the research midway. The success of an adsorbent in batch experi- used for such an industrial setup, many researchers have tested
ments is a necessary condition for the adsorbent to be a called as an their prepared nanoscale adsorbents in lab scale dynamic mode
efficient adsorbent but, in most cases, it is not the sufficient con- adsorption setups. One such study tested the Poly(vinyl) alco-
dition. Since most of the industries apply continuous adsorption hol/poly(acrylic) acid nanofiber membranes for adsorption of Pb(II)
columns for removal of heavy metal ions from their effluent, it is in fixed bed column setup and also explored the effect of operat-
very necessary for the adsorbents to perform well when packed ing parameters (like flow rate bed and height) onto the removal
inside the adsorption columns. Unfortunately, an adsorbent which capacity of the bed (Zhang et al., 2019a). It was observed that
has been successful in the batch mode of adsorption may not be on increasing the flow rate from 0.22 mL/min to 0.78 mL/min,
able to retain its success in the continuous mode of adsorption. the breakthrough capacity decreased from 76.55 to 55 mg/g. This
This is especially true for nanoparticles, which due to their high decrease can be attributed to the decrease in residence time of Pb(II)
agglomeration tendency, may agglomerate when packed inside the ions inside the bed with the increase in flow rate due to which less
bed column which might result into much decreased adsorption of number of metal ions are able to reach the micro and meso pores of
metal ions (Chang et al., 2018). In addition to this, a few adsorbents the adsorbent (Simate and Ndlovu, 2015). Similarly, with increase
also have a tendency to swell during the adsorption process. This in bed height (from 0.00227 to 0.00681 cm), the volume of efflu-
property of an adsorbent can lead to serious failure of the adsorp- ent treated increased from 1.2 mL to 3.6 mL. This was expected
tion column since swelling of adsorbent particles might block the since increase in adsorbent mass increases the total number of
passage for fluid flow through the bed(Vijayaraghavan and Joshi, sites available for adsorption resulting into increased volume of
2013). With all these concerns raised, it is important to test the effluent treatment (Zhang et al., 2019a). In another study, mechan-
synthesized nanomaterials in the continuous mode of adsorption. ically strong Sodium Alginate/Graphene/ l-Cysteine Nano-Beads
Before testing the nanomaterials in continuous mode, it is were packed into the column and used for adsorption of Cu(II) ions.
important to understand how continuous mode of adsorption In addition, a rotating magnetic field (RMF) was used to further
344
Fig. 9. Fixed-Bed column setup for continuous adsorption of metal ions.
Table 5
Performance of nanomaterials, for adsorption of heavy metal ions, when packed inside column bed.
S.No Adsorbent CD (cm); APH(cm); FR Results References

(mL/min); MI conc (mg/L)
1. Diatomite nanoparticles 2; 20a ; 5; 100 Saturation time for Cu: (Seifpanahi Shabani et al.,
169 min 2017)
a
2. Diatomite perlite nanoparticles 2; 20 ; 1; 100 Saturation time for Cu: (Seifpanahi Shabani et al.,
148 min 2017)
3. Sodium alginate nanobeads 5; 40a ; 2; 500 BT for Cd: 30 h (Aziz et al., 2020)
4. Sodium alginate - Activated charcoal nanobeads 5; 40a ; 2; 500 BT for Cd: 48 h (Aziz et al., 2020)
5. Perlite nanoparticles 2; 20a ; 1; 50 Saturation time for Cu: (Seifpanahi Shabani et al.,
131 min 2017)
6. Poly(vinyl) alcohol/poly(acrylic) acid nanofiber 1.27; 0.00227; 0.35; 1 EC for Pb: 288 mg/g (Zhang et al., 2019a)
membranes
7. Magnetic Chitosan nanobeads -; - ; 20; 20; AL: 50 mg Removal efficiency for (Subedi et al., 2019)
Cr(VI): 27.62 %
8. Chitosan/activated carbon/iron bio-nanocomposite 1; 0.25; 10; 100 EC for Cd(II): 243.13 (Sharififard et al., 2018)
mg/g
9. Multi-walled carbon nanotubes/ chitosan/ Fe3 O4 nanofiber 0.15; 1a ; 1; 50 EC for Cr(VI): 273.21 (Beheshti et al., 2016)
mg/g
10. Sugarcane straw nano-structure absorbent 3.4; 27; 50; 20 EC for Cd(II): 11.1 mg/g (Farzi et al., 2018)
a
Denotes column height and not adsorbent packaging height.
enhance the performance of the packed bed. It was observed that initial concentration, initial pH and contact time. Modelling the
RMF increased the adsorption capacity of the bed by 10.29 %, indi- removal process using traditional methods primarily depends on
cating that RMF has positive effect onto the adsorption process (Ma a deep understanding of adsorption mechanism and implementa-
et al., 2018). In yet another study, different adsorbent packaging tion of mechanistic models such as surface complexation model,
were prepared with TiO2 nanoparticles, Ag-TiO2 nanoparticles & and MUSIC model. A mechanistic model assumes that a complex
Fe-TiO2 nanoparticles coated on glass bead and used for continuous system can be divided and studied in individual parts and in the
removal of As(III). After efficient removal of As(III), the saturated manner in which they are coupled. Development of these models
bed was regenerated with 10 % NaOH solution. It was reported that involves many obvious simplifications and assumptions. Therefore,
86 % of the metal was recovered within 2–3 bed volumes of regener- although it is easy to obtain results using different models, few
ating agent and almost 99 % of the metal was recovered after 10 bed of these models could occasionally cause unacceptable predictions
volumes. This indicated that the adsorption of As(III) onto all these (Hamidian et al., 2019). But it is vital to use different models to pre-
three adsorbents was a reversible process and that the adsorption dict the results and get an idea about the adsorption process. Table 6
sites were easily accessible in the packaging. After regeneration, the shows the different software used for modelling and simulation.
packed beds retained almost 90 % of their metal removal capacity ANN is a computational intelligence paradigm that learns from
(Danish et al., 2013). Table 5 highlights the performance of other its environment and adapts to these changes to predict adsorption
nanomaterials which were applied for metal removal in continuous performance. It is composed of simple elements called neurons as
adsorption mode. processing units that are arranged in layer(s). The development
of the ANN model is done through many experimental sets. The
7. Modelling and simulation data is first collected from batch experiments and divided into
input matrix and target matrix. The ANN model builds the pre-
The removal performance of an adsorbent depends on many dicted mathematical model with scale inputs (adsorbent dosage,
factors including structure, effect of other coexisting substances, initial pH, temperature and contact time) and outputs which are
345
Table 6
Different Models used for simulating adsorption process.
Sr No Model Name Major Governing Summary Merits Remarks Limitations Ref No.
Equation
1. MLP-ANN yi (x) = Consists of input, output and Acceptable Hyperbolic tangent Determining the (Hamidian

n
hidden layers, training process representation of function is commonly number of layers et al., 2019)
f (b + xi wi ) is interconnections input/ output used function in is a difficult task
construction hidden layer
i=1
2. RBF-ANN yi (x) = Hidden layer has radial basis Simpler Structure Radial basis functions Determining the (Baghban et al.,

h activation function; neuron and faster training are used as activation number of layers 2017)
wki ∅(||x − xk ||) parameters of the model are process than functions in the hidden is a difficult task
the center, the distance scale MLP-ANN layer
k=1
and the precise shape of the
radial function.
3. SOS Xi, new = reproduces a new solution solution is Using new organism – (Gharehchopogh
Xi + rand (−1, 1) ∗ generation regarding constantly updated variables modify old et al., 2020)
(Xbest − Xi ) three-phase biological at every phase ones to better fitted
interactions between two values,
organisms in the ecosystem population-based
algorithm
4. LAMMPS Classical molecular System is modelled, simulation Performance can Choosing appropriate – (Garcia et al.,
dynamics code conditions are set up, energy be enhanced using potential functions is 2018; Yi et al.,
minimization to maintain packages such as very crucial 2014)
accuracy of results, setting of TIP3P and OPLS
simulation time
5. ANFIS (x) = x−c1 2bi combination of neural Eliminates Propagation methods Number of rules (Hussein,
1+ ai i networks and Fuzzy logic, structural can be forward pass or should be 2016)(Jang,
learns the rules and limitation by being backward pass decided 1993)
membership functions from not only feed empirically
data forward
the removal efficiencies of different heavy metal ions. All the data 8. Process optimization
is normalized (as shown in Eq. 20) between -1 and 1 to avoid
extremely small or large values (Hamidian et al., 2019). After the Adsorption is more efficient and cost effective than many other
training, the scaled values are rescaled to their original values. heavy metal removal methods. But it is important to derive the
optimal adsorption process parameters under different variables
such as pH, contact time, temperature and adsorption dosage to
X −X maximize efficiency. This process could be time-consuming. Fur-
min
X=2 −1 (20) ther, any human error occurrence during experiment may effect
Xmax − Xmin
accuracy of the results (Hamidian et al., 2019). Therefore, it is
imperative to adopt methods that allow determining the opti-
mal state of involved parameters and the amount of heavy metal
Variations of ANN models are often used in simulation pro-
adsorption.
cesses. Two popular types are RBF and MLP (shown in Table 6).
Statistical and mathematical method that is commonly
Often RBG-ANN is used over MLP-ANN as it has a faster training pro-
employed to determine the optimal reaction parameters is arti-
cess and also responds well to patterns not employed in the training
ficial neural network hybridized with an optimization algorithm
process. On the basis of batch adsorption experiments, many stud-
called ANN-GA. The GA optimization process continues until it
ies have revealed the use of models such as MLP ANN and RBF
approached the termination criteria or an approximate optimum
ANN for predicting the performance of heavy metal removal using
solution. GA process of optimization is repeated several times by
adsorbing materials. A comparative study of the predictive perfor-
varying the input space parameters until the suitable result was
mances of MLPANN, RBFANN, Langmuir and Freundlich removing
achieved (Singh et al., 2017). This dispenses, with mathematical
heavy metals using adsorbents is employed to determine the opti-
description, the complex nature of the underlying process. ANN
mal vales of initial adsorbent dosage, initial pH values, and contact
was derived using artificial intelligence and it can effectively elu-
times to maximize the removal percentage.
cidate multivariate nonlinear problems with the appropriate data
To ensure that the results of the simulation are accurate, it
and training algorithm. ANN has the ability to reasonably learn
is important to provide the software with precise inputs. Many
complex nonlinear functions and it is thereby used to approxi-
molecular dynamic simulations are also carried out on the LAMMPS
mate these unknown functions. It can also predict the degree of
package and used in combination with other software to ensure
the non-linearity of functions and process without detailed testing
better mirroring of the true adsorption process. For example, TIP3P
as compared to traditional mathematical models. Drawback of ANN
is used to model water interactions and OPLS (optimized potential
is that it is unable to solve all problems in wastewater treatment
for liquid simulation) parameters are used for metal ions, CNTs and
due to some inherent limitations such as not having the guarantee
functional groups ( COO, OH and C ONH2). These are some of
of obtaining absolute optimal solution.
the software used to obtain simulation results. Future challenges
The symbiotic organisms search (SOS) algorithm is also used as a
deal with making software more artificially intelligent. As they
numerical search tool which operates according to procedures that
learn from the environment and adapt to create better solution
resemble the principles of competition between organisms in real
with each trial, it is important to increase the capability of this
world. The SOS algorithm is founded on natural phenomena like
intelligence. We can validate these models by conducting batch
to other meta-heuristic algorithms. This algorithm selects a pop-
experiments under optimum operating conditions to compare the
ulation of candidate solutions in the search space to look for the
experimental values with predicted values under optimum oper-
optimal solution. Studies determine the optimal level of contribut-
ating conditions.
346
ing parameters to maximum heavy metals adsorption including mercial use (Yang et al., 2019). This implies the need for complex
adsorption dosage, initial pH, and contact time using SOS algorithm. matrix analysis and large-scale experiment designs (Alchouron
A combination of ANN with other optimization algorithm such et al., 2021).
ANN-GA and ANN-PSO (PSO is applied to optimize the weight and Current focus is also on magnetic nanoparticles and their indus-
bias parameters of ANN technique) are used to generate the global trial application (Baseri and Tizro, 2017)(Das et al., 2020). An
optimum operating variables for the adsorption processes. The interesting approach is identification of an industrial process capa-
learning rate of the network was set to the values that resulted ble to offer iron oxide nanoparticles as a cheap byproduct, thereby
in the optimal correlation coefficient (R2) for the neural network improving their accessibility. In general, materials in the form
(Eq. 21). Then, outputs obtained from the ANN were compared of their nanoparticles are quite expensive to produce, store and
with the experimental data to discuss their advantages and future handle often due to their production conditions and chemical sen-
developments. The network adaptability was shown in terms of sitivity to the environment. Magnetite nanoparticles can undergo
mean squared error (MSE) which stands for the statistical differ- undesirable oxidation reactions in ambient conditions but are rel-
ence between experimental and predicted values (Eq. 22). Use of atively stable when they possess high crystallinity. Magnetite is
this optimization algorithm is very useful. For example, maximum generated in nature through many processes and studies show that
adsorption capacity was found to be 1152.5 ␮g/g which was cor- it is reasonable to obtain it as a byproduct in a process aiming to
responding to the 99.4 % removal of As(III) at ANN-GA optimized produce other high purity chemicals (Pogorilyi et al., 2014).
process parameters. Process intensification technology is gaining a lot of traction

M in recent research. This is due to the fact that preparation done
i=1
(yi,pred − yi,exp ) in traditional batch reactors in which particle size, distribution
MSE = (21)
M could not be controlled, especially in case of a large volume of

M
M solution. The impinging stream-rotating packed bed (IS-RPB) can
(xi − xi,mean )2 − (xi − yi )2
2 i=1 i=1 generate a high-gravity environment to intensify the micro mixing
R =
M 2
(22)
i=1
(xi − yi ) and mass-transfer processes leading to homogeneous concentra-
tion, temperature and supersaturation, which is beneficial to the
In order to obtain the maximum response that jointly satisfies uniform nucleation and growth of particles. Moreover, IS-RPB has
all process conditions, optimization can also be carried out using been proved to be an ideal device for a continuous large-scale
the Design Expert software under RSM. In numerical optimization, industrialization preparation of nanoparticles It has successfully
the desired output is specified for each factor and response. A min- been employed to synthesize magnetic adsorbent materials with
imum and a maximum level must be provided for each parameter excellent adsorption performance (Fan et al., 2019).
included. A weight can be assigned to each output to adjust the On the other hand, according to most studies done on graphene-
shape of its specific desirability function. These outputs are then based nanomaterials, they are still in the preliminary stages of
combined into an overall desirability function. Desirability func- research and research on the practical application of these materi-
tion is an objective function that ranges from zero outside of the als in industrial wastewater treatment are still lacking, especially
limits, to one at the desired output. The output begins at random for actual wastewater as it contains multiple pollutants. Other alter-
starting point and proceeds to the maximum. There may be two or natives for large-scale production are also being studied, one of the
more maxima because of curvature in the response surfaces and methods is continuous synthesis, which provides for more produc-
their combination will become the desirability function. Starting tion volume for increased operating times. An example of this is
from several points in the design space will improve the chances of continuous production of iron oxide nanoparticles via high tem-
finding the most desirable local maximum (Bayuo et al., 2019). An perature synthesis (Besenhard et al., 2020).
example of the importance of optimization was its use in finding Besides adsorption performance, feasibility studies are equally
optimal operating conditions for Pb (II) adsorption. essential to nanomaterial application. The use-cost of the adsorbent
The function of desirability was applied using Design Expert is mainly dependent on the preparation process. The cost of this
Software (DES) version 11.0 and the operating condition with the preparation mainly involves three parts: chemical reactants, equip-
highest desirability was considered as selected by the software. The ment and energy consumption. For example, a study conducting
experimental condition with the highest desirability was selected feasibility study on microwave vs conventional heating concluded
and verified to optimize the adsorption process of Pb (II) ion. The that microwave heating assisted synthesis is more feasible. The ini-
optimum operating conditions for the adsorption of Pb (II) were: tial cost, handling capacity, reaction time and future development
Contact time = 90 min, pH = 8 and Initial concentration = 75 mg/L of microwave technology were taken into account (Du et al., 2021).
with the desirability of 0.966 after seeking 53 solutions to optimize Feasibility studies have also been done to increase the removal effi-
operating conditions for Pb (II) adsorption. The removal efficiency ciency of heavy metals by zero-valent iron (Cao et al., 2018; Hamdy
and adsorption capacity of Pb (II) under this operating condition et al., 2019).
were found to be 90.26 % and 3.428 mg/g respectively (Bayuo et al., It is important to conduct more research to bridge the gap
2019). between lab results and industrial applications by scalability per-
Optimization is very vital aspect for improving the heavy metal formance tests. These include multi-component testing, sorption
adsorption capacity. Carrying out proper analysis through opti- experiments in natural pollutant concentration media, real water
mization and deriving the most optimal conditions for adsorption tests and large-scale column tests (Alchouron et al., 2021; Celestin
is a very promising advantage to the industry. et al., 2020).
9. Scale up and feasibility studies
The commercial nanomaterials needed for heavy metal removal 10. Discussion and future
on an industry scale are rare and more efforts are needed to produce
market-available nanomaterials. The production should meet the Several important concerns and developments are under
requirements for green chemistry and the operating costs should progress and extensive research is being conducted about the appli-
be maintained for the sake of the economy. In this section, there cation of various nanomaterials in the remediation of wastewater
is brief discussion of different scale up of nanomaterials for com- and removal of wastewater pollutants.
347
• At present, there is no well-defined universal criterion to consider pathogens etc. simultaneously should be and efforts must be
what is a proper adsorbent or light active catalyst or disinfectant made to increase their stability and decrease the sensitivity with
that can be used for water remediation. It needs to be formulated respect to changes in pH and concentration of contaminated
considering the numerous factors especially those concerning wastewater.
environmental hazards, toxicity etc.(Byrne et al., 2018). 4 There are still discrepancies on the best-fitting kinetic model for
• Research needs to be done to formulate a set of regulations and some adsorbents. More detailed and accurate studies should be
specifications regarding the suitable number regeneration cycles conducted regarding these kinetic models.
and the finances associated with the nanoparticles that are recov- 5 Regeneration of nanomaterial-based absorbents is necessary to
ered from effluent streams, both at the industrial scale and in ensure the optimal use of them in the real wastewater treat-
laboratories (Zhang et al., 2019b). ment. This aspect also controls the economic viability and thus
• Most of the researches and studies emphasize on recyclability and it is very crucial. There is prevalent scope for more research and
regeneration during the treatment. However, what lacks is the modifications to be made to make adsorbents more efficient in
comparative analysis of regeneration and recyclability between regeneration.
multi component and mono component treatments. This is vital 6 With the increasing environmental awareness, more efficient,
for scaling up and industrialisation of the laboratory research inexpensive, highly selective, easily reusable or regenerable and
studies (Hlongwane et al., 2019). environment friendly adsorbents are highly in demand and stud-
• Besides comparative study of recyclability and regeneration in ies should be conducted to bridge this gap (Qin et al., 2020).
multi component system, multiple pollutants co-exist and deter- 7 The preparation, development and optimization of new gen-
mine the removal efficiency and significantly affect the order of eration adsorbents is crucial for industrial and commercial
degradation. This leads to wide mutabilities batch to batch. There- remediation of wastewater, especially using column operations
fore, effective studies focusing on competitive interactions are (Singh et al., 2018).
crucial to understand the underlying mechanisms, to predict the
efficiency losses due to comparative and preferential treatment The need of the hour is to overcome these challenges and draw-
and to gain insight on preventing these strategies (Abouzeid et al., backs and gain deeper insight and make widespread progress in
2019). this domain. The future of effective, economical and eco-friendly
• Adsorption based on nanotechnology has significantly been new generation adsorbents seems to be quite bright.
proven highly effective in lowering pollutant concentrations to
as low as 0.002 mg/L, which are sufficiently low as compared to Declaration of Competing Interest
the recommended levels of drinking water MCL. There however,
is a need to address and compare pollutant concentrations that We, the authors hereby declare that there is no conflict of inter-
are obtained post treatment to the MCL allowed for the kind of est associated with this work and we adhered to all the journal.
water that has undergone treatment (Peng et al., 2020).
• Majority of the proposed remediation applications for simultane- Acknowledgements
ous contaminant removal are not yet industrialised and revolver
around research based on laboratory experiments. They need to Authors would like to thank CSIR-HRDG, Scheme Number:
be field tested and directed towards actual process engineering 22(0783)/19/EMR-iI for funding this project and BITS Pilani Hyder-
and material development that can be utilised on a pilot scale and abad Campus for facilitating the same.
not remain saturated with research studies only (Ghasemzadeh
et al., 2014). References
• To facilitate this pilot scale industralisation and to effectively
commercialize nanomaterials for contaminant removal, analyt- A.O, D., 2012. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms
studies of equilibrium sorption of Zn 2+ unto phosphoric acid modified rice husk.
ical studies concerning the economic aspect of the proposed
IOSR J. Appl. Chem., http://dx.doi.org/10.9790/5736-0313845.
methods should be included in scientific researches. Modelling Abdel Maksoud, M.I.A., Elgarahy, A.M., Farrell, C., Al-Muhtaseb, A.H., Rooney, D.W.,
and techno-economic analysis using available hard water and Osman, A.I., 2020. Insight on water remediation application using magnetic
nanomaterials and biosorbents. Coord. Chem. Rev., http://dx.doi.org/10.1016/
associated environmental conditions should be significantly
j.ccr.2019.213096.
highlighted (Santhosh et al., 2016). Abdelbasir, S.M., Shalan, A.E., 2019. An overview of nanomaterials for industrial
wastewater treatment. Korean J. Chem. Eng., http://dx.doi.org/10.1007/s11814-
019-0306-y.
11. Conclusion Abedi, S., Zavvar Mousavi, H., Asghari, A., 2016. Investigation of heavy metal ions
adsorption by magnetically modified aloe vera leaves ash based on equilibrium,
kinetic and thermodynamic studies. Desalin. Water Treat., http://dx.doi.org/10.
This paper gives a concise yet vast overview of the scope of 1080/19443994.2015.1060536.
nanomaterials as adsorbents for heavy metal removal. Although Abouzeid, R.E., Khiari, R., El-Wakil, N., Dufresne, A., 2019. Current state and
new trends in the use of cellulose nanomaterials for wastewater treat-
there is a highly increasing momentum and fast pace improvement
ment. Biomacromolecules 20, 573–597, http://dx.doi.org/10.1021/acs.biomac.
in available literature on nanomaterials and their significance in 8b00839.
contaminant removal, there still are some concerns and gaps that Abraham, T.N., Kumar, R., Misra, R.K., Jain, S.K., 2012. Poly(vinyl alcohol)-based
require more attention and extensive research. The following are a MWCNT hydrogel for lead ion removal from contaminated water. J. Appl. Polym.
Sci., http://dx.doi.org/10.1002/app.35666.
few of these areas: Abshirini, Y., Esmaeili, H., Foroutan, R., 2019. Enhancement removal of Cr (VI) ion
using magnetically modified MgO nanoparticles. Mater. Res. Express, http://dx.
doi.org/10.1088/2053-1591/ab56ea.
1 Comparative studies need to be done highlighting the conditions, Adesodun, J.K., Atayese, M.O., Agbaje, T.A., Osadiaye, B.A., Mafe, O.F., Soretire, A.A.,
feasibility, effectiveness and economics of different adsorbents 2010. Phytoremediation potentials of sunflowers (Tithonia diversifolia and
Helianthus annuus) for metals in soils contaminated with zinc and lead nitrates.
that can be used at the industrial level.
Water Air Soil Pollut., http://dx.doi.org/10.1007/s11270-009-0128-3.
2 Eco-friendly adsorbents are of great importance now. But these Agarwal, A., Upadhyay, U., Sreedhar, I., Singh, S.A., Patel, C.M., 2020. A review on val-
are only being applied in laboratory scale so methods should be orization of biomass in heavy metal removal from wastewater. J. Water Process
developed for industrial scale applications. Eng. 38, http://dx.doi.org/10.1016/j.jwpe.2020.101602.
Ahmad, M., Manzoor, K., Ikram, S., 2017. Versatile nature of hetero-chitosan based
3 Adsorbents capable of removing multiple pollutants like organic derivatives as biodegradable adsorbent for heavy metal ions; a review. Int. J. Biol.
and inorganic dyes, toxic metal ions, fungal and bacterial Macromol. 105, 190–203, http://dx.doi.org/10.1016/j.ijbiomac.2017.07.008.
348
Ahmad, S.Z.N., Wan Salleh, W.N., Ismail, A.F., Yusof, N., Mohd Yusop, M.Z., Aziz, F., Balaji, S., Kalaivani, T., Shalini, M., Gopalakrishnan, M., Rashith Muhammad, M.A.,
2020. Adsorptive removal of heavy metal ions using graphene-based nanoma- Rajasekaran, C., 2016. Sorption sites of microalgae possess metal binding abil-
terials: toxicity, roles of functional groups and mechanisms. Chemosphere 248, ity towards Cr(VI) from tannery effluents—a kinetic and characterization study.
126008, http://dx.doi.org/10.1016/j.chemosphere.2020.126008. Desalin. Water Treat., http://dx.doi.org/10.1080/19443994.2015.1064032.
Ahmadi, M., Hazrati Niari, M., Kakavandi, B., 2017. Development of maghemite Bandar, S., Anbia, M., Salehi, S., 2021. Comparison of MnO2 modified and unmodified
nanoparticles supported on cross-linked chitosan (␥-Fe2O3@CS) as a recover- magnetic Fe3O4 nanoparticle adsorbents and their potential to remove iron and
able mesoporous magnetic composite for effective heavy metals removal. J. Mol. manganese from aqueous media. J. Alloys. Compd., http://dx.doi.org/10.1016/j.
Liq., http://dx.doi.org/10.1016/j.molliq.2017.10.014. jallcom.2020.156822.
Ahmaruzzaman, M., 2019. Nano-materials: novel and promising adsorbents for Bankole, M.T., Abdulkareem, A.S., Mohammed, I.A., Ochigbo, S.S., Tijani, J.O.,
water treatment. Asian J. Water, Environ. Pollut., http://dx.doi.org/10.3233/ Abubakre, O.K., Roos, W.D., 2019. Selected heavy metals removal from electro-
AJW190032. plating wastewater by purified and polyhydroxylbutyrate functionalized carbon
Aigbe, U.O., Osibote, O.A., 2020. A review of hexavalent chromium removal from nanotubes adsorbents. Sci. Rep. 9, 1–19, http://dx.doi.org/10.1038/s41598-018-
aqueous solutions by sorption technique using nanomaterials. J. Environ. Chem. 37899-4.
Eng., http://dx.doi.org/10.1016/j.jece.2020.104503. Barakat, M.A., 2011. New trends in removing heavy metals from industrial wastew-
Akpomie, K.G., Dawodu, F.A., 2016. Acid-modified montmorillonite for sorption of ater. Arab. J. Chem., http://dx.doi.org/10.1016/j.arabjc.2010.07.019.
heavy metals from automobile effluent. Beni-Suef Univ. J. Basic Appl. Sci. 5, 1–12, Baruah, S., Pal, S.K., Dutta, J., 2013. Nanostructured zinc oxide for water
http://dx.doi.org/10.1016/j.bjbas.2016.01.003. treatment. Nanosci. &Nanotechnology-Asia, http://dx.doi.org/10.2174/
Alam, M.S., Bishop, B., Chen, N., Safari, S., Warter, V., Byrne, J.M., Warchola, T., Kappler, 2210681211202020090.
A., Konhauser, K.O., Alessi, D.S., 2020. Reusable magnetite nanoparticles–biochar Baseri, H., Tizro, S., 2017. Treatment of nickel ions from contaminated water by mag-
composites for the efficient removal of chromate from water. Sci. Rep. 10, 1–12, netite based nanocomposite adsorbents: effects of thermodynamic and kinetic
http://dx.doi.org/10.1038/s41598-020-75924-7. parameters and modeling with Langmuir and Freundlich isotherms. Process Saf.
Alchouron, J., Navarathna, C., Rodrigo, P.M., Snyder, A., Chludil, H.D., Vega, A.S., Bosi, Environ. Prot. 109, 465–477, http://dx.doi.org/10.1016/j.psep.2017.04.022.
G., Perez, F., Mohan, D., Pittman, C.U., Mlsna, T.E., 2021. Household arsenic con- Bassyouni, D., Mohamed, M., El-Ashtoukhy, E.S., El-Latif, M.A., Zaatout, A.,
taminated water treatment employing iron oxide/bamboo biochar composite: Hamad, H., 2019. Fabrication and characterization of electrospun Fe3O4/o-
An approach to technology transfer. Journal of Colloid and Interface Science., MWCNTs/polyamide 6 hybrid nanofibrous membrane composite as an efficient
http://dx.doi.org/10.1016/j.jcis.2020.11.036, Elsevier Inc. and recoverable adsorbent for removal of Pb (II). Microchem. J. 149, 103998,
Alhan, S., Nehra, M., Dilbaghi, N., Singhal, N.K., Kim, K.H., Kumar, S., 2019. Poten- http://dx.doi.org/10.1016/j.microc.2019.103998.
tial use of ZnO@activated carbon nanocomposites for the adsorptive removal Bayuo, J., Pelig-ba, K.B., Abukari, M.A., 2019. Optimization of adsorption parameters
of Cd2+ ions in aqueous solutions. Environ. Res., http://dx.doi.org/10.1016/j. for effective removal of lead (II) from physical chemistry : an indian journal
envres.2019.03.061. optimization of adsorption parameters for effective removal of lead (II) from
Ali, H., Khan, E., Sajad, M.A., 2013. Phytoremediation of heavy metals-Concepts and aqueous solution. Phys Chem Ind J. 14, 123.
applications. Chemosphere, http://dx.doi.org/10.1016/j.chemosphere.2013.01. Beheshti, H., Irani, M., Hosseini, L., Rahimi, A., Aliabadi, M., 2016. Removal of Cr (VI)
075. from aqueous solutions using chitosan/MWCNT/Fe3O4 composite nanofibers-
Ali, M.E.A., Aboelfadl, M.M.S., Selim, A.M., Khalil, H.F., Elkady, G.M., 2018. Chitosan batch and column studies. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2015.08.
nanoparticles extracted from shrimp shells, application for removal of Fe(II) 158.
and Mn(II) from aqueous phases. Sep. Sci. Technol., http://dx.doi.org/10.1080/ Bertorelle, F., Wilhelm, C., Roger, J., Gazeau, F., Ménager, C., Cabuil, V., 2006.
01496395.2018.1489845. Fluorescence-modified superparamagnetic nanoparticles: intracellular uptake
Ali, H., Kim, K., Kumar, V., Kim, S., Park, J., 2019. Nanomaterials-based treatment and use in cellular imaging. Langmuir, http://dx.doi.org/10.1021/la052710u.
options for chromium in aqueous environments. Environ. Int. 130, 104748, Besenhard, M.O., Lagrow, A.P., Famiani, S., Pucciarelli, M., Lettieri, P., Thanh, N.T.K.,
http://dx.doi.org/10.1016/j.envint.2019.04.020. Gavriilidis, A., 2020. Continuous production of iron oxide nanoparticles: via fast
Alipour, A., Zarinabadi, S., Azimi, A., Mirzaei, M., 2020. Adsorptive removal and economical high temperature synthesis. React. Chem. Eng. 5, 1474–1483,
of Pb(II) ions from aqueous solutions by thiourea-functionalized magnetic http://dx.doi.org/10.1039/d0re00078g.
ZnO/nanocellulose composite: optimization by response surface methodology Bhardwaj, V., Kumar, P., Singhal, G., 2014. Toxicity of heavy metals pollutants in
(RSM). Int. J. Biol. Macromol., http://dx.doi.org/10.1016/j.ijbiomac.2020.02.109. textile mills effluents. Int. J. Sci. Eng. Res. 5, 664–666.
Almeida, J.C., Cardoso, C.E.D., Tavares, D.S., Freitas, R., Trindade, T., Vale, C., Pereira, Bhatia, M., Satish Babu, R., Sonawane, S.H., Gogate, P.R., Girdhar, A., Reddy, E.R., Pola,
E., 2019. Chromium removal from contaminated waters using nanomaterials – M., 2017. Application of nanoadsorbents for removal of lead from water. Int.
a review. TrAC - Trends Anal. Chem., http://dx.doi.org/10.1016/j.trac.2019.05. J. Environ. Sci. Technol. 14, 1135–1154, http://dx.doi.org/10.1007/s13762-016-
005. 1198-6.
Almomani, F., Bhosale, R., Khraisheh, M., kumar, A., Almomani, T., 2020. Heavy metal Bilecka, I., Niederberger, M., 2010. Microwave chemistry for inorganic nanomaterials
ions removal from industrial wastewater using magnetic nanoparticles (MNP). synthesis. Nanoscale., http://dx.doi.org/10.1039/b9nr00377k.
Appl. Surf. Sci., http://dx.doi.org/10.1016/j.apsusc.2019.144924. Brar, S.K., Verma, M., Surampalli, R.Y., Misra, K., Tyagi, R.D., Meunier, N., Blais,
Al-Sherbini, A.S.A., Ghannam, H.E.A., El-Ghanam, G.M.A., El-Ella, A.A., Youssef, A.M., J.F., 2006. Bioremediation of hazardous wastes - A review. Pract. Period. Haz-
2019. Utilization of chitosan/Ag bionanocomposites as eco-friendly photocat- ardous, Toxic, Radioact. Waste Manag., http://dx.doi.org/10.1061/(ASCE)1090-
alytic reactor for Bactericidal effect and heavy metals removal. Heliyon., http:// 025X(2006)10:2(59).
dx.doi.org/10.1016/j.heliyon.2019.e01980. Byrappa, K., Adschiri, T., 2007. Hydrothermal technology for nanotechnology. Prog.
Amin, M.T., Alazba, A.A., Manzoor, U., 2014. A review of removal of pollutants from Cryst. Growth Charact. Mater., http://dx.doi.org/10.1016/j.pcrysgrow.2007.04.
water/wastewater using different types of nanomaterials. Adv. Mater. Sci. Eng. 001.
Int. J. 2014, http://dx.doi.org/10.1155/2014/825910. Byrne, C., Subramanian, G., Pillai, S.C., 2018. Recent advances in photocatalysis for
Amjadi, M., Samadi, A., Manzoori, J.L., 2015. A composite prepared from halloysite environmental applications. J. Environ. Chem. Eng., http://dx.doi.org/10.1016/j.
nanotubes and magnetite (Fe3O4) as a new magnetic sorbent for the precon- jece.2017.07.080.
centration of cadmium(II) prior to its determination by flame atomic absorption Cao, C.Y., Li, P., Qu, J., Dou, Z.F., Yan, W.S., Zhu, J.F., Wu, Z.Y., Song, W.G., 2012. High
spectrometry. Microchim. Acta., http://dx.doi.org/10.1007/s00604-015-1491-y. adsorption capacity and the key role of carbonate groups for heavy metal ion
Anbia, M., Haqshenas, M., 2015. Adsorption studies of Pb(II) and Cu(II) ions on meso- removal by basic aluminum carbonate porous nanospheres. J. Mater. Chem. 22,
porous carbon nitride functionalized with melamine-based dendrimer amine. 19898–19903, http://dx.doi.org/10.1039/c2jm34138g.
Int. J. Environ. Sci. Technol., http://dx.doi.org/10.1007/s13762-015-0776-3. Cao, Y., Zhang, S., Zhong, Q., Wang, G., Xu, X., Li, T., Wang, L., Jia, Y., Li, Y., 2018.
Anitha, T., Kumar, P.S., Kumar, K.S., Sriram, K., Ahmed, J.F., 2016. Biosorption of Feasibility of nanoscale zero-valent iron to enhance the removal efficiencies of
lead(II) ions onto nano-sized chitosan particle blended polyvinyl alcohol (PVA): heavy metals from polluted soils by organic acids. Ecotoxicol. Environ. Saf. 162,
adsorption isotherms, kinetics and equilibrium studies. Desalin. Water Treat. 57, 464–473, http://dx.doi.org/10.1016/j.ecoenv.2018.07.036.
13711–13721, http://dx.doi.org/10.1080/19443994.2015.1061951. Castro, L., Blázquez, M.L., Muñoz, J.A., González, F., García-Balboa, C., Ballester, A.,
Anjum, M., Miandad, R., Waqas, M., Gehany, F., Barakat, M.A., 2019. Remediation of 2011. Biosynthesis of gold nanowires using sugar beet pulp. Process Biochem.,
wastewater using various nano-materials. Arab. J. Chem., http://dx.doi.org/10. http://dx.doi.org/10.1016/j.procbio.2011.01.025.
1016/j.arabjc.2016.10.004. Celestin, S., Qi, F., Li, R., Yu, T., Cheng, W., 2020. Evaluation of 32 simple equations
Anuradha, T.V., 2010. Template-Assisted Sol-Gel Synthesis of 7., pp. 894–898. against the penman–monteith method to estimate the reference evapotranspi-
Aziz, F., Achaby, M.El, Lissaneddine, A., Aziz, K., Ouazzani, N., Mamouni, R., Mandi, ration in the hexi corridor, northwest china. Water (Switzerland) 12, http://dx.
L., 2020. Composites with alginate beads: a novel design of nano-adsorbents doi.org/10.3390/w12102772.
impregnation for large-scale continuous flow wastewater treatment pilots. Chang, S., Fu, H., Wu, X., Liu, C., Li, Z., Dai, Y., Zhang, H., 2018. Batch and
Saudi J. Biol. Sci., http://dx.doi.org/10.1016/j.sjbs.2019.11.019. fixed-bed column studies for selective removal of cesium ions by compress-
Azizian, S., 2004. Kinetic models of sorption: a theoretical analysis. J. Colloid Interface ible Prussian blue/polyurethane sponge. RSC Adv., http://dx.doi.org/10.1039/
Sci., http://dx.doi.org/10.1016/j.jcis.2004.03.048. C8RA07665K.
Azzam, A.M., El-Wakeel, S.T., Mostafa, B.B., El-Shahat, M.F., 2016. Removal of Pb, Cd, Charerntanyarak, L., 1999. Heavy metals removal by chemical coagulation and pre-
Cu and Ni from aqueous solution using nano scale zero valent iron particles. J. cipitation. In: Water Science and Technology., http://dx.doi.org/10.1016/S0273-
Environ. Chem. Eng., http://dx.doi.org/10.1016/j.jece.2016.03.048. 1223(99)00304-2.
Baghban, A., Mohammadi, A.H., Taleghani, M.S., 2017. Rigorous modeling of CO2 Chawla, J., Kumar, R., Kaur, I., 2015. Carbon nanotubes and graphenes as adsorbents
equilibrium absorption in ionic liquids. Int. J. Greenh. Gas Control 58, 19–41, for adsorption of lead ions from water: a review. J. Water Supply Res. Technol. -
http://dx.doi.org/10.1016/j.ijggc.2016.12.009. AQUA 64, 641–659, http://dx.doi.org/10.2166/aqua.2015.102.
349
Chen, Y.H., Li, F.A., 2010. Kinetic study on removal of copper(II) using goethite and synthesis of amino-carboxyl functionalized cellulose for enhanced heavy metal
hematite nano-photocatalysts. J. Colloid Interface Sci. 347, 277–281, http://dx. removal. Chemosphere 268, 128833, http://dx.doi.org/10.1016/j.chemosphere.
doi.org/10.1016/j.jcis.2010.03.050. 2020.128833.
Chen, Z., Guo, B., Yang, Y., Cheng, C., 2014. Metamaterials-based enhanced energy Egodawatte, S., Greenstein, K.E., Vance, I., Rivera, E., Myung, N.V., Parkin, G.F.,
harvesting: a review. Phys. B Condens. Matter., http://dx.doi.org/10.1016/j. Cwiertny, D.M., Larsen, S.C., 2016. Electrospun hematite nanofiber/mesoporous
physb.2013.12.040. silica core/shell nanomaterials as an efficient adsorbent for heavy metals. RSC
Chen, R., Wang, P., Li, M., Tian, F., Xiao, J., Fu, X., Ding, C., Shi, Y., 2018. Removal of Adv. 6, 90516–90525, http://dx.doi.org/10.1039/c6ra19876g.
Cr(VI) by magnetic Fe/C crosslinked nanoparticle for water purification: rapid El-Nahhal, I.M., Chehimi, M., Selmane, M., 2018. Synthesis and structural charac-
contaminant removal property and mechanism of action. Water Sci. Technol. terization of G-SBA-IDA, G-SBA-EDTA and G-SBA-DTPA modified mesoporous
78, 2171–2182, http://dx.doi.org/10.2166/wst.2018.497. SBA-15 silica and their application for removal of toxic metal ions pollutants.
Chen, W., Lu, Z., Xiao, B., Gu, P., Yao, W., Xing, J., Asiri, A.M., Alamry, K.A., Wang, X., Silicon 10, 981–993, http://dx.doi.org/10.1007/s12633-017-9556-7.
Wang, S., 2019. Enhanced removal of lead ions from aqueous solution by iron Epifani, M., Giannini, C., Tapfer, L., Vasanelli, L., 2000. Sol – gel synthesis and char-
oxide nanomaterials with cobalt and nickel doping. J. Clean. Prod., http://dx.doi. acterization of Ag and Au nanoparticles in. J. Am. Ceram. Soc. 83, 2385–2393.
org/10.1016/j.jclepro.2018.11.254. Erdem, E., Karapinar, N., Donat, R., 2004. The removal of heavy metal cations by
Chenab, K.K., Sohrabi, B., Jafari, A., Ramakrishna, S., 2020. Water treatment: func- natural zeolites. J. Colloid Interface Sci., http://dx.doi.org/10.1016/j.jcis.2004.08.
tional nanomaterials and applications from adsorption to photodegradation. 028.
Mater. Today Chem., http://dx.doi.org/10.1016/j.mtchem.2020.100262. Fakhri, A., 2015. Investigation of mercury (II) adsorption from aqueous solution
Chowdhury, M., Mostafa, M.G., Biswas, T.K., Mandal, A., Saha, A.K., 2015. Character- onto copper oxide nanoparticles: optimization using response surface method-
ization of the effluents from leather processing industries. Environ. Sci. Process. ology. Process Saf. Environ. Prot., http://dx.doi.org/10.1016/j.psep.2014.06.
Impacts 2, 173–187, http://dx.doi.org/10.1007/s40710-015-0065-7. 003.
Corbett, J.F., 1972. Pseudo first-order kinetics. J. Chem. Educ., http://dx.doi.org/10. Fan, L., Luo, C., Sun, M., Li, X., Qiu, H., 2013. Highly selective adsorption of lead ions by
1021/ed049p663. water-dispersible magnetic chitosan/graphene oxide composites. Colloids Surf.
Corbierre, M.K., Beerens, J., Lennox, R.B., 2005. Gold nanoparticles generated by B Biointerfaces, http://dx.doi.org/10.1016/j.colsurfb.2012.11.006.
electron beam lithography of gold(I)-thiolate thin films. Chem. Mater. 17, Fan, H., Ma, X., Zhou, S., Huang, J., Liu, Yaqing, Liu, Youzhi, 2019. Highly efficient
5774–5779, http://dx.doi.org/10.1021/cm051085b. removal of heavy metal ions by carboxymethyl cellulose-immobilized Fe 3 O
Cui, L., Wang, Y., Gao, L., Hu, L., Yan, L., Wei, Q., Du, B., 2015. EDTA functionalized 4 nanoparticles prepared via high-gravity technology. Carbohydr. Polym. 213,
magnetic graphene oxide for removal of Pb(II), Hg(II) and Cu(II) in water treat- 39–49, http://dx.doi.org/10.1016/j.carbpol.2019.02.067.
ment: adsorption mechanism and separation property. Chem. Eng. J., http://dx. Fang, Y., Lv, X., Xu, X., Zhu, J., Liu, P., Guo, L., Yuan, C., Cui, B., 2020. Three-dimensional
doi.org/10.1016/j.cej.2015.06.043. nanoporous starch-based material for fast and highly efficient removal of heavy
Danish, M.I., Qazi, I.A., Zeb, A., Habib, A., Awan, M.A., Khan, Z., 2013. Arsenic removal metal ions from wastewater. Int. J. Biol. Macromol. 164, 415–426, http://dx.doi.
from aqueous solution using pure and metal-doped Titania nanoparticles coated org/10.1016/j.ijbiomac.2020.07.017.
on glass beads: adsorption and column studies. J. Nanomater., http://dx.doi.org/ Farzi, S., Farasati, M., Bansouleh, B.F., Pirsaheb, M., 2018. Evaluation of batch and
10.1155/2013/873694. continuous adsorption kinetic models of cadmium from aqueous solutions using
Darezereshki, E., Darban, Akhodadadi, Abdollahy, M., Jamshidi-Zanjani, A., 2018. sugarcane straw nano-structure absorbent. Desalin. Water Treat., http://dx.doi.
Influence of heavy metals on the adsorption of arsenate by magnetite nanopar- org/10.5004/dwt.2018.22450.
ticles: kinetics and thermodynamic. Environ. Nanotechnology, Monit. Manag., Fato, F.P., Li, D.W., Zhao, L.J., Qiu, K., Long, Y.T., 2019. Simultaneous removal of mul-
http://dx.doi.org/10.1016/j.enmm.2018.04.002. tiple heavy metal ions from river water using ultrafine mesoporous magnetite
Darr, J.A., Zhang, J., Makwana, N.M., Weng, X., 2017. Continuous hydrothermal syn- nanoparticles. ACS Omega, http://dx.doi.org/10.1021/acsomega.9b00731.
thesis of inorganic nanoparticles: applications and future directions. Chem. Rev. Febrianto, J., Kosasih, A.N., Sunarso, J., Ju, Y.H., Indraswati, N., Ismadji, S., 2009. Equi-
117, 11125–11238, http://dx.doi.org/10.1021/acs.chemrev.6b00417. librium and kinetic studies in adsorption of heavy metals using biosorbent: a
Das, T.K., Sakthivel, T.S., Jeyaranjan, A., Seal, S., Bezbaruah, A.N., 2020. Ultra-high summary of recent studies. J. Hazard. Mater. 162, 616–645, http://dx.doi.org/
arsenic adsorption by graphene oxide iron nanohybrid: removal mechanisms 10.1016/j.jhazmat.2008.06.042.
and potential applications. Chemosphere 253, 126702, http://dx.doi.org/10. Fu, F., Dionysiou, D.D., Liu, H., 2014. The use of zero-valent iron for groundwater
1016/j.chemosphere.2020.126702. remediation and wastewater treatment: a review. J. Hazard. Mater., http://dx.
Dave, P.N., Chopda, L.V., 2014. Application of iron oxide nanomaterials for the doi.org/10.1016/j.jhazmat.2013.12.062.
removal of heavy metals. J. Nanotechnol., http://dx.doi.org/10.1155/2014/ Fu, W., Ji, G., Chen, H., Yang, S., Guo, B., Yang, H., Huang, Z., 2020. Molybde-
398569. num sulphide modified chelating resin for toxic metal adsorption from acid
de Oliveira, H.A.L., Campos, A.F.C., Gomide, G., Zhang, Y., Ghoshal, S., 2020. Elabo- mine wastewater. Sep. Purif. Technol. 251, 117407, http://dx.doi.org/10.1016/j.
ration of a core@shell bimagnetic nanoadsorbent (CoFe2O4@␥-Fe2O3) for the seppur.2020.117407.
removal of As(V) from water. Colloids Surfaces A Physicochem. Eng. Asp., http:// Gadd, G.M., 2000. Bioremedial potential of microbial mechanisms of metal mobi-
dx.doi.org/10.1016/j.colsurfa.2020.125002. lization and immobilization. Curr. Opin. Biotechnol., http://dx.doi.org/10.1016/
Demirbas, A., 2008. Heavy metal adsorption onto agro-based waste materials: a S0958-1669(00)00095-1.
review. J. Hazard. Mater., http://dx.doi.org/10.1016/j.jhazmat.2008.01.024. Galdames, A., Ruiz-Rubio, L., Orueta, M., Sánchez-Arzalluz, M., Vilas-Vilela, J.L., 2020.
Deshpande, B.D., Agrawal, P.S., Yenkie, M.K.N., Dhoble, S.J., 2020. Prospective Zero-valent iron nanoparticles for soil and groundwater remediation. Int. J. Env-
of nanotechnology in degradation of waste water: a new challenges. Nano- iron. Res. Public Health, http://dx.doi.org/10.3390/ijerph17165817.
structures Nano-objects, http://dx.doi.org/10.1016/j.nanoso.2020.100442. Gan, Y.X., Jayatissa, A.H., Yu, Z., Chen, X., Li, M., 2020. Hydrothermal synthesis of
Devars, S., Avilés, C., Cervantes, C., Moreno-Sánchez, R., 2000. Mercury uptake nanomaterials. J. Nanomater., http://dx.doi.org/10.1155/2020/8917013.
and removal by euglena gracilis. Arch. Microbiol., http://dx.doi.org/10.1007/ Gao, S., Shi, Y., Zhang, S., Jiang, K., Yang, S., Li, Z., Takayama-Muromachi, E., 2008.
s002030000193. Biopolymer-assisted green synthesis of iron oxide nanoparticles and their mag-
Dey, S., Podder, S., Roychowdhury, A., Das, D., Kr, C., 2018. Facile synthesis of hierar- netic properties. J. Phys. Chem. C., http://dx.doi.org/10.1021/jp802500a.
chical nickel (III) oxide nanostructure : a synergistic remediating action towards Garcia, N.A., Raiteri, P., Vlieg, E., Gale, J.D., 2018. Water structure, dynamics and ion
water contaminants. J. Environ. Manage. 211, 356–366, http://dx.doi.org/10. adsorption at the aqueous {010} brushite surface. Minerals 8, 1–15, http://dx.
1016/j.jenvman.2018.01.009. doi.org/10.3390/min8080334.
Diab, M.A., Attia, N.F., Attia, A.S., El-Shahat, M.F., 2020. Green synthesis of cost- Gautam, P.K., Singh, A., Misra, K., Sahoo, A.K., Samanta, S.K., 2019. Synthesis and
effective and efficient nanoadsorbents based on zero and two dimensional applications of biogenic nanomaterials in drinking and wastewater treatment.
nanomaterials for Zn2+ and Cr3+ removal from aqueous solutions. Synth. Met., J. Environ. Manage. 231, 734–748, http://dx.doi.org/10.1016/j.jenvman.2018.10.
http://dx.doi.org/10.1016/j.synthmet.2020.116411. 104.
Dickie, W.S., 1929. Calcination. Ind. Eng. Chem., http://dx.doi.org/10.1021/ Geetha, P., Latha, M.S., Pillai, S.S., Koshy, M., 2015. Nanoalginate based biosorbent
ie50233a015. for the removal of lead ions from aqueous solutions: equilibrium and kinetic
Dil, E.A., Ghaedi, M., Asfaram, A., Hajati, S., Mehrabi, F., Goudarzi, A., 2016. Prepa- studies. Ecotoxicol. Environ. Saf. 122, 17–23, http://dx.doi.org/10.1016/j.ecoenv.
ration of nanomaterials for the ultrasound-enhanced removal of Pb2+ ions and 2015.06.032.
malachite green dye: chemometric optimization and modeling. Ultrason. - Sono- George, R., Bahadur, N., Singh, N., Singh, R., Verma, A., Shukla, A.K., 2016. Envi-
chemistry., http://dx.doi.org/10.1016/j.ultsonch.2016.07.001. ronmentally benign TiO2 nanomaterials for removal of heavy metal ions with
Dixit, R., Wasiullah, Malaviya, D., Pandiyan, K., Singh, U.B., Sahu, A., Shukla, R., Singh, interfering ions present in tap water. Mater. Today Proc. 3, 162–166, http://dx.
B.P., Rai, J.P., Sharma, P.K., Lade, H., Paul, D., 2015. Bioremediation of heavy metals doi.org/10.1016/j.matpr.2016.01.051.
from soil and aquatic environment: an overview of principles and criteria of Gerente, C., Lee, V.K.C., Le Cloirec, P., McKay, G., 2007. Application of chitosan
fundamental processes. Sustain, http://dx.doi.org/10.3390/su7022189. for the removal of metals from wastewaters by adsorption - Mechanisms
Do, D.D., 1998. Adsorption analysis: equilibria and kinetics. Chem. Eng. and models review. Crit. Rev. Environ. Sci. Technol., http://dx.doi.org/10.1080/
Dong, L., Zhu, Z., Qiu, Y., Zhao, J., 2010. Removal of lead from aqueous solution 10643380600729089.
by hydroxyapatite/magnetite composite adsorbent. Chem. Eng. J., http://dx.doi. Gharehchopogh, F.S., Shayanfar, H., Gholizadeh, H., 2020. A comprehensive survey
org/10.1016/j.cej.2010.10.027. on symbiotic organisms search algorithms. In: Artificial Intelligence Review.
Dorniani, D., Hussein, M.Z. Bin, Kura, A.U., Fakurazi, S., Shaari, A.H., Ahmad, Z., 2012. Springer, Netherlands, http://dx.doi.org/10.1007/s10462-019-09733-4.
Preparation of Fe3O4 magnetic nanoparticles coated with gallic acid for drug Ghasemzadeh, G., Momenpour, M., Omidi, F., Hosseini, M.R., Ahani, M., Barzegari,
delivery. Int. J. Nanomedicine, http://dx.doi.org/10.2147/IJN.S35746. A., 2014. Applications of nanomaterials in water treatment and environmental
Du, Z., Chen, H., Guo, X., Qin, L., Lin, D., Huo, L., Yao, Y., Zhang, Z., 2021. Mecha- remediation. Front. Environ. Sci. Eng. China, http://dx.doi.org/10.1007/s11783-
nism and industrial application feasibility analysis on microwave-assisted rapid 014-0654-0.
350
Ghorbani, M., Seyedin, O., Aghamohammadhassan, M., 2020. Adsorptive removal of Hussein, A.M., 2016. Adaptive Neuro-Fuzzy Inference System of friction factor and
lead (II) ion from water and wastewater media using carbon-based nanomateri- heat transfer nanofluid turbulent flow in a heated tube. Case Stud. Therm. Eng.
als as unique sorbents: a review. J. Environ. Manage., http://dx.doi.org/10.1016/ 8, 94–104, http://dx.doi.org/10.1016/j.csite.2016.06.001.
j.jenvman.2019.109814. Hutton-Ashkenny, M., Ibana, D., Barnard, K.R., 2015. Reagent selection for recovery
Gollavelli, G., Chang, C.C., Ling, Y.C., 2013. Facile synthesis of smart magnetic of nickel and cobalt from nitric acid nickel laterite leach solutions by solvent
graphene for safe drinking water: heavy metal removal and disinfection control. extraction. Miner. Eng., http://dx.doi.org/10.1016/j.mineng.2015.02.010.
ACS Sustain. Chem. Eng. 1, 462–472, http://dx.doi.org/10.1021/sc300112z. Ihsanullah, I., Sajid, M., Kabeer, M., Shemsi, A.M., Atieh, M.A., 2020. First investiga-
Gómez-Pastora, J., Bringas, E., Ortiz, I., 2014. Recent progress and future challenges tions on the removal of tungsten species from water using multi-walled carbon
on the use of high performance magnetic nano-adsorbents in environmental nanotubes. Water Air Soil Pollut. 231, http://dx.doi.org/10.1007/s11270-020-
applications. Chem. Eng. J. 256, 187–204, http://dx.doi.org/10.1016/j.cej.2014. 04485-2.
06.119. Izanloo, M., Esrafili, A., Jafari, A.J., Farzadkia, M., Behbahani, M., Sobhi, H.R.,
Gopalakrishnan, A., Krishnan, R., Thangavel, S., Venugopal, G., Kim, S.J., 2015. 2019. Application of a novel bi-functional nanoadsorbent for the simultaneous
Removal of heavy metal ions from pharma-effluents using graphene-oxide removal of inorganic and organic compounds: equilibrium, kinetic and thermo-
nanosorbents and study of their adsorption kinetics. J. Ind. Eng. Chem. 30, 14–19, dynamic studies. J. Mol. Liq., http://dx.doi.org/10.1016/j.molliq.2018.10.013.
http://dx.doi.org/10.1016/j.jiec.2015.06.005. Jakubov, T.S., Mainwaring, D.E., 2002. Modified Dubinin-Radushkevich/Dubinin-
Grozdanov, A., Atkovska, K., Lisickov, K., 2018. Removal of Heavy Metal Ions from Astakhov adsorption equations. J. Colloid Interface Sci., http://dx.doi.org/10.
Wastewater Using Bio- and Nanosorbents., http://dx.doi.org/10.1007/978-3- 1006/jcis.2002.8498.
319-71279-6. Jang, J.S.R., 1993. ANFIS: adaptive-network-Based fuzzy inference system. IEEE
Gu, P., Xing, J., Wen, T., Zhang, R., Wang, J., Zhao, G., Hayat, T., Ai, Y., Lin, Z., Wang, X., Trans. Syst. Man Cybern. 23, 665–685, http://dx.doi.org/10.1109/21.256541.
2018. Experimental and theoretical calculation investigation on efficient Pb(ii) Jegadeesan, G., Al-Abed, S.R., Sundaram, V., Choi, H., Scheckel, K.G., Dionysiou, D.D.,
adsorption on etched Ti3AlC2 nanofibers and nanosheets. Environ. Sci. Nano 5, 2010. Arsenic sorption on TiO2 nanoparticles: size and crystallinity effects.
946–955, http://dx.doi.org/10.1039/c8en00029h. Water Res., http://dx.doi.org/10.1016/j.watres.2009.10.047.
Guerra, F.D., Attia, M.F., Whitehead, D.C., Alexis, F., 2018. Nanotechnology for envi- Ji, L., Zhou, L., Bai, X., Shao, Y., Zhao, G., Qu, Y., Wang, C., Li, Y., 2012. Facile synthesis
ronmental remediation: materials and applications. Molecules, http://dx.doi. of multiwall carbon nanotubes/iron oxides for removal of tetrabromobisphenol
org/10.3390/molecules23071760. A and Pb(ii). J. Mater. Chem., http://dx.doi.org/10.1039/c2jm32896h.
Gunti, S., Kumar, A., Ram, M.K., 2018. Nanostructured photocatalysis in the visible Ji, S., Miao, C., Liu, H., Feng, L., Yang, X., Guo, H., 2018. A hydrothermal synthesis of
spectrum for the decontamination of air and water. Int. Mater. Rev., http://dx. Fe3O4@C hybrid nanoparticle and magnetic adsorptive performance to remove
doi.org/10.1080/09506608.2017.1379264. heavy metal ions in aqueous solution. Nanoscale Res. Lett. 13, http://dx.doi.org/
Gupta, M., Sharma, V., Shrivastava, J., Solanki, A., Singh, A.P., Satsangi, V.R., Dass, 10.1186/s11671-018-2580-8.
S., Shrivastav, R., 2009. Preparation and characterization of nanostructured ZnO Jiang, Li-ping, Shi, H., Chai, F., 2018a. An Effective One-pot Method for Preparing
thin films for photoelectrochemical splitting of water. Bull. Mater. Sci., http:// Covalently Bonded Nanocomposite Soft Magnetic Beadlike Microgels and Their
dx.doi.org/10.1007/s12034-009-0004-1. Evaluation As an Adsorbent for the Removal of Toxic Heavy Metals From Aque-
Hadadian, M., Goharshadi, E.K., Fard, M.M., Ahmadzadeh, H., 2018. Synergistic effect ous Solution †., pp. 19785–19794, http://dx.doi.org/10.1039/c8nj04101f.
of graphene nanosheets and zinc oxide nanoparticles for effective adsorption Jiang, Liying, Ye, Q., Chen, J., Chen, Z., Gu, Y., 2018b. Preparation of magnetically
of Ni (II) ions from aqueous solutions. Appl. Phys. A Mater. Sci. Process. 124, 0, recoverable bentonite–Fe3O4–MnO2 composite particles for Cd(II) removal
http://dx.doi.org/10.1007/s00339-018-1664-8. from aqueous solutions. J. Colloid Interface Sci., http://dx.doi.org/10.1016/j.jcis.
Hamdy, A., Mostafa, M.K., Nasr, M., 2019. Techno-economic estimation of elec- 2017.11.063.
troplating wastewater treatment using zero-valent iron nanoparticles: batch Jiao, X., Gutha, Y., Zhang, W., 2017. Application of chitosan/poly(vinyl alcohol)/CuO
optimization, continuous feed, and scaling up studies. Environ. Sci. Pollut. Res. (CS/PVA/CuO) beads as an adsorbent material for the removal of Pb(II) from
26, 25372–25385, http://dx.doi.org/10.1007/s11356-019-05850-3. aqueous environment. Colloids Surf. B Biointerfaces, http://dx.doi.org/10.1016/
Hamidian, A.H., Esfandeh, S., Zhang, Y., Yang, M., 2019. Simulation and optimization j.colsurfb.2016.10.024.
of nanomaterials application for heavy metal removal from aqueous solutions. Jorfi, S., Shooshtarian, M.R., Pourfadakari, S., 2020. Decontamination of cadmium
Inorg. Nano-Metal Chem. 0, 1–14, http://dx.doi.org/10.1080/24701556.2019. from aqueous solutions using zeolite decorated by Fe3O4 nanoparticles: adsorp-
1653321. tion modeling and thermodynamic studies. Int. J. Environ. Sci. Technol. (Tehran),
Han, Q., Chen, L., Li, W., Zhou, Z., Fang, Z., Xu, Z., Qian, X., 2018. Self-assembled http://dx.doi.org/10.1007/s13762-019-02350-2.
three-dimensional double network graphene oxide/polyacrylic acid hybrid Journal, O.A., 2020. Biointerface Research in Applied Chemistry 10, 5556–5563.
aerogel for removal of Cu2+ from aqueous solution. Environ. Sci. Pollut. Res. Jung, K.W., Lee, S.Y., Choi, J.W., Lee, Y.J., 2019. A facile one-pot hydrothermal syn-
25, 34438–34447, http://dx.doi.org/10.1007/s11356-018-3409-9. thesis of hydroxyapatite/biochar nanocomposites: adsorption behavior and
He, J., Wei, M., Li, B., Kang, Y., Evans, D.G., Duan, X., 2005. Preparation of layered mechanisms for the removal of copper(II) from aqueous media. Chem. Eng. J.
double hydroxides. Struct. Bond., http://dx.doi.org/10.1007/430 006. 369, 529–541, http://dx.doi.org/10.1016/j.cej.2019.03.102.
He, Y., Luo, L., Liang, S., Long, M., Xu, H., 2018. Synthesis of mesoporous silica-calcium Kalantari, K., Ahmad, M.Bin, Shameli, K., Khandanlou, R., 2015a. Size-controlled syn-
phosphate hybrid nanoparticles and their potential as efficient adsorbent for thesis of Fe3O4 magnetite nanoparticles on the exterior of talc layers. Res. Chem.
cadmium ions removal from aqueous solution. J. Colloid Interface Sci. 525, Intermed., http://dx.doi.org/10.1007/s11164-013-1336-4.
126–135, http://dx.doi.org/10.1016/j.jcis.2018.04.037. Kalantari, K., Ahmad, M.B., Fard Masoumi, H.R., Shameli, K., Basri, M., Khan-
He, F., Zhao, D., 2005. Preparation and characterization of a new class of starch- danlou, R., 2015b. Rapid and high capacity adsorption of heavy metals by
stabilized bimetallic nanoparticles for degradation of chlorinated hydrocarbons Fe3O4/montmorillonite nanocomposite using response surface methodology:
in water. Environ. Sci. Technol., http://dx.doi.org/10.1021/es048743y. preparation, characterization, optimization, equilibrium isotherms, and adsorp-
Herrera-Becerra, R., Rius, J.L., Zorrilla, C., 2010. Tannin biosynthesis of iron oxide tion kinetics study. J. Taiwan Inst. Chem. Eng., http://dx.doi.org/10.1016/j.jtice.
nanoparticles. Appl. Phys. A Mater. Sci. Process., http://dx.doi.org/10.1007/ 2014.10.025.
s00339-010-5903-x. Kalia, S., Kango, S., Kumar, A., Haldorai, Y., Kumari, B., Kumar, R., 2014. Magnetic
Hiew, B.Y.Z., Lee, L.Y., Lee, X.J., Thangalazhy-Gopakumar, S., Gan, S., Lim, S.S., Pan, G.T., polymer nanocomposites for environmental and biomedical applications. Col-
Yang, T.C.K., Chiu, W.S., Khiew, P.S., 2018. Review on synthesis of 3D graphene- loid Polym. Sci. 292, 2025–2052, http://dx.doi.org/10.1007/s00396-014-3357-
based configurations and their adsorption performance for hazardous water y.
pollutants. Process Saf. Environ. Prot. 116, 262–286, http://dx.doi.org/10.1016/ Karoyo, A.H., Wilson, L.D., 2015. Nano-Sized cyclodextrin-based molecularly
j.psep.2018.02.010. imprinted polymer adsorbents for perfluorinated compounds—a mini-review.
Hlongwane, G.N., Sekoai, P.T., Meyyappan, M., Moothi, K., 2019. Simultaneous Nanomaterials, http://dx.doi.org/10.3390/nano5020981.
removal of pollutants from water using nanoparticles: a shift from single pollu- Kenawy, I.M.M., Abou El-Reash, Y.G., Hassanien, M.M., Alnagar, N.R., Mortada,
tant control to multiple pollutant control. Sci. Total Environ., http://dx.doi.org/ W.I., 2018. Use of microwave irradiation for modification of mesoporous sil-
10.1016/j.scitotenv.2018.11.257. ica nanoparticles by thioglycolic acid for removal of cadmium and mercury.
Huang, Z.M., Zhang, Y.Z., Kotaki, M., Ramakrishna, S., 2003. A review on polymer Microporous Mesoporous Mater., http://dx.doi.org/10.1016/j.micromeso.2017.
nanofibers by electrospinning and their applications in nanocomposites. Com- 09.021.
pos. Sci. Technol., http://dx.doi.org/10.1016/S0266-3538(03)00178-7. Khaligh, N.G., Johan, M.R., 2018. Recent application of the various nanomaterials and
Huang, D., Yan, X., Yan, M., Zeng, G., Zhou, C., Wan, J., Cheng, M., Xue, W., nanocatalysts for the heavy metals’ removal from wastewater. Nano, http://dx.
2018a. Graphitic carbon nitride-based heterojunction photoactive nanocom- doi.org/10.1142/S1793292018300062.
posites: applications and mechanism insight. ACS Appl. Mater. Interfaces 10, Khan, N.A., Khan, S.U., Ahmed, S., Farooqi, I.H., Dhingra, A., Hussain, A., Changani,
21035–21055, http://dx.doi.org/10.1021/acsami.8b03620. F., 2019. Applications of nanotechnology in water and wastewater treatment:
Huang, Q., Chen, Y., Yu, H., Yan, L., Zhang, J., Wang, B., Du, B., Xing, L., 2018b. a review. Asian J. Water, Environ. Pollut. 16, 81–86, http://dx.doi.org/10.3233/
Magnetic graphene oxide/MgAl-layered double hydroxide nanocomposite: one- AJW190051.
pot solvothermal synthesis, adsorption performance and mechanisms for Pb2+, Khin, M.M., Nair, A.S., Babu, V.J., Murugan, R., Ramakrishna, S., 2012. A review on
Cd2+, and Cu2+. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2018.01.156. nanomaterials for environmental remediation. Energy Environ. Sci., http://dx.
Huang, D., Xu, B., Wu, J., Brookes, P.C., Xu, J., 2019. Adsorption and desorption of doi.org/10.1039/c2ee21818f.
phenanthrene by magnetic graphene nanomaterials from water: roles of pH, Klemm, D., Kramer, F., Moritz, S., Lindström, T., Ankerfors, M., Gray, D., Dorris, A.,
heavy metal ions and natural organic matter. Chem. Eng. J. 368, 390–399, http:// 2011. Nanocelluloses: a new family of nature-based materials. Angew. Chemie
dx.doi.org/10.1016/j.cej.2019.02.152. - Int. Ed., http://dx.doi.org/10.1002/anie.201001273.
351
Krause, R.W., Mamba, B.B., Bambo, F.M., Malefetse, T.J., 2010. Cyclodextrin polymers: Liu, G., Wang, K., Hoivik, N., Jakobsen, H., 2012a. Progress on free-standing and flow-
synthesis and application in water treatment. Cyclodextrins Chem. Phys. through TiO 2 nanotube membranes. Sol. Energy Mater. Sol. Cells, http://dx.doi.
Krishna Kumar, A.S., Jiang, S.J., Warchoł, J.K., 2017. Synthesis and characterization org/10.1016/j.solmat.2011.11.004.
of two-dimensional transition metal dichalcogenide magnetic MoS2@Fe3O4 Liu, Z., Yang, H., Zhang, H., Huang, C., Li, L., 2012b. Oil-field wastewater purifica-
nanoparticles for adsorption of Cr(VI)/Cr(III). ACS Omega 2, 6187–6200, http:// tion by magnetic separation technique using a novel magnetic nanoparticle. in:
dx.doi.org/10.1021/acsomega.7b00757. Cryogenics., http://dx.doi.org/10.1016/j.cryogenics.2012.05.015.
Kulkarni, S., Kaware, J., 2014. Regeneration and recovery in adsorption- a review. Liu, P., Sehaqui, H., Tingaut, P., Wichser, A., Oksman, K., Mathew, A.P., 2014a. Cel-
Int. J. Innov. Sci. Eng. Technol. lulose and chitin nanomaterials for capturing silver ions (Ag+) from water via
Kumar Reddy, K.S., Al Shoaibi, A., Srinivasakannan, C., 2015. Sulfur-leaching facts surface adsorption. Cellulose 21, 449–461, http://dx.doi.org/10.1007/s10570-
from sulfur-impregnated porous carbons in the mercury removal process. 013-0139-5.
Energy Fuels, http://dx.doi.org/10.1021/acs.energyfuels.5b00995. Liu, X., Yan, L., Yin, W., Zhou, L., Tian, G., Shi, J., Yang, Z., Xiao, D., Gu, Z., Zhao, Y., 2014b.
Kumar Reddy, K.S., Prabhu, A., Al Shoaibi, A., Srinivasakannan, C., 2016. Application of A magnetic graphene hybrid functionalized with beta-cyclodextrins for fast and
sulfonated carbons for mercury removal in gas processing. Energy Fuels, http:// efficient removal of organic dyes. J. Mater. Chem. A Mater. Energy Sustain., http://
dx.doi.org/10.1021/acs.energyfuels.5b02630. dx.doi.org/10.1039/c4ta00753k.
Kumari, P., Singh, P., Singhal, A., Alka, 2020. Cyclodextrin-based nanostructured Liu, P., Borrell, P.F., Božič, M., Kokol, V., Oksman, K., Mathew, A.P., 2015. Nanocellu-
materials for sustainable water remediation applications. Environ. Sci. Pollut. loses and their phosphorylated derivatives for selective adsorption of Ag+, Cu2+
Res., http://dx.doi.org/10.1007/s11356-020-09519-0. and Fe3+ from industrial effluents. J. Hazard. Mater. 294, 177–185, http://dx.doi.
Kyzas, G.Z., Matis, K.A., 2015. Nanoadsorbents for pollutants removal: A review. J. org/10.1016/j.jhazmat.2015.04.001.
Mol. Liq. 203, 159–168, http://dx.doi.org/10.1016/j.molliq.2015.01.004. Liu, R., Zhou, J., Gao, X., Li, J., Xie, Z., Li, Z., Zhang, S., 1700122 2017a. Graphdiyne
Kyzas, G.Z., Lazaridis, N.K., Kostoglou, M., 2014. Adsorption/desorption of a dye by a Filter for Decontaminating Lead-Ion-Polluted Water., pp. 1–6, http://dx.doi.org/
chitosan derivative: experiments and phenomenological modeling. Chem. Eng. 10.1002/aelm.201700122.
J., http://dx.doi.org/10.1016/j.cej.2014.03.063. Liu, Y., Wang, X., Wu, H., 2017b. Biosensors and Bioelectronics Reusable DNA-
Lal, S., Singhal, A., Kumari, P., 2020. Exploring carbonaceous nanomaterials for functionalized-graphene for ultrasensitive mercury (II) detection and removal.
arsenic and chromium removal from wastewater. J. Water Process Eng., http:// Biosens. Bioelectron. 87, 129–135, http://dx.doi.org/10.1016/j.bios.2016.07.059.
dx.doi.org/10.1016/j.jwpe.2020.101276. Liu, X., Ma, R., Wang, Xiangxue, Ma, Y., Yang, Y., Zhuang, L., Zhang, S., Jehan, R., Chen,
Lam, C.W., James, J.T., McCluskey, R., Arepalli, S., Hunter, R.L., 2006. A review J., Wang, Xiangke, 2019. Graphene oxide-based materials for efficient removal
of carbon nanotube toxicity and assessment of potential occupational and of heavy metal ions from aqueous solution: a review. Environ. Pollut., http://dx.
environmental health risks. Crit. Rev. Toxicol., http://dx.doi.org/10.1080/ doi.org/10.1016/j.envpol.2019.05.050.
10408440600570233. Liu, J., He, S.H., Wang, J.P., 2020. High-yield gas-phase condensation synthesis of
Lam, S.M., Sin, J.C., Abdullah, A.Z., Mohamed, A.R., 2012. Degradation of wastewaters nanoparticles to enable a wide array of applications. ACS Appl. Nano Mater. 3,
containing organic dyes photocatalysed by zinc oxide: a review. Desalin. Water 7942–7949, http://dx.doi.org/10.1021/acsanm.0c01400.
Treat., http://dx.doi.org/10.1080/19443994.2012.664698. Lu, F., Astruc, D., 2018. Nanomaterials for removal of toxic elements from water.
Lasheen, M.R., El-Sherif, I.Y., Sabry, D.Y., El-Wakeel, S.T., El-Shahat, M.F., 2016. Coord. Chem. Rev. 356, 147–164, http://dx.doi.org/10.1016/j.ccr.2017.11.003.
Adsorption of heavy metals from aqueous solution by magnetite nanopar- Lu, A.H., Salabas, E.L., Schüth, F., 2007. Magnetic nanoparticles: synthesis, protection,
ticles and magnetite-kaolinite nanocomposite: equilibrium, isotherm and functionalization, and application. Angew. Chemie - Int. Ed., http://dx.doi.org/
kinetic study. Desalin. Water Treat., http://dx.doi.org/10.1080/19443994.2015. 10.1002/anie.200602866.
1085446. Lu, W., Shen, Y., Xie, A., Zhang, W., 2010. Green synthesis and characterization of
Lata, S., Samadder, S.R., 2016. Removal of arsenic from water using nano adsorbents superparamagnetic Fe3O4 nanoparticles. J. Magn. Magn. Mater., http://dx.doi.
and challenges: a review. J. Environ. Manage. 166, 387–406, http://dx.doi.org/ org/10.1016/j.jmmm.2009.12.035.
10.1016/j.jenvman.2015.10.039. Lv, X., Xue, X., Jiang, G., Wu, D., Sheng, T., Zhou, H., Xu, X., 2014. Nanoscale Zero-Valent
Lata, S., Singh, P.K., Samadder, S.R., 2015. Regeneration of adsorbents and recovery Iron (nZVI) assembled on magnetic Fe3O4/graphene for Chromium (VI) removal
of heavy metals: a review. Int. J. Environ. Sci. Technol. (Tehran), http://dx.doi. from aqueous solution. J. Colloid Interface Sci., http://dx.doi.org/10.1016/j.jcis.
org/10.1007/s13762-014-0714-9. 2013.11.044.
Lee, C.R., Kim, H.S., Jang, I.H., Im, J.H., Park, N.G., 2011. Pseudo first-order adsorption Ma, J., Ma, Y., Yu, F., Dai, X., 2018. Rotating magnetic field-assisted adsorption
kinetics of N719 dye on TiO2 surface. ACS Appl. Mater. Interfaces, http://dx.doi. mechanism of pollutants on mechanically strong sodium Alginate/Graphene/
org/10.1021/am2001696. l -Cysteine beads in batch and fixed-bed column systems. Environ. Sci. Technol.,
Lee, K.M., Lai, C.W., Ngai, K.S., Juan, J.C., 2016. Recent developments of zinc oxide http://dx.doi.org/10.1021/acs.est.8b05409.
based photocatalyst in water treatment technology: a review. Water Res., http:// Machida, M., Fotoohi, B., Amamo, Y., Ohba, T., Kanoh, H., Mercier, L., 2012. Cad-
dx.doi.org/10.1016/j.watres.2015.09.045. mium(II) adsorption using functional mesoporous silica and activated carbon. J.
Lei, C., Wang, C., Chen, W., He, M., Huang, B., 2020. Polyaniline@magnetic chitosan Hazard. Mater., http://dx.doi.org/10.1016/j.jhazmat.2012.04.039.
nanomaterials for highly efficient simultaneous adsorption and in-situ chemical Mahfoudhi, N., Boufi, S., 2017. Nanocellulose as a novel nanostructured adsorbent
reduction of hexavalent chromium: removal efficacy and mechanisms. Sci. Total for environmental remediation: a review. Cellulose 24, 1171–1197, http://dx.
Environ., http://dx.doi.org/10.1016/j.scitotenv.2020.139316. doi.org/10.1007/s10570-017-1194-0.
Leudjo Taka, A., Klink, M.J., Yangkou Mbianda, X., Naidoo, E.B., 2020. Chitosan Mahmoud, M.E., Saleh, M.M., Zaki, M.M., Nabil, G.M., 2020. A sustainable nanocom-
nanocomposites for water treatment by fixed-bed continuous flow column posite for removal of heavy metals from water based on crosslinked sodium
adsorption: a review. Carbohydr. Polym., http://dx.doi.org/10.1016/j.carbpol. alginate with iron oxide waste material from steel industry. J. Environ. Chem.
2020.117398. Eng. 8, 104015, http://dx.doi.org/10.1016/j.jece.2020.104015.
Li, F., Duan, X., 2005. Applications of layered double hydroxides. Struct. Bond., http:// Maiti, M., Sarkar, M., Malik, M.A., Xu, S., Li, Q., Mandal, S., 2018. Iron oxide nps facili-
dx.doi.org/10.1007/430 007. tated a smart building composite for heavy-metal removal and dye degradation.
Li, X.Q., Elliott, D.W., Zhang, W.X., 2006. Zero-valent iron nanoparticles for abate- ACS Omega 3, 1081–1089, http://dx.doi.org/10.1021/acsomega.7b01545.
ment of environmental pollutants: materials and engineering aspects. Crit. Rev. Malathi, A., Arunachalam, P., Madhavan, J., Al-Mayouf, A.M., Ghanem, M.A., 2018.
Solid State Mater. Sci., http://dx.doi.org/10.1080/10408430601057611. Rod-on-flake ␣-FeOOH/BiOI nanocomposite: facile synthesis, characterization
Li, L., Fan, L., Duan, H., Wang, X., Luo, C., 2014. Magnetically separable functionalized and enhanced photocatalytic performance. Colloids Surfaces A Physicochem.
graphene oxide decorated with magnetic cyclodextrin as an excellent adsorbent Eng. Asp., http://dx.doi.org/10.1016/j.colsurfa.2017.10.036.
for dye removal. RSC Adv., http://dx.doi.org/10.1039/c4ra06292b. Mani, D., Kumar, C., 2014. Biotechnological advances in bioremediation of heavy
Li, H., Liu, H., Zhang, J., Cheng, Y., Zhang, C., Fei, X., Xian, Y., 2017a. Platinum nanoparti- metals contaminated ecosystems: an overview with special reference to phy-
cle encapsulated metal-organic frameworks for colorimetric measurement and toremediation. Int. J. Environ. Sci. Technol. (Tehran), http://dx.doi.org/10.1007/
facile removal of mercury(II). ACS Appl. Mater. Interfaces, http://dx.doi.org/10. s13762-013-0299-8.
1021/acsami.7b13695. Mansur, A.A.P., Mansur, H.S., Ramanery, F.P., Oliveira, L.C., Souza, P.P., 2014. “Green”
Li, S., Wang, W., Liang, F., Zhang, W.X., 2017b. Heavy metal removal using nanoscale colloidal ZnS quantum dots/chitosan nano-photocatalysts for advanced oxida-
zero-valent iron (nZVI): theory and application. J. Hazard. Mater. 322, 163–171, tion processes: study of the photodegradation of organic dye pollutants. Appl.
http://dx.doi.org/10.1016/j.jhazmat.2016.01.032. Catal. B Environ., http://dx.doi.org/10.1016/j.apcatb.2014.04.026.
Li, G., Zhao, P., Zheng, H., Yang, L., Lu, S., Peng, P., 2018. Research on the removal Martinson, C.A., Reddy, K.J., 2009. Adsorption of arsenic(III) and arsenic(V) by
mechanism of antimony on A-MnO 2 nanorod in aqueous solution: DFT + U cupric oxide nanoparticles. J. Colloid Interface Sci., http://dx.doi.org/10.1016/
method. J. Hazard. Mater. 354, 8–16, http://dx.doi.org/10.1016/j.jhazmat.2018. j.jcis.2009.04.075.
04.055. Mauter, M.S., Elimelech, M., 2008. Environmental applications of carbon-based
Lidström, P., Tierney, J., Wathey, B., Westman, J., 2001. Microwave assisted nanomaterials. Environ. Sci. Technol., http://dx.doi.org/10.1021/es8006904.
organic synthesis - A review. Tetrahedron., http://dx.doi.org/10.1016/S0040- Meouche, W., Branger, C., Beurroies, I., Denoyel, R., Margaillan, A., 2012. Inverse
4020(01)00906-1. suspension polymerization as a new tool for the synthesis of ion-imprinted poly-
Lingamdinne, L.P., Koduru, J.R., Choi, Y.L., Chang, Y.Y., Yang, J.K., 2016. Studies on mers. Macromol. Rapid Commun., http://dx.doi.org/10.1002/marc.201200039.
removal of Pb(II) and Cr(III) using graphene oxide based inverse spinel nickel fer- Milonjić, S.K., 2007. A consideration of the correct calculation of thermodynamic
rite nano-composite as sorbent. Hydrometallurgy., http://dx.doi.org/10.1016/j. parameters of adsorption. J. Serbian Chem. Soc. 72, 1363–1367, http://dx.doi.
hydromet.2015.11.005. org/10.2298/JSC0712363M.
Linghu, W., Yang, H., Sun, Y., Sheng, G., Huang, Y., 2017. One-pot synthesis of LDH/GO Mittal, A.K., Chisti, Y., Banerjee, U.C., 2013. Synthesis of metallic nanoparticles using
composites as highly effective adsorbents for decontamination of U(VI). ACS plant extracts. Biotechnol. Adv., http://dx.doi.org/10.1016/j.biotechadv.2013.01.
Sustain. Chem. Eng., http://dx.doi.org/10.1021/acssuschemeng.7b01303. 003.
352
Mondal, P., Anweshan, A., Purkait, M.K., 2020. Green synthesis and environmental on the total environment: an overview. Environ. Monit. Assess., http://dx.doi.
application of iron-based nanomaterials and nanocomposite: a review. Chemo- org/10.1007/s10661-019-7528-7.
sphere 259, 127509, http://dx.doi.org/10.1016/j.chemosphere.2020.127509. Ram, B., Chauhan, G.S., 2018. New spherical nanocellulose and thiol-based adsorbent
Monthioux, M., Serp, P., Caussat, B., Flahaut, E., Razafinimanana, M., Valensi, F., for rapid and selective removal of mercuric ions. Chem. Eng. J., http://dx.doi.org/
Laurent, C., Peigney, A., Mesguich, D., Weibel, A., Bacsa, W., Broto, J.M., 2017. 10.1016/j.cej.2017.08.128.
Carbon nanotubes. in: Springer Handbooks., http://dx.doi.org/10.1007/978-3- Rashid, K., Suresh Kumar Reddy, K., Shoaibi, A.Al, Srinivasakannan, C., 2013. Sulfur-
662-54357-3 8. impregnated porous carbon for removal of mercuric chloride: optimization
Nadagouda, M.N., Varma, R.S., 2007. A greener synthesis of core (Fe, Cu)-shell (Au, using RSM. Clean Technol. Environ. Policy., http://dx.doi.org/10.1007/s10098-
Pt, Pd, and Ag) nanocrystals using aqueous vitamin C. Cryst. Growth Des., http:// 012-0564-4.
dx.doi.org/10.1021/cg070554e. Razzaz, A., Ghorban, S., Hosayni, L., Irani, M., Aliabadi, M., 2016. Chitosan nanofibers
Nasirimoghaddam, S., Zeinali, S., Sabbaghi, S., 2015. Chitosan coated magnetic functionalized by TiO2 nanoparticles for the removal of heavy metal ions. J.
nanoparticles as nano-adsorbent for efficient removal of mercury contents from Taiwan Inst. Chem. Eng., http://dx.doi.org/10.1016/j.jtice.2015.06.003.
industrial aqueous and oily samples. J. Ind. Eng. Chem., http://dx.doi.org/10. Reddy, D.H.K., Yun, Y.S., 2016. Spinel ferrite magnetic adsorbents: alternative future
1016/j.jiec.2014.12.020. materials for water purification? Coord. Chem. Rev., http://dx.doi.org/10.1016/
Naushad, M., Ahamad, T., Sharma, G., Al-Muhtaseb, A.H., Albadarin, A.B., Alam, M.M., j.ccr.2016.01.012.
ALOthman, Z.A., Alshehri, S.M., Ghfar, A.A., 2016. Synthesis and characterization Reddy, K.S.K., Shoaibi, A.Al, Srinivasakannan, C., 2018. Mercury removal using metal
of a new starch/SnO2 nanocomposite for efficient adsorption of toxic Hg2+ metal sulfide porous carbon complex. Process Saf. Environ. Prot., http://dx.doi.org/10.
ion. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2016.04.084. 1016/j.psep.2017.12.022.
Neeli, S.T., Ramsurn, H., Ng, C.Y., Wang, Y., Lu, J., 2020. Removal of Cr (VI), As (V), Cu Renu, Agarwal, M., Singh, K., 2017. Heavy metal removal from wastewater using
(II), and Pb (II) using cellulose biochar supported iron nanoparticles: a kinetic various adsorbents: a review. J. Water Reuse Desalin., http://dx.doi.org/10.2166/
and mechanistic study. J. Environ. Chem. Eng. 8, 103886, http://dx.doi.org/10. wrd.2016.104.
1016/j.jece.2020.103886. Romero-González, J., Peralta-Videa, J.R., Rodriíguez, E., Ramirez, S.L., Gardea-
Nguyen, C., Do, D.D., 2001. The Dubinin-Radushkevich equation and the underlying Torresdey, J.L., 2005. Determination of thermodynamic parameters of Cr(VI)
microscopic adsorption description. Carbon, http://dx.doi.org/10.1016/S0008- adsorption from aqueous solution onto Agave lechuguilla biomass. J. Chem.
6223(00)00265-7. Thermodyn. 37, 343–347, http://dx.doi.org/10.1016/j.jct.2004.09.013.
Nizamuddin, S., Siddiqui, M.T.H., Mubarak, N.M., Baloch, H.A., Abdullah, E.C., Mazari, Sadegh, H., Ali, G.A.M., Gupta, V.K., Makhlouf, A.S.H., Shahryari-ghoshekandi, R.,
S.A., Griffin, G.J., Srinivasan, M.P., Tanksale, A., 2018. Iron Oxide Nanomaterials Nadagouda, M.N., Sillanpää, M., Megiel, E., 2017. The role of nanomaterials as
for the Removal of Heavy Metals and Dyes From Wastewater, Nanoscale Mate- effective adsorbents and their applications in wastewater treatment. J. Nano-
rials in Water Purification. Elsevier Inc, http://dx.doi.org/10.1016/B978-0-12- structure Chem., http://dx.doi.org/10.1007/s40097-017-0219-4.
813926-4.00023-9. Sadeghi, M.H., Tofighy, M.A., Mohammadi, T., 2020. One-dimensional graphene for
Özlem Kocabaş-Atakli, Z., Yürüm, Y., 2013. Synthesis and characterization of anatase efficient aqueous heavy metal adsorption: rapid removal of arsenic and mercury
nanoadsorbent and application in removal of lead, copper and arsenic from ions by graphene oxide nanoribbons (GONRs). Chemosphere 253, http://dx.doi.
water. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2013.03.106. org/10.1016/j.chemosphere.2020.126647.
Pareek, V., Bhargava, A., Gupta, R., Jain, N., Panwar, J., 2017. Synthesis and applica- Saha, S., Sarkar, P., 2012. Arsenic remediation from drinking water by synthesized
tions of noble metal nanoparticles: a review. Adv. Sci. Eng. Med. 9, 527–544, nano-alumina dispersed in chitosan-grafted polyacrylamide. J. Hazard. Mater.,
http://dx.doi.org/10.1166/asem.2017.2027. http://dx.doi.org/10.1016/j.jhazmat.2012.05.001.
Park, W.K., Yoon, Y., Kim, S., Yoo, S., Do, Y., Kang, J.W., Yoon, D.H., Yang, W.S., 2016. Saha, S., Zubair, M., Khosa, M.A., Song, S., Ullah, A., 2019. Keratin and chitosan biosor-
Feasible water flow filter with facilely functionalized Fe3O4-non-oxidative bents for wastewater treatment: a review. J. Polym. Environ. 27, 1389–1403,
graphene/CNT composites for arsenic removal. J. Environ. Chem. Eng. 4, http://dx.doi.org/10.1007/s10924-019-01439-6.
3246–3252, http://dx.doi.org/10.1016/j.jece.2016.06.028. Saharan, P., Chaudhary, G.R., Mehta, S.K., Umar, A., 2014. Removal of water contami-
Park, C.M., Kim, Y.M., Kim, K.H., Wang, D., Su, C., Yoon, Y., 2019. Potential utility of nants by Iron oxide nanomaterials. J. Nanosci. Nanotechnol. 14, 627–643, http://
graphene-based nano spinel ferrites as adsorbent and photocatalyst for remov- dx.doi.org/10.1166/jnn.2014.9053.
ing organic/inorganic contaminants from aqueous solutions: a mini review. Saif, S., Tahir, A., Chen, Y., 2016. Green synthesis of iron nanoparticles and their
Chemosphere., http://dx.doi.org/10.1016/j.chemosphere.2019.01.063. environmental applications and implications. Nanomaterials., http://dx.doi.org/
Parsons, J.G., Lopez, M.L., Peralta-Videa, J.R., Gardea-Torresdey, J.L., 2009. Deter- 10.3390/nano6110209.
mination of arsenic(III) and arsenic(V) binding to microwave assisted Saini, J., Garg, V.K., Gupta, R.K., 2020. Green synthesized SiO2@OPW nanocomposites
hydrothermal synthetically prepared Fe3O4, Mn3O4, and MnFe2O4 nanoadsor- for enhanced Lead (II) removal from water. Arab. J. Chem. 13, 2496–2507, http://
bents. Microchem. J., http://dx.doi.org/10.1016/j.microc.2008.08.012. dx.doi.org/10.1016/j.arabjc.2018.06.003.
Patel, H., 2019. Fixed-bed column adsorption study: a comprehensive review. Appl. Sakakibara, M., Ohmori, Y., Ha, N.T.H., Sano, S., Sera, K., 2011. Phytoremediation of
Water Sci., http://dx.doi.org/10.1007/s13201-019-0927-7. heavy metal-contaminated water and sediment by Eleocharis acicularis. Clean
Paterson, E., 1999. The Iron oxides. structure, properties, reactions, occurrences and (Weinh), http://dx.doi.org/10.1002/clen.201000488.
uses. Clay Miner., http://dx.doi.org/10.1180/claymin.1999.034.1.20. Salvador, F., Martin-Sanchez, N., Sanchez-Hernandez, R., Sanchez-Montero, M.J.,
Peng, Z., Liu, X., Zhang, W., Zeng, Z., Liu, Z., Zhang, C., Liu, Y., Shao, B., Liang, Q., Izquierdo, C., 2015. Regeneration of carbonaceous adsorbents. Part II: Chemical,
Tang, W., Yuan, X., 2020. Advances in the application, toxicity and degradation Microbiological and Vacuum Regeneration. Microporous Mesoporous Mater.,
of carbon nanomaterials in environment: a review. Environ. Int., http://dx.doi. http://dx.doi.org/10.1016/j.micromeso.2014.08.019.
org/10.1016/j.envint.2019.105298. Sankararamakrishnan, N., Jaiswal, M., Verma, N., 2014. Composite nanofloral clusters
Plohl, O., Ajdnik, U., Gyergyek, S., Ban, I., Vesel, A., Glaser, T.K., Zemljič, L.F., 2019. of carbon nanotubes and activated alumina: an efficient sorbent for heavy metal
Superior stability and high biosorbent efficiency of carboxymethylchitosan removal. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2013.08.070.
covalently linked to silica-coated core-shell magnetic nanoparticles for appli- Santhosh, C., Velmurugan, V., Jacob, G., Jeong, S.K., Grace, A.N., Bhatnagar, A., 2016.
cation in copper removal. J. Environ. Chem. Eng. 7, http://dx.doi.org/10.1016/j. Role of nanomaterials in water treatment applications: a review. Chem. Eng. J.,
jece.2019.102913. http://dx.doi.org/10.1016/j.cej.2016.08.053.
Pogorilyi, R.P., Melnyk, I.V., Zub, Y.L., Carlson, S., Daniel, G., Svedlindh, P., Seisenbaeva, Santhosh, C., Malathi, A., Dhaneshvar, E., Bhatnagar, A., Grace, A.N., Madhavan, J.,
G.A., Kessler, V.G., 2014. New product from old reaction: uniform magnetite 2018. Iron oxide nanomaterials for Water purification. In: Nanoscale Materials in
nanoparticles from iron-mediated synthesis of alkali iodides and their protec- Water Purification., http://dx.doi.org/10.1016/B978-0-12-813926-4.00022-7.
tion from leaching in acidic media. RSC Adv. 4, 22606–22612, http://dx.doi.org/ Savasari, M., Emadi, M., Bahmanyar, M.A., Biparva, P., 2015. Optimization of Cd
10.1039/c4ra02217c. (II) removal from aqueous solution by ascorbic acid-stabilized zero valent iron
Pourjavadi, A., Hosseini, S.H., Seidi, F., Soleyman, R., 2013. Magnetic removal of nanoparticles using response surface methodology. J. Ind. Eng. Chem., http://dx.
crystal violet from aqueous solutions using polysaccharide-based magnetic doi.org/10.1016/j.jiec.2014.06.014.
nanocomposite hydrogels. Polym. Int., http://dx.doi.org/10.1002/pi.4389. Sayato, Y., 1989. WHO guidelines for drinking-water quality. Eisei Kagaku 35,
Primo, A., Atienzar, P., Sanchez, E., Delgado, J.M., García, H., 2012. From biomass 307–312, http://dx.doi.org/10.1248/jhs1956.35.307.
wastes to large-area, high-quality, N-doped graphene: catalyst-free carboniza- Seifpanahi Shabani, K., Doulati Ardejani, F., Badii, K., Olya, M.E., 2017. Preparation
tion of chitosan coatings on arbitrary substrates. Chem. Commun. (Camb.), and characterization of novel nano-mineral for the removal of several heavy
http://dx.doi.org/10.1039/c2cc34978g. metals from aqueous solution: batch and continuous systems. Arab. J. Chem.,
Prof, B., Singh, B.P., Drexler, K.E., 1986. TOP-DOWN AND BOTTOM-UP APPROACHES http://dx.doi.org/10.1016/j.arabjc.2013.12.001.
FOR SYNTHESIS OF NANOMATERIALS introduction. In: Key Issues in the Fabri- Shabani, N., Sayadi, M.H., 2012. Evaluation of heavy metals accumulation by two
cation of Nanomaterials. emergent macrophytes from the polluted soil: an experimental study. Environ-
Qin, H., Hu, T., Zhai, Y., Lu, N., Aliyeva, J., 2020. The improved methods of heavy mentalist., http://dx.doi.org/10.1007/s10669-011-9376-z.
metals removal by biosorbents: a review. Environ. Pollut., http://dx.doi.org/10. Shah, M., Fawcett, D., Sharma, S., Tripathy, S.K., Poinern, G.E.J., 2015. Green synthesis
1016/j.envpol.2019.113777. of metallic nanoparticles via biological entities. Materials (Basel)., http://dx.doi.
Qiu, J., Zhang, X.F., Zhang, X., Feng, Y., Li, Y., Yang, L., Lu, H., Yao, J., 2018. Constructing org/10.3390/ma8115377.
Cd0.5Zn0.5S@ZIF-8 nanocomposites through self-assembly strategy to enhance Shahrokhi-Shahraki, R., Benally, C., El-Din, M.G., Park, J., 2021. High efficiency
Cr(VI) photocatalytic reduction. J. Hazard. Mater. 349, 234–241, http://dx.doi. removal of heavy metals using tire-derived activated carbon vs commercial acti-
org/10.1016/j.jhazmat.2018.02.009. vated carbon: insights into the adsorption mechanisms. Chemosphere., http://
Rahman, Z., Singh, V.P., 2019. The relative impact of toxic heavy metals (THMs) dx.doi.org/10.1016/j.chemosphere.2020.128455.
(arsenic (As), cadmium (Cd), chromium (Cr)(VI), mercury (Hg), and lead (Pb)) Shalaby, T.I., Fikrt, N.M., Mohamed, M.M., El Kady, M.F., 2014. Preparation and char-
acterization of iron oxide nanoparticles coated with chitosan for removal of
353
Cd(II) and Cr(VI) from aqueous solution. Water Sci. Technol. 70, 1004–1010, FeS nanoparticles: stabilization effects and removal mechanism. Chem. Eng. J.,
http://dx.doi.org/10.2166/wst.2014.315. http://dx.doi.org/10.1016/j.cej.2018.03.126.
Sharififard, H., shahraki, Z.H., Rezvanpanah, E., Rad, S.H., 2018. A novel natu- Suresh Kumar Reddy, K., Al Shoaibi, A., Srinivasakannan, C., 2014a. Elemental
ral chitosan/activated carbon/iron bio-nanocomposite: sonochemical synthesis, mercury adsorption on sulfur-impregnated porous carbon-A review. Environ.
characterization, and application for cadmium removal in batch and continuous Technol. (United Kingdom)., http://dx.doi.org/10.1080/21622515.2013.804589.
adsorption process. Bioresour. Technol., http://dx.doi.org/10.1016/j.biortech. Suresh Kumar Reddy, K., Al Shoaibi, A., Srinivasakannan, C., 2014b. Gas-phase mer-
2018.09.094. cury removal through sulfur impregnated porous carbon. J. Ind. Eng. Chem.,
Sharma, Ajit, Verma, N., Sharma, Ashutosh, Deva, D., Sankararamakrishnan, N., 2010. http://dx.doi.org/10.1016/j.jiec.2013.10.067.
Iron doped phenolic resin based activated carbon micro and nanoparticles by Suryawanshi, A., Biswal, M., Mhamane, D., Gokhale, R., Patil, S., Guin, D., Ogale,
milling: synthesis, characterization and application in arsenic removal. Chem. S., 2014. Large scale synthesis of graphene quantum dots (GQDs) from waste
Eng. Sci., http://dx.doi.org/10.1016/j.ces.2010.02.052. biomass and their use as an efficient and selective photoluminescence on-off-on
Sheha, R.R., 2012. Synthesis and characterization of magnetic hexacyanoferrate (II) probe for Ag+ ions. Nanoscale., http://dx.doi.org/10.1039/c4nr02494j.
polymeric nanocomposite for separation of cesium from radioactive waste solu- Tang, W.W., Zeng, G.M., Gong, J.L., Liang, J., Xu, P., Zhang, C., Huang, B.Bin, 2014.
tions. J. Colloid Interface Sci., http://dx.doi.org/10.1016/j.jcis.2012.08.042. Impact of humic/fulvic acid on the removal of heavy metals from aqueous solu-
Sherlala, A.I.A., Raman, A.A.A., Bello, M.M., Buthiyappan, A., 2019. Adsorption of tions using nanomaterials: a review. Sci. Total Environ. 468–469, 1014–1027,
arsenic using chitosan magnetic graphene oxide nanocomposite. J. Environ. http://dx.doi.org/10.1016/j.scitotenv.2013.09.044.
Manage., http://dx.doi.org/10.1016/j.jenvman.2019.05.117. Theil Hansen, L., Kühle, A., Sørensen, A.H., Bohr, J., Lindelof, P.E., 1998. A technique for
Shipley, H.J., Engates, K.E., Grover, V.A., 2013. Removal of Pb(II), Cd(II), Cu(II), and positioning nanoparticles using an atomic force microscope. Nanotechnology 9,
Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, tem- 337–342, http://dx.doi.org/10.1088/0957-4484/9/4/006.
perature, and exhaustion. Environ. Sci. Pollut. Res., http://dx.doi.org/10.1007/ Theodore, L., Kunz, R.G., Nanotechnology: Environmental Implications and Solutions
s11356-012-0984-z. 2005. Nanotechnology: Environmental Implications and Solutions., http://dx.
Shivaprasad, P., Kaushik, S., Sivasamy, A., Nethaji, S., 2020. Superparamagnetic doi.org/10.1002/0471711705.
nanocomposites derived from waste polyurethane foam for the removal of Tirtom, V.N., Dinçer, A., Becerik, S., Aydemir, T., Çelik, A., 2012. Removal of lead (II)
Rhodamine B: batch and continuous column studies. Sep. Sci. Technol. 55, ions from aqueous solution by using crosslinked chitosan-clay beads. Desalin.
2879–2889, http://dx.doi.org/10.1080/01496395.2019.1657147. Water Treat., http://dx.doi.org/10.1080/19443994.2012.669161.
Siddiquee, S., Rovina, K., Azad, S.Al, 2015. Heavy metal contaminants removal from Tonelli, D., Scavetta, E., Gualandi, I., 2019. Electrochemical deposition of nanoma-
wastewater using the potential filamentous Fungi biomass: a review. J. Microb. terials for electrochemical sensing. Sensors (Switzerland) 19, http://dx.doi.org/
Biochem. Technol., http://dx.doi.org/10.4172/1948-5948.1000243. 10.3390/s19051186.
Simate, G.S., Ndlovu, S., 2015. The removal of heavy metals in a packed bed column Tong, S., Deng, H., Wang, L., Huang, T., Liu, S., Wang, J., 2018. Multi-functional nanohy-
using immobilized cassava peel waste biomass. J. Ind. Eng. Chem. 21, 635–643, brid of ultrathin molybdenum disulfide nanosheets decorated with cerium oxide
http://dx.doi.org/10.1016/j.jiec.2014.03.031. nanoparticles for preferential uptake of lead (II) ions. Chem. Eng. J. 335, 22–31,
Simonin, J.P., 2016. On the comparison of pseudo-first order and pseudo-second http://dx.doi.org/10.1016/j.cej.2017.10.056.
order rate laws in the modeling of adsorption kinetics. Chem. Eng. J., http://dx. Trujillo-Reyes, J., Peralta-Videa, J.R., Gardea-Torresdey, J.L., 2014. Supported and
doi.org/10.1016/j.cej.2016.04.079. unsupported nanomaterials for water and soil remediation: are they a useful
Singh, S., Barick, K.C., Bahadur, D., 2013. Functional oxide nanomaterials and solution for worldwide pollution? J. Hazard. Mater. 280, 487–503, http://dx.doi.
nanocomposites for the removal of heavy metals and dyes. Int. J. Nanomater. org/10.1016/j.jhazmat.2014.08.029.
Nanotechnol. Nanomed., http://dx.doi.org/10.5772/57237. Upadhyay, U., Sreedhar, I., Singh, S.A., Patel, C.M., Anitha, K.L., 2020. Recent advances
Singh, D., Verma, S., Gautam, R.K., Krishna, V., 2016a. Copper adsorption onto in heavy metal removal by chitosan based adsorbents. Carbohydr. Polym.,
synthesized nitrilotriacetic acid functionalized Fe3O4 nanoparticles: kinetic, 117000.
equilibrium and thermodynamic studies. J. Environ. Chem. Eng., http://dx.doi. Vakili, M., Deng, S., Cagnetta, G., Wang, W., Meng, P., Liu, D., Yu, G., 2019. Regener-
org/10.1016/j.jece.2015.07.020. ation of chitosan-based adsorbents used in heavy metal adsorption: a review.
Singh, N.K., Raghubanshi, A.S., Upadhyay, A.K., Rai, U.N., 2016b. Arsenic and other Sep. Purif. Technol. 224, 373–387, http://dx.doi.org/10.1016/j.seppur.2019.05.
heavy metal accumulation in plants and algae growing naturally in contami- 040.
nated area of West Bengal, India. Ecotoxicol. Environ. Saf., http://dx.doi.org/10. Vangronsveld, J., Herzig, R., Weyens, N., Boulet, J., Adriaensen, K., Ruttens, A., Thewys,
1016/j.ecoenv.2016.04.024. T., Vassilev, A., Meers, E., Nehnevajova, E., van der Lelie, D., Mench, M., 2009. Phy-
Singh, D.K., Verma, D.K., Singh, Y., Hasan, S.H., 2017. Preparation of CuO nanoparti- toremediation of contaminated soils and groundwater: lessons from the field.
cles using Tamarindus indica pulp extract for removal of As(III): optimization of Environ. Sci. Pollut. Res., http://dx.doi.org/10.1007/s11356-009-0213-6.
adsorption process by ANN-GA, Journal of Environmental Chemical Engineering. Varadwaj, G.B.B., Oyetade, O.A., Rana, S., Martincigh, B.S., Jonnalagadda, S.B.,
Elsevier B.V., http://dx.doi.org/10.1016/j.jece.2017.01.046. Nyamori, V.O., 2017. Facile synthesis of three-dimensional Mg-Al layered double
Singh, N.B., Nagpal, G., Agrawal, S., Rachna, 2018. Water purification by using adsor- Hydroxide/Partially reduced graphene oxide nanocomposites for the effective
bents: a review. Environ. Technol. Innov., http://dx.doi.org/10.1016/j.eti.2018. removal of Pb2+ from aqueous solution. ACS Appl. Mater. Interfaces, http://dx.
05.006. doi.org/10.1021/acsami.6b16528.
Siró, I., Plackett, D., 2010. Microfibrillated cellulose and new nanocomposite mate- Venkateswarlu, S., Yoon, M., 2015. Surfactant-free green synthesis of Fe3O4
rials: a review. Cellulose., http://dx.doi.org/10.1007/s10570-010-9405-y. nanoparticles capped with 3,4-dihydroxyphenethylcarbamodithioate: stable
Siskova, K.M., Straska, J., Krizek, M., Tucek, J., Machala, L., Zboril, R., 2013. Formation recyclable magnetic nanoparticles for the rapid and efficient removal of Hg(II)
of zero-valent Iron nanoparticles mediated by amino acids. Procedia Environ. ions from water. Dalton Trans., http://dx.doi.org/10.1039/c5dt03155a.
Sci., http://dx.doi.org/10.1016/j.proenv.2013.04.109. Vijayaraghavan, K., Joshi, U.M., 2013. Hybrid Sargassum-sand sorbent: a novel
Song, D., Yang, R., Long, F., Zhu, A., 2019. Applications of magnetic nanoparticles in adsorbent in packed column to treat metal-bearing wastewaters from induc-
surface-enhanced Raman scattering (SERS) detection of environmental pollu- tively coupled plasma-optical emission spectrometry. J. Environ. Sci. Heal. - Part
tants. J. Environ. Sci. (China)., http://dx.doi.org/10.1016/j.jes.2018.07.004. A Toxic/Hazardous Subst. Environ. Eng., http://dx.doi.org/10.1080/10934529.
Sreedhar, I., Upadhyay, U., Roy, P., Thodur, S.M., Patel, C.M., 2020. Carbon Capture 2013.815503.
and Utilization by graphenes-path covered and ahead. J. Clean. Prod., http://dx. Vikrant, K., Kim, K.H., 2019. Nanomaterials for the adsorptive treatment of Hg(II)
doi.org/10.1016/j.jclepro.2020.124712. ions from water. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2018.10.022.
Su, C., 2017. Environmental implications and applications of engineered nanoscale Vojoudi, H., Badiei, A., Bahar, S., Mohammadi Ziarani, G., Faridbod, F., Ganjali,
magnetite and its hybrid nanocomposites: a review of recent literature. J. Haz- M.R., 2017. A new nano-sorbent for fast and efficient removal of heavy metals
ard. Mater. 322, 48–84, http://dx.doi.org/10.1016/j.jhazmat.2016.06.060. from aqueous solutions based on modification of magnetic mesoporous silica
Subbiah, T., Bhat, G.S., Tock, R.W., Parameswaran, S., Ramkumar, S.S., 2005. Elec- nanospheres. J. Magn. Magn. Mater. 441, 193–203, http://dx.doi.org/10.1016/j.
trospinning of nanofibers. J. Appl. Polym. Sci., http://dx.doi.org/10.1002/app. jmmm.2017.05.065.
21481. Volpin, F., Fons, E., Chekli, L., Kim, J.E., Jang, A., Shon, H.K., 2018. Hybrid for-
Subedi, N., Lähde, A., Abu-Danso, E., Iqbal, J., Bhatnagar, A., 2019. A comparative ward osmosis-reverse osmosis for wastewater reuse and seawater desalination:
study of magnetic chitosan (Chi@Fe3O4) and graphene oxide modified magnetic understanding the optimal feed solution to minimise fouling. Process Saf. Envi-
chitosan (Chi@Fe3O4GO) nanocomposites for efficient removal of Cr(VI) from ron. Prot., http://dx.doi.org/10.1016/j.psep.2018.05.006.
water. Int. J. Biol. Macromol., http://dx.doi.org/10.1016/j.ijbiomac.2019.06.151. Wadhawan, S., Jain, A., Nayyar, J., Mehta, S.K., 2020. Role of nanomaterials as adsor-
Sun, X., Zheng, C., Zhang, F., Yang, Y., Wu, G., Yu, A., Guan, N., 2009. Size-controlled bents in heavy metal ion removal from waste water: a review. J. Water Process
synthesis of magnetite (Fe3O4) nanoparticles coated with glucose and gluconic Eng., http://dx.doi.org/10.1016/j.jwpe.2019.101038.
acid from a single Fe(III) precursor by a sucrose bifunctional hydrothermal Wang, C., Xu, C., Zeng, H., Sun, S., 2009. Recent progress in syntheses and appli-
method. J. Phys. Chem. C., http://dx.doi.org/10.1021/jp9038682. cations of dumbbell-like nanoparticles. Adv. Mater., http://dx.doi.org/10.1002/
Sun, L., Tian, C., Li, M., Meng, X., Wang, L., Wang, R., Yin, J., Fu, H., 2013. From coconut adma.200900320.
shell to porous graphene-like nanosheets for high-power supercapacitors. J. Wang, X., Wang, Z., Chen, H., Wu, Z., 2017. Removal of Cu(II) ions from contaminated
Mater. Chem. A Mater. Energy Sustain., http://dx.doi.org/10.1039/c3ta10897j. waters using a conducting microfiltration membrane. J. Hazard. Mater., http://
Sun, W., Pan, W., Wang, F., Xu, N., 2015. Removal of Se(IV) and Se(VI) by MFe2O4 dx.doi.org/10.1016/j.jhazmat.2017.06.038.
nanoparticles from aqueous solution. Chem. Eng. J., http://dx.doi.org/10.1016/j. Wang, M., Payne, K.A., Tong, S., Ergas, S.J., 2018a. Hybrid algal photosynthesis and ion
cej.2015.03.061. exchange (HAPIX) process for high ammonium strength wastewater treatment.
Sun, Y., Liu, Y., Lou, Z., Yang, K., Lv, D., Zhou, J., Baig, S.A., Xu, X., 2018. Enhanced per- Water Res., http://dx.doi.org/10.1016/j.watres.2018.05.043.
formance for Hg(II) removal using biomaterial (CMC/gelatin/starch) stabilized Wang, N., Yang, D., Wang, Xiangxue, Yu, S., Wang, H., Wen, T., Song, G., Yu, Z.,
Wang, Xiangke, 2018b. Highly efficient Pb(ii) and Cu(ii) removal using hollow
354
Fe3O4@PDA nanoparticles with excellent application capability and reusability. Yang, J., Hou, B., Wang, J., Tian, B., Bi, J., Wang, N., Li, X., Huang, X., 2019. Nanomaterials
Inorg. Chem. Front., http://dx.doi.org/10.1039/c8qi00541a. for the removal of heavy metals from wastewater. Nanomaterials 9, http://dx.
Wang, C., Yang, R., Wang, H., 2020a. Synthesis of ZIF-8/Fly ash composite for adsorp- doi.org/10.3390/nano9030424.
tion of Cu2+, Zn2+ and Ni2+ from aqueous solutions. Materials (Basel). 13, http:// Yang, Y., Sun, F., Li, J., Chen, J., Tang, M., 2020. The effects of different factors on the
dx.doi.org/10.3390/ma13010214. removal mechanism of Pb(ii) by biochar-supported carbon nanotube compos-
Wang, L., Wang, K., Huang, R., Qin, Z., Su, Y., Tong, S., 2020b. Chemosphere Hier- ites. RSC Adv., http://dx.doi.org/10.1039/c9ra09470a.
archically fl ower-like WS 2 microcrystals for capture and recovery of Au Yao, W., Wang, J., Wang, P., Wang, Xiangxue, Yu, S., Zou, Y., Hou, J., Hayat, T., Alsaedi,
(III), Ag (I) and Pd (II). Chemosphere 252, 126578, http://dx.doi.org/10.1016/ A., Wang, Xiangke, 2017. Synergistic coagulation of GO and secondary adsorp-
j.chemosphere.2020.126578. tion of heavy metal ions on Ca/Al layered double hydroxides. Environ. Pollut.,
Wang, N., Su, Z., Deng, N., Qiu, Y., Ma, L., Wang, J., Chen, Y., Hu, K., Huang, C., Xiao, T., http://dx.doi.org/10.1016/j.envpol.2017.06.084.
2020c. Removal of thallium(I) from aqueous solutions using titanate nanoma- Yaqoob, A.A., Parveen, T., Umar, K., Ibrahim, M.N.M., 2020. Role of nanomaterials in
terials: the performance and the influence of morphology. Sci. Total Environ., the treatment of wastewater: a review. Water (Switzerland) 12, http://dx.doi.
http://dx.doi.org/10.1016/j.scitotenv.2020.137090. org/10.3390/w12020495.
Wang, X., Li, X., Wang, J., Zhu, H., 2020d. Recent Advances in Carbon Nitride-based Yi, C., Wang, W., Shen, C., 2014. The adsorption properties of CO molecules on single-
Nanomaterials for the Removal of Heavy Metal Ions from Aqueous Solution. Wuji layer graphene nanoribbons. AIP Adv. 4, http://dx.doi.org/10.1063/1.4868521.
Cailiao Xuebao/Journal Inorg. Mater., http://dx.doi.org/10.15541/jim20190436. Zarei, S., Niad, M., Raanaei, H., 2018. The removal of mercury ion pollution by using
Wang, Z., Wang, Y., Cao, S., Liu, S., Chen, Z., Chen, J., Chen, Y., Fu, J., 2020e. Fabrica- Fe3O4-nanocellulose: synthesis, characterizations and DFT studies. J. Hazard.
tion of core@shell structural Fe-Fe2O3@PHCP nanochains with high saturation Mater., http://dx.doi.org/10.1016/j.jhazmat.2017.10.009.
magnetization and abundant amino groups for hexavalent chromium adsorp- Zhang, W.X., 2003. Nanoscale iron particles for environmental remediation: an
tion and reduction. J. Hazard. Mater. 384, 121483, http://dx.doi.org/10.1016/j. overview. J. Nanopart. Res., http://dx.doi.org/10.1023/A:1025520116015.
jhazmat.2019.121483. Zhang, J., Zhai, S., Li, S., Xiao, Z., Song, Y., An, Q., Tian, G., 2013a. Pb (II) removal of Fe
Wu, G., Kang, H., Zhang, X., Shao, H., Chu, L., Ruan, C., 2010. A critical review on 3 O 4 @ SiO 2 – NH 2 core – shell nanomaterials prepared via a controllable sol
the bio-removal of hazardous heavy metals from contaminated soils: issues, – gel process. Chem. Eng. J. 216, 461–471, http://dx.doi.org/10.1016/j.cej.2012.
progress, eco-environmental concerns and opportunities. J. Hazard. Mater., 11.043.
http://dx.doi.org/10.1016/j.jhazmat.2009.09.113. Zhang, J., Zhai, S., Li, S., Xiao, Z., Song, Y., An, Q., Tian, G., 2013b. Pb(II) removal of
Wu, Z., Li, W., Webley, P.A., Zhao, D., 2012. General and controllable synthesis Fe3O4@SiO2-NH2 core-shell nanomaterials prepared via a controllable sol-gel
of novel mesoporous magnetic iron oxide@carbon encapsulates for efficient process. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2012.11.043.
arsenic removal. Adv. Mater., http://dx.doi.org/10.1002/adma.201103789. Zhang, Y., Ye, Y., Liu, Z., Li, B., Liu, Qinzhuang, Liu, Qiangchun, Li, X., 2016a. Monodis-
Wu, Z., Su, X., Lin, Z., Owens, G., Chen, Z., 2019. Mechanism of As(V) removal by green persed hierarchical aluminum/iron oxides composites micro/nanoflowers for
synthesized iron nanoparticles. J. Hazard. Mater., http://dx.doi.org/10.1016/j. efficient removal of As(V) and Cr(VI) ions from water. J. Alloys. Compd., http://
jhazmat.2019.120811. dx.doi.org/10.1016/j.jallcom.2015.12.062.
Xiao, G., Wang, Y., Xu, S., Li, P., Yang, C., Jin, Y., Sun, Q., Su, H., 2018. PT. Chinese J. Zhang, Y., Zhou, X., Liu, Z., Li, B., Liu, Q., Li, X., 2016b. RSC advances. RSC Adv. 6,
Chem. Eng. #pagerange#., http://dx.doi.org/10.1016/j.cjche.2018.09.028. 6695–6701, http://dx.doi.org/10.1039/C5RA23915J.
Xiao, G., Wang, Y., Xu, S., Li, P., Yang, C., Jin, Y., Sun, Q., Su, H., 2019a. Superior adsorp- Zhang, S., Shi, Q., Christodoulatos, C., Korfiatis, G., Meng, X., 2019a. Adsorptive fil-
tion performance of graphitic carbon nitride nanosheets for both cationic and tration of lead by electrospun PVA/PAA nanofiber membranes in a fixed-bed
anionic heavy metals from wastewater. Chinese J. Chem. Eng., http://dx.doi.org/ column. Chem. Eng. J., http://dx.doi.org/10.1016/j.cej.2019.03.294.
10.1016/j.cjche.2018.09.028. Zhang, Y.N., Niu, Q., Gu, X., Yang, N., Zhao, G., 2019b. Recent progress on carbon
Xiao, X., Wang, Q., Owens, G., Chiellini, F., Chen, Z., 2019b. Reduced graphene nanomaterials for the electrochemical detection and removal of environmental
oxide/iron nanoparticles used for the removal of Pb (II) by one step green synthe- pollutants. Nanoscale., http://dx.doi.org/10.1039/c9nr02935d.
sis. J. Colloid Interface Sci. 557, 598–607, http://dx.doi.org/10.1016/j.jcis.2019. Zhang, X., Yan, L., Li, J., Yu, H., 2020. Adsorption of heavy metals by L-cysteine inter-
09.058. calated layered double hydroxide: kinetic, isothermal and mechanistic studies.
Xu, X., Zhang, Z., Fei, B., Ge, X., Zhang, M., 1998. Inverse suspension polymeriza- J. Colloid Interface Sci. 562, 149–158, http://dx.doi.org/10.1016/j.jcis.2019.12.
tion of sodium acrylate. Acta Polym. Sin., http://dx.doi.org/10.1002/(sici)1097- 028.
4628(19970725)65:4<789::aid-app16>3.3.co;2-1. Zhao, Z., Sun, Y., Dong, F., 2015. Graphitic carbon nitride based nanocomposites: a
Xu, J., Cao, Z., Zhang, Y., Yuan, Z., Lou, Z., Xu, X., Wang, X., 2018a. A review of function- review. Nanoscale., http://dx.doi.org/10.1039/c4nr03008g.
alized carbon nanotubes and graphene for heavy metal adsorption from water: Zheng, Y., Li, C., Meng, X., Zhang, Z., 2016. A conjugated composite of ␣-Fe2O3 and
preparation, application, and mechanism. Chemosphere 195, 351–364, http:// BiOBr with enhanced visible-light-induced photocatalytic activity. J. Mol. Catal.
dx.doi.org/10.1016/j.chemosphere.2017.12.061. A Chem., http://dx.doi.org/10.1016/j.molcata.2016.05.004.
Xu, L., Xu, X., Cao, G., Liu, S., Duan, Z., Song, S., Song, M., Zhang, M., 2018b. Optimiza- Zhou, S., Wang, D., Sun, H., Chen, J., Wu, S., Na, P., 2014. Synthesis, character-
tion and assessment of Fe–electrocoagulation for the removal of potentially toxic ization, and adsorptive properties of magnetic cellulose nanocomposites for
metals from real smelting wastewater. J. Environ. Manage. 218, 129–138, http:// arsenic removal. Water Air Soil Pollut. 225, http://dx.doi.org/10.1007/s11270-
dx.doi.org/10.1016/j.jenvman.2018.04.049. 014-1945-6.
Yan, Q., Street, J., Yu, F., 2015. Synthesis of carbon-encapsulated iron nanoparti- Zhou, C., Zhu, H., Wang, Q., Wang, J., Cheng, J., Guo, Y., Zhou, X., Bai, R., 2017.
cles from wood derived sugars by hydrothermal carbonization (HTC) and their Adsorption of mercury(ii) with an Fe3O4 magnetic polypyrrole-graphene oxide
application to convert bio-syngas into liquid hydrocarbons. Biomass Bioenergy, nanocomposite. RSC Adv., http://dx.doi.org/10.1039/c7ra01147d.
http://dx.doi.org/10.1016/j.biombioe.2015.09.002. Zong, P., Wang, S., Zhao, Y., Wang, H., Pan, H., He, C., 2013. Synthesis and application
Yan, L., Li, S., Yu, H., Shan, R., Du, B., Liu, T., 2016. Facile solvothermal synthesis of of magnetic graphene/iron oxides composite for the removal of U(VI) from aque-
Fe3O4/bentonite for efficient removal of heavy metals from aqueous solution. ous solutions. Chem. Eng. J. 220, 45–52, http://dx.doi.org/10.1016/j.cej.2013.01.
Powder Technol., http://dx.doi.org/10.1016/j.powtec.2016.06.051. 038.
Yan, Y., Yuvaraja, G., Liu, C., Kong, L., Guo, K., Reddy, G.M., Zyryanov, G.V., 2018.
Removal of Pb(II) ions from aqueous media using epichlorohydrin crosslinked
chitosan Schiff’s base@Fe3O4 (ECCSB@Fe3O4). Int. J. Biol. Macromol., http://dx.
doi.org/10.1016/j.ijbiomac.2018.05.204.
355

Paper 1

Uploaded by

Copyright:

Available Formats

Paper 1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Paper 1

Uploaded by

Copyright:

Available Formats

Process Safety and Environmental Protection 150 (2021) 323–355

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

Heavy metal removal from wastewater using nanomaterials-process

3.1.4. Zinc based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335

1. Introduction (Gollavelli et al., 2013) and adsorption. Most of these methods

Fig. 1. Dependence of Synthesis Protocols on structure of adsorbent.

Process Safety and Environmental Protection 150 (2021) 323–355

Process Safety and Environmental Protection 150 (2021) 323–355

Fig. 2. Top-down and Bottom-up approach of nanoparticle synthesis.

S.S. Kolluru et al.

order kinetics isotherm eliminate radionuclides.

Process Safety and Environmental Protection 150 (2021) 323–355

Process Safety and Environmental Protection 150 (2021) 323–355

order kinetics model 240 min,

Process Safety and Environmental Protection 150 (2021) 323–355

model responsible for lead adsorption

Process Safety and Environmental Protection 150 (2021) 323–355

Process Safety and Environmental Protection 150 (2021) 323–355

Fig. 3. Classiﬁcation of Nanoparticle Materials.

spinel nickel ferrite (NiFe2O4), which acts as an effective adsorbent

Nanoparticle Biochemical Agent Size Morphology Reference

1 indicates linear adsorption leading to identical adsorption ener-

RL is a dimensionless parameter used to foresee the nature of

carbon nitride nanosheets follows Langmuir, Freundlich, Redlich-

Isotherm constant (BDR), calculated from slope of the Dubinine-

Fig. 9. Fixed-Bed column setup for continuous adsorption of metal ions.

S.No Adsorbent CD (cm); APH(cm); FR Results References

9. Scale up and feasibility studies

You might also like