Jeon 2020

Chemosphere 261 (2020) 127781
Contents lists available at ScienceDirect
Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
Review
A review on MXene-based nanomaterials as adsorbents in aqueous

solution
Minjung Jeon a, Byung-Moon Jun a, Sewoon Kim a, Min Jang b, Chang Min Park c,
Shane A. Snyder d, e, Yeomin Yoon a, *
a
Department of Civil and Environmental Engineering, University of South Carolina, Columbia, 300 Main Street, SC, 29208, USA
b
Department of Environmental Engineering, Kwangwoon University, 447-1 Wolgye-Dong Nowon-Gu, Seoul, Republic of Korea
c
Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu, 41566, Republic of Korea
d
School of Civil & Environmental Engineering, Nanyang Technological University, 1 Cleantech Loop, 637141, Singapore
e
Department of Chemical and Environmental Engineering, University of Arizona, Tucson, AZ, 85721, USA
h i g h l i g h t s
Removal of inorganic and organic contaminants by MXene-based nanomaterials was reviewed.

Valuable information was provided for applications of MXene-based nanomaterials in wastewater treatment.
Areas of future research for the removal of various contaminants in MXene-based nanomaterials were suggested.
a r t i c l e i n f o a b s t r a c t
Article history: Environmental pollution has intensified and accelerated due to a steady increase in the number of in-
Received 15 June 2020 dustries, and finding methods to remove hazardous contaminants, which can be typically divided into
Received in revised form inorganic and organic compounds, have become inevitable. One of the widely used water treatment
16 July 2020
technologies is adsorption and various kinds of adsorbents for the removal of inorganic and organic
Accepted 17 July 2020
Available online 24 July 2020
contaminants from water have been discovered. Recently, MXene, as an emerging nanomaterial, has
gained rapid attention owing to its unique characteristics and various applicability. Particularly, in the
Handling Editor: Xiangru Zhang area of adsorptive application, MXene and MXene-based adsorbents have shown great potential in a
large number of studies. In this regard, a comprehensive understanding of the adsorptive behavior of
Keywords: MXene-based nanomaterials is necessary in order to explain how they remove inorganic and organic
Adsorption contaminants in water. Adsorption by MXene-based adsorbents tends to be highly influenced by not only
MXene nanoadsorbents the physicochemical properties of these adsorbents but also water quality, such as pH value, tempera-
Heavy metal ture, background ion, and natural organic matter. Therefore, in this review paper, the effect of various
Dye
water quality on the adsorption of inorganic and organic contaminants by various types of MXene and
Water/wastewater treatment
MXene-based adsorbents is explored. Furthermore, this review also covers general trends in the syn-
thesis of MXene and regeneration of MXene-based adsorbents in order to assess their stability.
© 2020 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Fabrication and characteristics of MXene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. General fabrication process of MXene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Etching method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.1. HF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.2. In situ HF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
* Corresponding author.
E-mail address: [email protected] (Y. Yoon).
https://doi.org/10.1016/j.chemosphere.2020.127781
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
2 M. Jeon et al. / Chemosphere 261 (2020) 127781
2.3. Delamination method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.3.1. Intercalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.2. Sonication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Removal of inorganic contaminants by MXene nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Effects of contaminant and MXene properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Effects of water quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.2. Background ions and NOM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Removal of organic contaminants by MXene nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1. Effects of contaminant and MXene properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2. Effects of water quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.2. Background ions and NOM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Regeneration of MXene nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
6. Conclusions and areas of future study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1. Introduction attracted great attention as emerging adsorbents for the effective

removal of various environmental contaminants due to their
Various contaminants have been discharged into water inade- distinct properties, which can result in significant adsorptive
quately treated and cause severe environmental pollution and remediation (Fu et al., 2018; Wu et al., 2019). The unique properties
harm to human health, as rapid developments in industrialization of 2D nanomaterials, such as carbon-based nanomaterials, have
continue (Jasper et al., 2017). The contaminants can generally be increased the tendency to employ nanomaterial-based adsorbents
divided into two groups: organic and inorganic. Among the organic for the treatment of inorganic and organic pollutants in water
contaminants are typically dye compounds such as methylene blue, (Atkovska et al., 2018; Liu et al., 2017b). Compared to the large and
which are discharged generally by factories manufacturing textile, bulky formation of the conventional adsorbents, nanomaterial-
paint, paper, etc. (Karaçetin et al., 2014). For inorganic contami- based adsorbents often possess thin structures, large specific sur-
nants, heavy metal ions and radionuclides are the dominant pol- face area, and abundant functional sites (Novoselov et al., 2004;
lutants in water (Zhang et al., 2018). They have adverse effects on Zhang et al., 2018). Since it is important for adsorbents to display
living things and the natural environment in general due to their great interaction with adsorbates and have large surface area for
toxicity and carcinogenicity. Since some of them can be bio- better performance, nanomaterials are regarded as having the po-
accumulated, the damage they cause in living organisms could be tential to treat not only organic but also inorganic adsorbates (Tan
more severe than that caused by other pollutants, which cannot be et al., 2015; Yang et al., 2019).
bioaccumulated (Berrios et al., 2012; Fu et al., 2018; Karaçetin et al., Recently, an emerging class of 2D nanomaterials from a family of
2014). Thus, the implementation of appropriate treatment methods transition metal carbide or nitrate materials, known as MXene, has
for the removal of these contaminants has been regarded as one of aroused tremendous interest in various fields. Due to their prop-
the main determinants of the prosperity of industries in the long erties such as environmental-friendly characteristics, large surface
run. area, high chemical stability, thermal/electrical conductivity, and
To date various techniques have been used for the removal of hydrophilicity, MXenes can be employed as suitable materials in
several organic and inorganic pollutants from water, such as various applications including lithium-ion battery (Naguib et al.,
coagulation (Fu and Wang, 2011; Moghaddam et al., 2010), ion 2012a), hydrogen storage (Hu et al., 2013), semiconductor (Gao
exchange (Dabrowski et al., 2004; Fu and Wang, 2011), sorption (Fu et al., 2016), supercapacitor (Zhu et al., 2016), and environmental
and Wang, 2011; Gong et al., 2007), membrane filtration (Blo €cher applications (Ciou et al., 2019; Liu et al., 2018a; Peng et al., 2014).
et al., 2003; Fu and Wang, 2011), chemical precipitation (Fu and In particular, the possible environmental applications include
Wang, 2011; Fu et al., 2012), sonodegradation (Ertugay and Acar, adsorption, photocatalysis, and membrane filtration to remove
2014; Wang et al., 2010b), and photocatalytic oxidation (Ertugay contaminants, and adsorption using MXenes and MXene-based
and Acar, 2014; Sakthivel et al., 2003). Among these techniques, materials as adsorbents for the removal of organic and inorganic
adsorption is one of the most widely used due to its attractive pollutants from water has been widely studied (Guo et al., 2016a,
characteristics such as cost-effectiveness, simplicity, and practi- 2016b; Rasool et al., 2017). Since MXene-based adsorbents can
cality (Burakov et al., 2018; Wu et al., 2019). In addition, employing adsorb various environmental pollutants owing to their unique
adsorbents for the removal of environmental pollutants prevents structures (Ying et al., 2015), it is important to fully understand the
the formation of secondary pollutants since the adsorbents adsorb adsorption mechanisms and interaction between pollutants and
the contaminants, not react with them (Wu et al., 2019; Zhang et al., the adsorbents. Additionally, the adsorption process of both kinds
2018). There are several conventional adsorbents, such as granular of pollutants in water is highly affected by not only the adsorbents’
or powdered activated carbon (Oguz and Keskinler, 2005), kaolin, properties but also by the water quality conditions such as tem-
and chitosan (Wang et al., 2010a; Zhu et al., 2010), to name a few, perature, pH, and the presence of natural organic matter (NOM). In
which are widely used due to their high porosity and large surface this regard, it is critical to evaluate the influence of the water
area. In recent years, two-dimensional (2D) nanomaterials have quality properties on the adsorption performance, leading to better
M. Jeon et al. / Chemosphere 261 (2020) 127781 3
understanding of the adsorbents and ultimately the removal of from the discovery in 2011 to the recent electronic applications.
pollutants.
In this review paper, the main purpose is to deliver the overall 2.2. Etching method
knowledge of MXene and MXene-based nanomaterials and their
properties and to provide an overview of the adsorptive applica- The purpose of etching in the fabrication process is to success-
tions of various functionalized MXene-based nanomaterials as fully exfoliate A layers from MAX phases (Naguib and Gogotsi,
novel adsorbents for the removal of inorganic and organic pollut- 2015). In Fig. 2a, the schematic and atomic model of well-etched
ants from water. Although a few review studies have already Ti3C2Tx and its scanning electron microscopy (SEM) image are
covered the use of MXenes as adsorbents in water treatment (Jun shown. There are generally two etching methods: HF method and
et al., 2018; Rasool et al., 2019; Zhang et al., 2018), their adsorp- in situ HF method (Alhabeb et al., 2017). HF method involves
tive application with regard to their water quality properties, literally using various concentrations of HF solution as etchants. In
including pH, background ions and NOM, and temperature, has not situ HF method, on the other hand, does not utilize HF solution
been thoroughly explored yet. Additionally, since one of the ad- directly, but uses HF-containing or HF-forming etchants. In situ HF
vantages of adsorbents is that they can be recycled after some method was invented because high concentrations of HF solution
proper regenerating processes, regeneration methods and adsorp- could expose people to considerable risks due to its hazards (Feng
tive performance after regeneration of the used adsorbents are et al., 2017). It was also expected that the etchants used in in situ HF
included in this review to clarify the stability and economic feasi- method could act as intercalants as well (Halim et al., 2014).
bility of MXenes and MXene-based nanomaterials from various Exceptionally, there is another way to etch A layers without
literature. employing a fluoride-containing etchant, but by using other re-
agents, such as NaOH and H2SO4, although much research has not
2. Fabrication and characteristics of MXene been conducted in that regard (Xie et al., 2014). Depending on what
kinds and concentration of etchants are used, the further process,
2.1. General fabrication process of MXene as discussed later in the section on delamination, could be influ-
enced accordingly. To conduct a successful wet chemical etching
MXenes can be synthesized from MAX phases, a family of process, appropriate etchants and synthesis conditions are neces-
ternary carbides and nitrides, as the pristine formula, which con- sary, and the characteristics of the etched materials vary depending
sists of M, A, and X, representing an early transition metal (Ti, Nb, V, on them (Alhabeb et al., 2017; Hong Ng et al., 2017; Lei et al., 2015;
Ta, etc.), an A-group element from groups 13 and 14 (such as Al or Lipatov et al., 2016).
Si), and C and/or N, respectively (Lei et al., 2015). Generally, the
fabrication process includes etching and delamination. By etching A 2.2.1. HF
layers in MAX phases, which is probable owing to A layers being HF solution is one of the most common etchants used to etch A
relatively weakly bound with M elements compared to M-X bonds, layers in the parent MAX phases (Alhabeb et al., 2017; Chang et al.,
the general formation of MAX phases, Mnþ1AXn (n ¼ 1, 2 or 3), turns 2013; Hong Ng et al., 2017). Fig. 2b briefly describes the process of
into the multilayered Mnþ1Xn (Chang et al., 2013). Following the etching of a MAX phase using HF solution. By immersing the MAX
etching step, delamination is also conducted to yield single-layered phase in HF solution, the A element (Al being a typical example)
MXene by enlarging the space in between the layers with inter- reacts with fluorine from the etchant and eventually becomes
calants and sonicating the result of the intercalation if the specific etched in the MAX phases to form aluminum fluoride (AlF3) (Lei
size of flakes or concentration is required (Alhabeb et al., 2017). et al., 2015). HF also reacts with multilayered MXene, thus having
The general history of fabrication of MXenes has been thor- MXene consist of F on its surface as part of its functional groups
oughly covered by a few studies (Alhabeb et al., 2017; Anasori et al., (Hong Ng et al., 2017). Etching conditions, including the concen-
2017; Naguib et al., 2012a, 2014), and, according to them, fabrica- tration of HF solution, temperature, and duration of immersion,
tion of MXene has gone through a series of development beginning greatly affect the resulting MXene, which is the reason why finding
from 2011 when for the first time MXene was discovered by sci- an optimum combination of the etching conditions is necessary for
entists at Drexel University (Naguib et al., 2011). The reported better performance of the resultant (Lei et al., 2015; Lipatov et al.,
etching method was conducted with 50% concentrated hydroflu- 2016; Naguib and Gogotsi, 2015). Concentration of the etchant
oric acid (HF) solution, which is one of the typical and effective varies from 5 to 50 wt % HF and so does exposure time vary ac-
etchants used even till today (Alhabeb et al., 2017). Following their cording to the concentration, from 5 to 24 h. The influence of in-
discovery, other types of multilayered MXenes with different ele- dividual etching conditions on the result of the etching process can
ments of MAX phases were synthesized by the wet chemical be confirmed by SEM, energy dispersive X-ray (EDX), and powder
etching technique. Intercalation, which is a part of the delamina- X-ray diffraction (XRD) (Alhabeb et al., 2017; Chang et al., 2013;
tion step, was presented afterwards in order to produce single- Ying et al., 2015).
layered MXenes by introducing large organic compounds, such as By varying the concentration of HF solution, MXenes with
urea, hydrazine monohydrate, dimethyl sulfoxide, isopropylamine, different morphology can be fabricated. It was reported that more
and tetrabutylammonium hydroxide, in between the layers sophisticatedly etched Ti3C2Tx can be synthesized by using HF so-
(Mashtalir et al., 2013, 2015; Naguib et al., 2015). From 2014, new lutions at higher concentrations (Alhabeb et al., 2017). The etching
approaches to etching were reported, which did not use HF solution performance of three different concentrations (5, 10, and 30 wt %)
but ammonium bifluoride (Halim et al., 2014) or HCl with LiF of HF etchants were compared and it was confirmed, through their
(Ghidiu et al., 2014; Lipatov et al., 2016) in order to satisfy the high SEM images, that the resulting MXene of 30 wt % HF solution has a
demand for etchants less dangerous than HF solution. Furthermore, well-etched, almost accordion-like structure. Compared to the
to date, the application of MXene has been expanded to electronic 30 wt % HF, the resulting morphology of the MXenes of the 10 wt %
fields such as in antennas for wireless communication and nano- and 5 wt % HF solution were less open, and also hardly expanded in
wire electrodes for flexible organic solar cells employing its unique case of the 5 wt %. Although it was observed by XRD and EDX that
conductivity, hydrophilicity, and thin structure (Sarycheva et al., all three different concentrations of the etchant played their roles
2018; Tang et al., 2019). Fig. 1 shows the overall timeline of the as reagents for the exfoliation of the A layer effectively, the highest
development of MXene and MXene-based materials, including concentration of HF was able to synthesize MXene with a distinct
Fig. 1. Timeline of MXenes: from Ti3C2 discovery to the current development (Al-Hamadani et al., 2020; Alhabeb et al., 2017).
Fig. 2. (a) Schematic of (a) Ti3C2Tx layered structure with a side view atomic model of a single sheet and SEM image of a Ti3C2Tx particle (Mashtalir et al., 2014), (b) the exfoliation of
MAX phases and formation of MXenes (Naguib et al., 2012b), (c) structures of Ti3C2Tx with summary of routes 1 and 2 (Lipatov et al., 2016), and (d) structural illustrations of the
parental Ti3AlC2 MAX phase and the post-etching MXene before and after alkalization treatment (Zhu et al., 2017).
accordion-like structure and larger surface area (Alhabeb et al., found that the layers of etched MXene became thinner and,
2017). The duration of immersion of the MAX phase in HF solu- accordingly, the space between layers was enlarged by exfoliating
tion also affects the result of the etching process (Chang et al., the A-group. The XRD patterns of the pristine Ti3AlC2 and the HF-
2013). In this study, Ti3AlC2 powders were etched by 40 wt % HF treated resultant showed a weakening trend in the diffraction
solution at room temperature after being ball-milled for 5 h and peaks of the former as the duration of immersion prolonged from 4
sintered at 1350 C for 2 h. As the time of reaction increased, it was to 20 h. On the other hand, the peaks of the latter were shown
clearly, and no peak changes could be noted after 2 h, which could as large organic compounds, various ions from the etchant, and etc.
imply that the resulting multilayered MXene likely possessed The next step is sonication and the purpose of this process is to
thinner-layered morphology due to the extended reaction time produce the desired size of flakes or concentration of 2D MXene by
(Chang et al., 2013). sonicating intercalated MXene. In other words, sonication could be
optional if there is no requirement of a particular concentration or
2.2.2. In situ HF flake size for the resulting MXene (Alhabeb et al., 2017; Mashtalir
In order to avoid the use of high concentrations of HF solution et al., 2013; Naguib et al., 2015).
due to the high risks attributed to the critical corrosiveness of HF, in
situ HF etching method was discovered as a safer way to synthesize 2.3.1. Intercalation
MXene (Halim et al., 2014). The reagents used in this method Intercalation is conducted after etching to accommodate ions or
generally contain HF or form HF through reaction, thus employing a organic compounds in order to expand the space in between the
similar effect to HF method to exfoliate A layers from MAX phases. layers of un-delaminated MXene, considered as a pre-treatment
Some of the typical etchants that are used for in situ HF method are before sonication, which ultimately leads to the delamination of
ammonium bifluoride, ammonium fluoride, and LiF/HCl (Ghidiu the layers (Alhabeb et al., 2017; Mashtalir et al., 2013). Generally,
et al., 2014; Halim et al., 2014; Lipatov et al., 2016; Shahzad et al., after HF etching, the eOH and eF functional groups first become
2019a; Zhang et al., 2019a). Additional advantages other than less part of the surface of the resulting multilayered MXene (Lukatskaya
hazards compared to HF are that etching and intercalation, as we et al., 2013). Then, other cations from the intercalants could replace
would see later, could be conducted at the same time and soni- some of the initial functional groups, which may increase the
cation is not compulsory in the process of fabrication (Halim et al., selectivity of the resultant for the target pollutants after the inter-
2014; Hong Ng et al., 2017; Naguib et al., 2015). Also, other newly calation process (Peng et al., 2014). Some of the possible inter-
invented etchants, such as FeF3/HCl (Wang et al., 2017b), in which calants are dimethyl sulfoxide and tetraalkylammonium
LiF is replaced with FeF3, are consistently being investigated. compounds, such as tetrabutylammonium hydroxide and tetra-
In order to simplify the etching process, including carrying out methylammonium hydroxide (Ma and Sasaki, 2015; Mashtalir et al.,
etching and intercalation as one step, 2D thin Ti3C2 films was 2013). LiF/HCl, which is one of the etchants used in in situ HF
fabricated using ammonium bifluoride as an etchant (Halim et al., method, could play two roles as an etchant and an intercalant
2014). By immersing Ti3AlC2 in the etchant, it was found that it is owing to the high likability of Liþ ions intercalated in between
possible for Al to be selectively etched by forming (NH4)3AlF6, and layers (Ghidiu et al., 2014; Lipatov et al., 2016). Ammonium
from their X-ray photoelectron spectroscopy (XPS) analysis of ni- bifluoride may also have a similar effect as LiF/HCl, which could be
trogen, they concluded that NH3 or NHþ 4 could be intercalated in attributed to the intercalation of the ammonia species, NH3 and
between the etched phases, thus making the interlayers more NHþ 4 (Halim et al., 2014). Water molecules could sometimes be one
spacious. They also discovered that the c lattice parameter, of the intercalated species which greatly expand the c lattice
confirmed by XRD, of Ti3C2Tx etched by ammonium bifluoride is parameter (Ghidiu et al., 2014; Wang et al., 2017a). Up until now,
2.47 nm while that of the same Ti3C2Tx etched by HF is 1.98 nm, research on intercalation effect and potential intercalants, such as
showing almost a 25% increase in the c lattice parameter. They alkaline intercalant (Wang et al., 2017b; Zhu et al., 2017), has been
concluded from this result that intercalation and etching were steadily conducted. Fig. 2d illustrates the synthesis process of
successfully performed at the same time (Halim et al., 2014). Ti3C2Tx intercalated by an alkaline solution.
LiF/HCl is also one of the widely used in situ HF etchants and the
concentrations of LiF and HCl vary depending on the desired con- 2.3.2. Sonication
dition of MXene (Ghidiu et al., 2014; Lipatov et al., 2016; Zhang Sonication is considered the last step of the fabrication of
et al., 2019c). By using 5 M LiF and 6 M HCl to etch Al in Ti3AlC2, MXene and its aim is to manage the size of flakes and concentration
the A layers were well etched, indicated by XRD analysis showing of MXene (Alhabeb et al., 2017). In fact, there are several ways to
absence of peaks belonging to Ti3AlC2. Comparing the lattice pa- control the size of the flakes, one of which involves using centri-
rameters of c, the one of MXene etched by LiF/HCl was 2.8 nm while fugation to separate larger-sized MXene particles from the solution
that of the one etched by HF is 2.0 nm. Furthermore, the c lattice of containing smaller sizes of MXene in colloidal state (Ghidiu et al.,
hydrated MXene produced by LiF/HCl was 4.0 nm, which can be 2014; Lipatov et al., 2016; Wang et al., 2017b). Another method is
assumed to be swollen owing to the intercalation of H2O and the to reduce the size of MXene by sonication before centrifugation so
cations in the solution. It was also reported that this LiF/HCl method that the un-delaminated particles could be exfoliated, thereby
can reduce the time of synthesis of MXene by shortening the increasing the concentration of colloidal MXene in the solution
duration of sonication step from 4 h to 30e60 min (Ghidiu et al., (Backes et al., 2017; Mashtalir et al., 2015). Although the size and
2014). Concentrations of LiF higher than 5 M and of HCl higher concentration of MXene can be controlled by centrifugation,
than 6 M can be used to minimize the necessity of the sonication centrifugation alone is considered a limited option, and controlling
step (Lipatov et al., 2016). Schematic structures of MXene etched the concentration and size by centrifugation after sonication is
with different concentrations of LiF are shown in Fig. 2c. more effective for various possible applications since it yields a
higher concentration or smaller flakes of MXene (Alhabeb et al.,
2.3. Delamination method 2017).
After etching, delamination follows, which is accomplished 3. Removal of inorganic contaminants by MXene
through intercalation and sonication (Alhabeb et al., 2017). Inter- nanomaterials
calation is the introduction of various ions or molecules between
layers of etched MXene, thus enlarging the interspace between the 3.1. Effects of contaminant and MXene properties
layers, which results in an increase in the surface area and even the
delamination of the layers into a 2D structure (Guo et al., 2015; The most common inorganic contaminants in water that can be
Mashtalir et al., 2013; Naguib et al., 2015). As mentioned earlier, removed by MXene-based nanomaterials are heavy metals and
there are two steps for delaminating layered MXene, which are radionuclides (Zhang et al., 2018). MXene can be electrostatically
intercalation and sonication. Various intercalants can be used, such charged and the surface charge of MXene is attributed to functional
groups on the surface (Naguib et al., 2012b). During etching and of 0.11 cm3 g1. Accordingly, the highest adsorption capacity of
intercalation, various functional groups are formed on the surface 250 mg g1 was achieved by the MXene using 10 wt % of HF so-
of MXene, such as eO, eF, and eOH. A wide variety of functional lution, whereas the corresponding values for the other concentra-
groups which support adsorption reaction are formulated by tions were slightly less. Due to the positive surface charge of Ti3C2Tx
etchants and intercalants (Mu et al., 2018; Peng et al., 2014). In below a pH of 2, Cr ions in the form of Cr2O2 7 can be removed from
other words, they could electrostatically interact with opposite water as a result of the electrostatic interaction between the two
charges from target compounds in water. Also, the charge on charges. Additionally, through the adsorption, Cr(VI) was reduced
MXene depends on the pH of the solution due to protonation by to Cr(III) during adsorption. Cr(VI) can be reduced to Cr(III) in the
hydrogen ions, MXene could adsorb negatively or positively presence of Hþ ions and electrons to produce water molecules.
charged targets depending on its charge (Khan et al., 2019; Mu Since MXene plays the role of electron donors, providing the
et al., 2018; Shahzad et al., 2017). Due to their electrostatic prop- adsorbed Cr2O2 7 electrons, Cr(VI) is reduced, thus leading to a
erty, various ions of heavy metals and radionuclides could be reduction in the hazards associated with Cr. MXene is not only
removed by MXene since they are oppositely charged to the MXene effective in the reduction of Cr, but also Fe, Mn, and Au, in the forms
functional groups. Thus, there is electrostatic interaction between of K3[Fe(CN)6], KMnO4, and NaAuCl4, respectively (Ying et al., 2015).
MXene and inorganic contaminants which is the main adsorption Other studies on heavy metal adsorption by MXene have been
mechanism of MXene (Ying et al., 2015). Fig. 3 describes, with the conducted and most agree that the target contaminants are
aid of schematic diagrams, the adsorption of inorganic contami- oppositely charged to the synthesized MXene and can interact
nants by MXene. Although electrostatic interaction is the dominant electrostatically, thus enabling the adsorption process (Fard et al.,
mechanism for the removal of inorganic pollutants, other mecha- 2017; Li et al., 2019; Shahzad et al., 2019a; Wang et al., 2017a).
nisms, such as ion exchange (Peng et al., 2014; Shahzad et al., 2017; Another example of heavy metal adsorption is the use of alk-
Wang et al., 2016), and some factors, such as specific surface area, intercalated MXene (Ti3C2(OH/ONa)xF2-x) to remove Pb(II) in wa-
pH, and temperature, also greatly influence the adsorption process. ter in 5% NaOH solution for the intercalation of Na ions (Peng et al.,
Information regarding adsorptive removal of selected inorganic 2014). By XRD and EDX analysis, it was confirmed that Na ions were
contaminants by MXene nanomaterials is summarized in Table 1. successfully intercalated, and they expanded the space between
Heavy metal adsorption of Cr(VI) using 2D Ti3C2Tx MXene, layers, thus increasing the diffusion rate of the area which could
which was etched by HF solutions of different concentrations (10, react with Pb(II) ions. The obtained adsorption capacity was up to
25, and 50 wt %) and sonicated to exfoliate the respective layers, 140 mg g1, which is considered high compared to the capacities of
was carried out (Ying et al., 2015). Confirmed by Bru- other conventional Pb(II) adsorbents. Also, the alk-MXene attained
nauereEmmetteTeller (BET) results, the Ti3C2Tx-10% nanosheets equilibrium in 120 s, and this could be attributed to its ability to
turned out to have 57 m2 g1, the highest specific surface area react extraordinarily with Pb(II) because of its distinct formation.
among the fabricated MXenes used in this study, and pore volume The main mechanism used in this study was ion exchange, assumed
Fig. 3. (a) Schematic diagram of (a) thorium sorption onto Ti2CTx MXene (Li et al., 2019), (b) the adsorption of radioactive barium ions (Mu et al., 2018), (c) the removal mechanism
of Cr(VI) by the Ti3C2Tx nanosheets (Ying et al., 2015), and (d) hydrated intercalation synthesis strategy of Ti3C2Tx MXene for efficient U(VI) uptake and imprisonment (Wang et al.,
2017a).
Table 1
Summary of adsorptive removal of selected inorganic contaminants by MXene nanomaterials.
MXene Species Co (mg L1) Experimental condition qm (mg g1) Main finding Ref.
Ti3C2Tx Ba 1e55 pH 3-9 9.3 The maximum adsorption capacity at Fard et al. (2017)
temp. ¼ 298 K Ba ¼ 55 mg L1 is 9.3 mg g1, which is much greater
synthetic water value than those of other adsorbents.
Ti3C2Tx Cu 25 pH 2-6 86.5 Compared to a commercial activated carbon, the Shahzad et al. (2017)
temp. ¼ 293e318 K adsorption capacity of Ti3C2Tx was nearly three
synthetic water times higher.
Ti3C2Tx U 100 pH 5 214 Owing to the flexibility and large interlayer space, Wang et al. (2017a)
temp. ¼ 293 K the adsorption of U(VI) on hydrated Ti3C2Tx was
synthetic water significantly enhanced, compared to dry Ti3C2Tx.
Magnetic Ti3C2Tx Hg 25-1000 pH 2-9 1128 Magnetic Ti3C2Tx has much better maximum Hg(II) Shahzad et al. (2018)
temp. ¼ 288e318 K adsorption capacity than other two dimensional
synthetic water nanocomposite and nano-materials.
Ti3C2(OH)0.8F1.2 Cr 10 pH 3-6 62 MXene which is chemically exfoliated in solutions Zou et al. (2016)
temp. ¼ 298 K having F ions consequently has the surface covered
synthetic water with F groups
Sodium alginate/Ti3C2Tx Cu 0e10 mM pH 1-7 87.6 By having abundant adsorption sites, the MXene/ Dong et al. (2019b)
Pb temp. ¼ 298e333 K 383 alginate composite was able to achieve high
synthetic water adsorption capacity of selected inorganic
compounds and reach equilibrium in 15 min.
Ti2CTx-hydrated Th(IV) 5e180 pH 1e3.5 213 Inner-sphere complexation from strong attraction Li et al. (2019)
temp. ¼ 282e312 K between TieOH and Th(IV) is the mechanism for
synthetic water removal of Th(IV) by Ti2CTx in water.
MX-SA2:20 Hg 25e994 pH 0-11 365 Owing to high binding capacity and an affinity for Shahzad et al. (2019a)
MX-SA4:20 temp. ¼ 298 K 933 Hg2þ, MX-SA4:20 adsorbed Hg2þ extraordinarily
synthetic water well even under very acidic conditions (pH < 0).
e-TACSs Pb(II) 200 pH 2-11 218 The fabrication of e-TACFs and e-TACSs was Gu et al. (2018)
e-TACFs temp. ¼ 298e328 K 284 performed via a hydrothermal and fluoride-free
synthetic water method and the adsorption capacity for Pb(II) was
significantly high.
Ti3C2Tx-10% Cr(VI) 208 pH 2-13 250 The Cr(VI) could be effectively reduced to less toxic Ying et al. (2015)
temp. ¼ RT Cr(III) species and the residual Cr(VI) in treated
synthetic water water was far below the drinking water standard
recommended by the World Health Organization.
Alk-Ti2Csheet Cd 19.6e562 pH 2-9 326 Ti2AlC MAX phase which is exfoliated with NaOH, Shahzad et al. (2019b)
temp. ¼ RT fluoride-free, could successfully adsorb both heavy
synthetic water metals and other contaminants.
Ti3C2Tx-DMSO-hydated U 5e220 pH 2-6 214 Hydrated and intercalated MXene adsorbed dye Wang et al. (2017a)
temp. ¼ RT chemicals and heavy metal ions more considerably
synthetic water and their application is considered greatly
favorable.
Ti3C2Tx Cs 5e300 pH 2-12 25.4 The obtained maximum adsorption capacity of Csþ Khan et al. (2019)
temp. ¼ 273e303 K removal on Ti3C2Tx is due to the reaction at room
synthetic water temperature within 1 min which is more effective
than other adsorbents.
Ti3C2Tx Ba 50e500 pH 1-10 12 The maximum adsorption capacity of Ba2þ on Alk- Mu et al. (2018)
Alk-Ti3C2Tx temp. ¼ RT 46.5 Ti3C2Tx was 46 mg g1 which is approximately three
synthetic water times greater than unmodified Ti3C2Tx, presenting
important selectivity of Ba2þ among other
inorganics.
Mxene-25 Pd 100 pH 0-5 119 The interlayer structure and morphology of MXene Mu et al. (2019)
Mxene-35 temp. ¼ 293e313 K 164 nanomaterials are greatly affected by the exfoliation
Mxene-45 synthetic water 185 temperature and the higher exfoliation
temperature could yield larger d-spacing and
surface area.
Ti3C2Tx Cr 100 Kinetic ¼ 14 h temp. ¼ 298 K 80 A constant adsorption capacity (80 mg g1) can be Tang et al. (2018)
synthetic water achieved by accordion-like Ti3C2 materials when
msorbent/Vsolution was 1 g L1, achieving equilibrium
in 8 h.
K-HTNs Eu(III) 20e300 pH 2-10 203 Owing to electrostatic interaction and H bonding, Zhang et al. (2019a)
Na-HTNs temp. ¼ 298 K 222 Eu(III) could be exchanged with cations in the active
synthetic water sites on MXene, therefore causing improved
sorption.
MTC-P Re(VII) 5e400 Kinetic ¼ 6 h pH 1e10 42.1 The modification of Ti2CTx nanosheets produced Wang et al. (2019)
TCNS-P synthetic water 363 high advantage in terms of Re(VII) removal, causing
that the application of this technique on Tc(VII)
removal can have potential possibility.
Ti2CTx U(VI) 5e400 Kinetic ¼ 100 h pH 1e10 470 Over a wide pH range, the adsorbent well-adsorbed Wang et al. (2018)
synthetic water and decreased U(VI), reaching equilibrium within
48 h and the adsorption capacity at pH 3 with
C0[U(VI)] over 160 mg L1 was 470 mg g1.
Alk-MXene Pb(II) 10e300 pH 1-7 140 The adsorbent achieved equilibrium within 2 min Peng et al. (2014)
temp. ¼ 293e325 K and exhibited high adsorption performance with
synthetic water large adsorption capacities, rapid and reversible
adsorption reaction.
(continued on next page)
Table 1 (continued )
MXene Species Co (mg L1) Experimental condition qm (mg g1) Main finding Ref.
DL-Ti3C2Tx Cu 10e350 pH 2e5.5 78.5 Owing to large surface area, functional groups and Shahzad et al. (2017)
temp. ¼ 298e318 K dispersibility, strong adsorption of Cu was observed
synthetic water and it achieved equilibrium within 3 min.
V2CTx U(VI) 5e120 pH 3-5 174 (qe) The dominant adsorption mechanism is ion- Wang et al. (2016)
temp. ¼ RT exchange and, using multilayered V2CTx, it achieved
synthetic water equilibrium after 4.5 h with different functional
groups on surface. The maximum adsorption
capacity (174 mg g1) was achieved at pH 5 when
C0[U] was 100 mg L1.
Co ¼ initial concentration; qm ¼ maximum adsorption capacity; temp. ¼ temperature; SA ¼ sodium alginate; TACSs ¼ Ti3AlC2 nanosheets; TACFs ¼ Ti3AlC2 nanofibers;
DMSO ¼ dimethyl sulfoxide; HTNs ¼ hierarchical titanate nanostructures; PDDA ¼ poly(diallyldimethylammonium chloride); MTC-P ¼ multilayered Ti2CTx/PDDA composite;
TCNS-P ¼ Ti2CTx nanosheet/PDDA composite; DL ¼ delaminated.
from the elemental compositions of used alk-MXene and XPS result could be because Ba2þ ions were captured on the alk-MXene
analysis. The elemental composition confirmed that several ele- in exchange for Naþ ions; the MXene has higher affinity for Ba2þ
ments including Ti, F, Na, O, and Pb were present, and it is plausible than Hþ or Naþ, thus leading to successful Ba2þ adsorption. The
that intercalated Hþ or Naþ ions, attached to the negatively charged decrease of Na on the surface of alk-MXene could also be explained
TieO, would be exchanged with Pb(II) (Giammar et al., 2007). In by the XPS results, since the peak of Na on the alk-MXene became
addition, by observing the XPS spectra, particularly the emergence weakened after Ba2þ adsorption, again owing to the ion exchange
of the peak of Pb and the disappeared Na 1s peak after adsorption, process (Mu et al., 2018). Although there are not very much studies,
ion exchange could be considered the mechanism in this adsorp- particularly experimental studies, on the adsorption of radionu-
tion process (Peng et al., 2014). This is in good agreement with clides and radioactive elements besides U adsorption (Zhang et al.,
several other Pb adsorption studies which demonstrate that ion 2016, 2017, 2018), some studies were conducted on the analogues
exchange is the adsorption mechanism of Pb (Gu et al., 2018; Zhao of radionuclides, such as Eu(III) and Th(IV) (Li et al., 2019; Zhang
et al., 2011). et al., 2019a). Th(IV) adsorption on MXene was explored, and
Besides heavy metals, radionuclides could also be adsorbed by Ti2CTx, etched with LiF/HCl, was used as an adsorbent (Li et al.,
various synthesized MXenes owing to their solid resistance against 2019). Compared to the dry adsorbent sample, much greater up-
radiation (Mu et al., 2018; Wang et al., 2016, 2017a). One of the most take capacity of Th (158 mg g1) was achieved by Ti2CTx-hydrated
well-known radionuclide species is uranium, and several studies due to the increase in the space between layers, caused by the
have dealt with the removal of U(VI) using MXene. Experiments intercalated water molecules. The adsorption followed pseudo-
were conducted to investigate the removal of U(VI) by hydrated and second order and Freundlich model, and regarding the adsorption
dry Ti3C2Tx, which was HF-etched and intercalated with NaOH, mechanism, Ti2CTx-hydrated could electrostatically adsorb posi-
dimethyl sulfoxide, or none (Wang et al., 2017a). The main mech- tively charged Th(IV) because of its functional groups; considering
anism of this U adsorption is electrostatic interaction, but consid- the decrease of the solution pH after the adsorption process, we can
ering that there was not much difference between the zeta conjecture that hydrogen ions were exchanged with Th(IV) by be-
potentials of both the original Ti3C2Tx and intercalated Ti3C2Tx, the ing released to water. Similar trends were often encountered in
main influencing factor, in this case, could be the surface area and other studies regarding the sequestration of metal ions by MXenes
the space in between the layers. Comparing the c lattice parameters (Mu et al., 2018; Peng et al., 2014), suggesting that the analysis is in
of the pristine Ti3C2Tx and the intercalated MXenes, the dry pristine the right track (Li et al., 2019).
MXene had the smallest c lattice parameter of 0.152 nm, whereas MXene is intrinsically positively charged under very acidic
the parameters of the hydrated Ti3C2Tx-NaOH and Ti3C2Tx- environment and negatively charged above pHpzc, which could lead
dimethyl sulfoxide greatly increased up to 1.228 nm and 2.018 nm. to the adsorption of oppositely charged contaminants highly
The results show that adsorption performance could greatly be affected by pH. In other words, anions can be removed by positively
influenced by intercalation and hydration of MXene. Supporting charged MXene at very low pH, but it is hard to apply since the
the aforementioned results, the hydrated Ti3C2Tx, intercalated with water quality of very low pH is not general. However, Ti2CTx was
dimethyl sulfoxide, achieved the highest adsorption capacity of fabricated in order to treat ReO 4 , which has some similarity with
160 mg g1, reaching equilibrium in approximately 6 h, out of all TcO4 , the ultimate target, so that related concept and insight could
the adsorbents owing to its larger surface area, which meant it had be obtained (Wang et al., 2019). The pristine MXene was modified
more reactive sites on the surface. The adsorption was well with diallyldimethylammonium chloride, making the material
explained by the Freundlich model, which can also mean that it has positively charged at a wide range of pH. Both multilayered and
heterogenous adsorption sites which are the various surface func- single-layered Ti2CTx modified with diallyldimethylammonium
tional groups in this case (Wang et al., 2017a) A separate study chloride possessed positive charges at pH from 1 to 10, which was
explored the adsorption of the radioactive Ba2þ ions, a homologue confirmed by their zeta potential values, compared to the non-
of 226Ra, by alk-Ti3C2Tx through ion exchange mechanism (Mu et al., modified MXene with pHpzc around 2 to 3. In particular, nano-
2018). The specific surface area of the alk-Ti3C2Tx, immersed in 5% sheets of the modified MXene, although with a smaller surface area
NaOH, was 76.4 m2 g1 whereas that of the pristine MXene was (18 m2 g1) than those of the unmodified one (31 m2 g1) because
9.78 m2 g1, and this increase surface area due to immersion in of the presumable diallyldimethylammonium chloride connecting
NaOH enlarged the interspace of the MXene, as was also the case in the nanosheets, exhibited better adsorption performance over the
other studies (Li et al., 2019; Mu et al., 2018; Peng et al., 2014; Wang wide range of pH from 1 to 10 than the unmodified nanosheets of
et al., 2017a). After the adsorption process involving alk-Ti3C2Tx, it the MXene, in which it could be assumed that electrostatic inter-
was found that the concentration of Naþ ions slightly increased and action was the dominant adsorption mechanism. Also, as an
there was a marginal change in the concentration of Hþ ions. This extension of adsorption, it was confirmed that some of the Re(VII)
adsorbed as ReO 4 were reduced to Re(IV), probably in the form of environment, but also a very limited option. By analyzing the zeta
ReO2, by diallyldimethylammonium chloride (Wang et al., 2019). potential value of the modified Ti2CTx nanosheets, the charge on
Reduction of inorganic ions can be found in several other studies the MXene was found to be constantly positive regardless of pH
(Wang et al., 2018; Ying et al., 2015). value varying from 1 to 10, which was necessary to adsorb Re(VII)
anions in the form of ReO 4 . Subjecting the MXene to very low pH
3.2. Effects of water quality would have adversely affected its stability owing to the dissolution
of Ti. However, after the modification, the extent of dissolution
3.2.1. pH slightly decreased, which implies that the modification enhanced
The pH value is one of the most influential factors that affect the stability of the diallyldimethylammonium chloride. In terms of
adsorption. Since the value is related to the concentration of posi- their adsorption performance, the modified multilayered Ti2CTx
tively charged Hþ in water, it could affect the surface charge of achieved much less adsorption capacity with increase in the solu-
MXene and the adsorptive efficiency of its surface functional tion pH than the modified Ti2CTx nanosheets since the external
groups. Under a low pH value, below pH 2 for example, abundant surface area that could react with diallyldimethylammonium
Hþ ions could react, competing with positively charged ions of the chloride was reduced. Therefore, the unmodified inner layers of the
target compounds, with negatively charged functional groups, such multilayered Ti2CTx could remain negatively charged, thus causing
as eO, eOH, and eF, in water and eventually protonate the surface electrostatic repulsion (Wang et al., 2019).
of MXene (Shahzad et al., 2017). The protonated MXene would be
no longer negatively charged, which means that electrostatic 3.2.2. Background ions and NOM
attraction would not occur any longer unless the MXene is depro- In order to examine the practicality of MXene-based adsorbent
tonated (Gu et al., 2018). However, under high pH, there would be and if it is appropriate for the removal of specific target compounds
less concentration of Hþ, therefore MXene could remain negatively in the presence of other ions and NOM which exist in municipal/
charged. This can be confirmed by measuring the zeta potential industrial wastewater or effluent, the effect of background ions and
value for various pH. Generally, if the pH is below pHpzc, which is NOM, such as humic acid, was investigated. For an adsorbent to be
the specific pH at which the zeta potential value is 0, the zeta po- considered effective for the removal of a target compound, it must
tential value of MXene is positive, and if the pH becomes higher have a higher selectivity and affinity for the target material than
than pHpzc, the value of the zeta potential becomes lower, which other competing background ions (Mu et al., 2018; Wang et al.,
could probably be affected by functional groups on the surface of 2017a). In general, MXene-based adsorbents have high affinity for
MXene (Wang et al., 2019). Higher pH value is not always preferred divalent cations, compared to monovalent cations, and the exis-
for heavy metal adsorption. Since, at high pH, metal ions could react tence of humic acid in water may yield slightly better adsorption
with abundant amounts of hydroxide in water, although higher pH performance owing to a bridge effect (Jun et al., 2020b; Mu et al.,
could induce more negatively charged MXene, the metal adsorp- 2018; Peng et al., 2014).
tion performance of MXene could be less effective at high pH (Fard Since several water resources are hard, including wastewater,
et al., 2017). the effect of Ca2þ and Mg2þ on adsorption by MXene in terms of ion
One of the typical examples showing the effect of pH is the competition is considered worthy of attention. The affinity of alk-
experiments on Pb2þ adsorption by MXene nanofiber sheets (Gu Ti3C2Tx for several positively charged ions was tested: Ca2þ, Mg2þ,
et al., 2018). At low pH, pH less than pHpzc in particular, the zeta and the target ion, Pb2þ (Peng et al., 2014). The result shows that
potential of MXene was positive, which means that the MXene was alk-MXene had higher selectivity for Pb2þ than Ca2þ or Mg2þ,
unlikely to adsorb Pb ions by electrostatic interaction. The results of which is attributed to relatively low hydration energies of Pb2þ
the adsorption experiments also confirmed that below pHpzc the than the other cations. This was compared with the result of
removal percentage was low, compared to the percentage at higher adsorption by ion exchange resin, and even though the initial
pH. However, as the pH went higher than pHpzc, the adsorption rate removal rate of the resin without competing cations was higher
increased up to pH 7, and from pH 7 the removal rate fairly than that of the MXene, overall uptake of Pb ions significantly
decreased, and this could be explained by the possible reaction of decreased with increase in the concentration of Ca or Mg ions (Peng
Pb ions and hydroxides to form metal hydroxide salts (Gu et al., et al., 2014). Similar studies have been conducted regarding the
2018). These results are in good agreement with other studies on competition of cations including Ca(II) and Mg(II), and one is a
the adsorption of inorganic contaminants (Khan et al., 2019; Li research on U(VI) removal and the possible influence of various
et al., 2019; Mu et al., 2018; Shahzad et al., 2018; Wang et al., cations (Wang et al., 2017a). The hydrated Ti3C2Tx-dimethyl sulf-
2017a, 2018; Zhang et al., 2019a). Not always is the charge on oxide showed great selectivity for U(VI) among various metal ions
MXene negative for the adsorption of inorganic contaminants in such as Co, Ni, Zn, Sr, La, Nd, Sm, Gd, and Yb, and the same result
water; positively charged MXene could capture negatively charged was also obtained in the experiment with Naþ, Mg2þ, and Ca2þ,
target contaminants. In the study on Cr(VI) removal (Ying et al., which aimed for any influence caused by ion strength (Wang et al.,
2015), since the surface charge of Ti3C2Tx-10% became positive 2017a). Another study focusing on the competing effect of cations
when the solution pH was below pHpzc, pH 2.4 in this case, the ionic explored the impact of cations such as Ca2þ, Mg2þ, Sr, La, and Ce,
form of Cr(VI), which is Cr2O2 7 , was attracted to the protonated which are regarded as typical ions in nuclear industry effluent, on
functional groups of the MXene. Also, if Cr(VI) acquired enough Hþ Ba2þ adsorption by MXene and alk-MXene (Mu et al., 2018). It was
and electrons, it could be converted to Cr(III), and at low pH, Hþ shown that both MXene and alk-MXene achieved high removal rate
ions were abundant and electrons could be provided from MXene, of Ba2þ, compared to their removal rates for the other cations, and
thus offering conditions conducive for Cr(VI) to be converted to the in particular, alk-MXene showed almost more than 95% efficiency
less hazardous Cr(III) (Ying et al., 2015). while MXene achieved less than 80% efficiency for Ba2þ adsorption,
In one study, adsorption by MXene was almost independent of which was still higher than for the other cations. Thus, they
pH value, that is the MXene remained positively charged from pH 1 concluded that since Ba has a smaller radius, it could be more likely
to 10. The research, on Re(VII) anion adsorption by modified for Ba ions to enter the interlayers, increasing reactive sites, and the
MXene, was conducted, using positively charged Ti2CTx modified adsorbent could have a greater affinity for the divalent ions, which
with diallyldimethylammonium chloride (Wang et al., 2019). is in good agreement with the findings of the previously mentioned
Adsorbing anions with MXene is possible under very acidic study (Mu et al., 2018; Peng et al., 2014).
To study anion adsorption on MXene and the influence of rises, standard free energy decreases, but enthalpy and entropy
background ions, the selectivity of diallyldimethylammonium increase. A positive value of standard enthalpy change indicates
chloride for rhenium was tested (Wang et al., 2019). Dia- that the adsorption reaction is endothermic, a positive value of
llyldimethylammonium chloride showed a much higher selectivity standard entropy change implies that the reaction is feasible, and a

for Re ions than for SO2 4 and Cl in the presence of Re ions and negative value of standard free energy change indicates a sponta-
other anionic ions such as SO4 , Cl, ClO
2
4 , and NO3 at pH 4, neous reaction. According to the general trend of thermodynamic
considering the distribution coefficient of more than analysis, higher temperature may be beneficial to adsorption
2.1 104 mL g1. However, the adsorption capacity of dia- process.
llyldimethylammonium chloride for Re ion, when compared with The effect of temperature on adsorption reaction has been
its capacity for ClO
4 and NO3 , decreased considerably due to, for widely explored in several studies (Khan et al., 2019; Li et al., 2019;

ClO4 , its ionic radius, similar chemical formation with Re ion, and Shahzad et al., 2017, 2018). Experiments were carried out to
energy of hydration. In sum, NO 3 turned out to be the most investigate the effect of temperature on Pb adsorption by Ti3C2-
competitive and inhibiting ion, followed by ClO 2
4 , Cl , and SO4 , in based nanomaterials etched with NaOH (Gu et al., 2018). The study
the removal of Re ions (Wang et al., 2019). showed that the adsorbent performed better at a higher tempera-
Effects of background ions on U(VI) sequestration and reduction ture, demonstrated by carrying out experiments to obtain adsorp-
by Ti2CTx were explored using synthesized acidic wastewater from tion isotherms at three different temperatures: 298, 313, and 328 K.
mine industries (Wang et al., 2018). In the synthesized solution, The achieved qe value under the lowest temperature was lower
various ions, including U, Naþ, Mg2þ, Ca2þ, Fe3þ. Al3þ, SO2 4 , and than the qe values achieved at the higher temperatures. In detail,
NHþ 4 , were present with the MXene, and the experiments were the qe value at 298 K was 286 mg g1, compared to the values of
conducted under aerobic and anaerobic conditions. A removal rate 380 mg g1 and 549 mg g1 achieved at 313 K and 328 K, respec-
of more than 99% was achieved, while competing for other cations, tively. In order to demonstrate this relationship, thermodynamic
under anaerobic condition for 2 d, which may be an indication that analysis was carried out by calculating thermodynamic parameters.
the MXene had high selectivity for U. The result regarding the U ion The positive value of enthalpy change and entropy change showed
selectivity of MXene is in good agreement with the previous study that the adsorption reaction was endothermic process with high
on U capture using V2CTx, which exhibited great selectivity for U likability. Also, the negative value of free energy change showed
among other various metal cations, bolstered by the selectivity that the reaction was spontaneous and bolstered the analysis of
coefficient value, which was above 10 (Wang et al., 2016). However, temperature preference by presenting lower values of free energy
in the presence of dissolved oxygen, the reduced U(IV), adsorbed on change as temperature increased (Gu et al., 2018). A similar study
the MXene, was released to some extent as time passed, confirmed showed the temperature preference of adsorption reaction, but
by the reduced removal rate below 50% after 20 d. This could be explained that the trend could not be related to the effect of tem-
attributed to the oxidation by the dissolved oxygen of U(IV) to perature (Dong et al., 2019b). The study investigated the effect of
U(VI), which is soluble in water and whose solubility could have temperature on the adsorption of Pb and Cu ions by Ti3C2/alginate
jeopardized both its reduction and sequestration. The effect of Fe adsorbent and observed an increasing trend of adsorption at the
ions, under the aforementioned conditions, on U reduction was also temperature range from 298 to 333 K. An approximately 10% in-
examined, and it turned out that the trend of release of U(VI) under crease in adsorption was observed for a 35 C total increase in
aerobic condition was initially affected by Fe ions, occurring at a temperature. It was concluded that the increase was not significant
slightly more rapid pace than it did in the absence of Fe ions, until and that the adsorbent’s distinct structure could have contributed
13 d of reaction time had elapsed. However, after 15 d or so, the to the marginal result by ensuring that its adsorption mechanism
removal rate of U(VI) showed insignificant difference from the rate was less dependent on temperature (Dong et al., 2019b).
when Fe ions were absent, suggesting the Fe ion slightly affects U A study focused on the effect of temperature on Pb adsorption
sequestration (Wang et al., 2018). by 2D MXene exhibited a behavior different from the general trend.
The effect of NOM on adsorption reactions involving MXene has Experiments were conducted at 293, 303, and 313 K in order to
been explored. One of the studies focused on the effect of humic investigate the effect of temperature on MXene Pb adsorption (Mu
acid on Pb2þ adsorption by MXene (Jun et al., 2020b). They con- et al., 2019). Interestingly, the values of enthalpy and entropy
ducted experiments by varying the concentration of humic acid change were negative, unlike in other studies. For MXene-25, -35,
from 0 to 10 mg L1 and examined Pb2þ adsorption efficiency and and 45, 22.36, 22.24, and 23.10 kJ mol1 were the respective
capacity (qe) of Ti3C2Tx. According to the result, there was an in- enthalpy changes and 66.34, 62.91, and 63.04 J mol1 were the
crease in the efficiency and qe value as the concentration of humic respective entropy changes. Accordingly, the calculated values of
acid increased. They explained that the phenomenon might be the free energy change were negative, and the values of the free
attributed to the bridging effect of humic acid; since the behavior of energy change for all the three synthesized MXenes increased
humic acid resembles that of divalent anions at pH 6, humic acid approximately by 1.3 kJ mol1 on average, while the temperature
might be able to bind to Pb ions, making connections like a bridge, increased from 295 to 313 K. In sum, all the three thermodynamic
which favored Pb2þ adsorption. The result is similar to the effect of parameters turned out to be negative, which means that the
divalent anions on adsorption by MXene, and the bridge effect is adsorption reaction was spontaneous, exothermic and reversible
also mentioned in other studies (Jun et al., 2020b; Liu et al., 2018b). (Mu et al., 2019).
3.3.3. Temperature 4. Removal of organic contaminants by MXene nanomaterials

Temperature affects physical and chemical reactions. Increase in
temperature generally leads to increased adsorption capacity. In 4.1. Effects of contaminant and MXene properties
order to evaluate the effect of temperature on adsorption, standard
enthalpy, standard entropy, and standard free energy, which may Organic contaminants can also be removed from water by
be obtained by Gibbs free energy equation, can be used to verify the MXene-based adsorbents. Typical organic contaminants are dye
characteristics of the adsorption process, such as whether it is compounds. Since MXene-based adsorbents are negatively charged
endothermic/exothermic, spontaneous/nonspontaneous, and etc. in general, positively charged dye compounds, such as methylene
(Gu et al., 2018; Khan et al., 2019; Li et al., 2019). When temperature blue, can be effectively removed from water. There are a few
Fig. 4. (a) Plausible schematic diagram for adsorption mechanisms of methylene blue (MB) and acid blue 80 (AB) by MXene (Jun et al., 2020a). (b) Proposed mechanism for the
adsorption of MB on the surface of MXene@Fe3O4 (Zhang et al., 2019b). (c) Schematic illustration of the fabrication of MXene-COOH and layer-by-layer -assembled composites by
chemical modification and layer-by-layer self-assembly (Li et al., 2018). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version
of this article.)
adsorption mechanisms, frequently mentioned in several studies similar surface areas or structures. On the other hand, acid blue 80
on dye adsorption by MXene, which are electrostatic interaction was not adsorbed on the MXene since the dye is negatively charged,
(Huang et al., 2019; Meng et al., 2018; Rozmysłowska- like the adsorbent, causing electrostatic repulsion. After 2 h of
Wojciechowska et al., 2019), ion exchange (Wei et al., 2018), and adsorption of methylene blue, the adsorption reaction weakened
etc. In Fig. 4aeb, mechanisms of adsorption of dyes by MXene are over time, and this may be attributed to the oxidation of MXene and
illustrated. The adsorption reaction of organic contaminants, like change in the structure of the adsorbent owing to the intercalation
the removal of inorganic contaminants, is highly influenced by of the adsorbate molecules, which resulted in flawed stacking
water quality parameters such as pH, temperature, and the pres- (Mashtalir et al., 2014).
ence of background ions and NOM; the effect of these parameters is The effect of intercalation on methylene blue adsorption was
explained in the following section. Besides dye contaminants, more explored with three adsorbent (MXenes) kinds: Ti3C2Tx-hydrated,
research on the removal of different organic contaminants, such as Ti3C2Tx-dimethyl sulfoxide-hydrated, and Ti3C2Tx-dry (Wang et al.,
urea (Meng et al., 2018), lysozyme (Rozmysłowska-Wojciechowska 2017a). Comparing the adsorption capacity of the adsorbents, it was
et al., 2019) and deoxyribonucleic acid (Huang et al., 2019), has observed that Ti3C2Tx-dimethyl sulfoxide-hydrated achieved an
been explored for various potential applications. In addition, the uptake capacity of 125 mg g1, showing 99.8% removal of methy-
removal of organic contaminants by gaseous adsorption on MXene lene blue, which was much higher than the 78 mg g1 achieved by
has been investigated for the adsorption of air pollutants such as Ti3C2Tx-hydrated and the 8 mg g1 by Ti3C2Tx-dry. The enlarged
aroma molecules (Ciou et al., 2019), carbon dioxide (Morales-García space between layers brought about by the effect of the intercala-
et al., 2018), and methane (Liu et al., 2016, 2017a). Table 2 presents tion with dimethyl sulfoxide resulted in the availability of more
the adsorptive removal of selected organic contaminants by MXene adsorption sites for the methylene blue molecules. The intercala-
nanomaterials. tion of dimethyl sulfoxide could also have led to the co-
Dye adsorption on MXene was exhibited, which used methylene intercalation of methylene blue, thus expanding the space be-
blue and acid blue 80 as adsorbates and Ti3C2Tx as the adsorbent tween layers even more. Water molecules might have played the
(Mashtalir et al., 2014). The dyes, methylene blue and acid blue 80, role of intercalant for Ti3C2Tx-hydrated, leading to a reasonable
were representative of cationic and anionic dye, respectively. From adsorption performance much greater than that of Ti3C2Tx-dry
the analysis of the adsorption isotherm it was found that the (Mashtalir et al., 2014). Intercalation using the alkaline solutions,
adsorption of methylene blue followed the Freundlich isotherm LiOH, NaOH, and KOH, was also found to affect methylene blue
model more than Langmuir isotherm model, and this conclusion adsorption on Ti3C2Tx (Wei et al., 2018). Based on the ionic radius of
was arrived at after comparing the Pearson’s correlation co- Li, Na, and K, the ion having a smaller radius, such as Liþ and Naþ,
efficients of both isotherm models. Following the Freundlich model could be loaded more than the one having a larger radius, Kþ in this
may imply that the adsorbent had heterogenous adsorption sites, case; Na ions and Li ions were likely to be piled twice or thrice
and this is supported by the fact that various functional groups, while K ions might hardly stack once. This resulted in the difference
such as eF, -OH, and eO, of the MXene took part in the adsorption in the enlarged spaces in between the layers of the MXenes for the
reaction. The adsorption capacity of methylene blue was up to adsorbents treated with KOH, NaOH and LiOH, confirmed by their
39 mg g1, which is smaller than the that of commercially available respective c lattice parameters of 2.49, 2.62, and 2.64 nm. On the
activated carbon but comparable to those of adsorbents with other hand, the adsorption performance of the three MXenes did
Table 2
Summary of adsorptive removal of selected organic contaminants by MXene nanomaterials.
MXene Species Co (mg L1) Experimental condition qm (mg Main finding Ref.
g1)
Ti3C2Tx Methylene 50 Kinetic ¼ 8 h temp. ¼ 293 K 38.9 The adsorption of methylene blue on Ti3C2Tx Mashtalir et al.
blue synthetic water was not extremely effective, compared to (2014)
activated carbon, but, considering its unique
properties and possible application, Ti3C2Tx
could be decent adsorbent.
Ti3C2Tx Methylene 50 Kinetic ¼ 3 h temp. ¼ 298 K 99.9 The alkali-treated adsorbent has enhanced Wei et al. (2018)
LiOHeTi3C2Tx blue synthetic water 121 interlayer spacing and surface functional group,
NaOHeTi3C2Tx 189 resulting in improved adsorption performance.
KOHeTi3C2Tx 77
Ti3C2Tx Urea 30e450 mg/ Kinetic ¼ 1 h temp. ¼ RT-333 K 21.7 The qm (21.7 mg g1) was calculated by Meng et al. (2018)
dL synthetic water/Dialysate Langmuir-Freundlich model at 310 K. The
finding exhibited rapid and selective adsorption
of urea on MXene and the adsorption capacity
reached 94%, showing no important impact on
cell viability and hemocompatibility.
Ti3C2Tx Methylene 5e40 pH 3.5e9.5 140 MXene achieved equilibrium in a short amount Jun et al. (2020a)
blue temp. ¼ 293e313 K of time (within 30 min) and the main
synthetic water mechanism of the adsorption was electrostatic
interaction between MXene and Methylene
blue.
Ti3C2Tx-dry Methylene 100 Kinetic ¼ 6 h temp. ¼ RT 8 Important MB adsorption capacity was Wang et al. (2017a)
Ti3C2Tx-hydrated blue synthetic water 78 exhibited in the adsorption result of Ti3C2Tx-
Ti3C2Tx-DMSO-hydrated 125 DMSO-hydrated, up to 125 mg g1, compared to
other adsorbents.
MXene Methylene 10 Kinetic ¼ 200 min 86.8 The MXene-COOH@(PEI/PAA)n was employed Li et al. (2018)
MXene-COOH blue temp. ¼ 298 K 71 to determine the adsorption capability of three
MXene-COOH@(PEI/ synthetic water 82 different dyes and the target contaminants
PAA)10 were effectively adsorbed owing to its layered
structure and modified functional groups.
MXene@Fe3O4 Methylene 1e40 pH 3-11 11.7 The key mechanism in the pH above 5.1 is Zhang et al. (2019b)
blue temp. ¼ 298e328 K electrostatic force due to pHpzc of the adsorbent.
synthetic water In addition, other adsorption mechanism could
be owing to the Ti site and OH groups.
Ti3C2eSO3H Methylene 25e250 pH 2-12 723 The maximum adsorption capacity at Lei et al. (2019)
blue temp. ¼ 318e358 K C0[MB] ¼ 250 mg L1, 298 K and pH 7 was
synthetic water 723 mg g1. By exhibiting the different
adsorption capacity between pristine Ti3C2
(21 mg g1) and Ti3C2eSO3H (111 mg g1), it
proved that Ti3C2eSO3H can be an ideal
adsorbent.
Co ¼ initial concentration; qm ¼ maximum adsorption capacity; temp. ¼ temperature; PEI ¼ polyethylene polyimide; PAA ¼ poly acrylic acid.
not follow the increasing order of the expanded spaces, as polyimide/poly acrylic acid)10 achieved the highest adsorption ca-
confirmed by the isotherm experiment; NaOHeTi3C2Tx achieved pacity among the three prepared adsorbents, followed by MXene-
the highest adsorption capacity of 189 mg g1, followed by COOH, and then the pristine material. The result followed the
LiOHeTi3C2Tx (121 mg g1), pristine Ti3C2Tx (100 mg g1), and pseudo-second-order kinetic model and showed that the reaction
KOHeTi3C2Tx (77 mg g1). The result of the LiOH-treated MXene was affected by increase in temperature, confirmed by the results
indicates that the expansion of the interlayer spaces led to the obtained for conducting the adsorption experiments at tempera-
exfoliation of the layers, thus causing the MXene to experience no tures of 298, 308, and 318 K. From the analysis of the adsorption
effect due to the intercalation of the cations and, accordingly, isotherm model it was found that the pristine MXene and MXene-
decreasing the adsorption capacity more than expected. It was COOH followed the Freundlich isotherm model, as confirmed by the
concluded, for KOHeTi3C2Tx, that the enlarged space might inhibit R2 value. However, MXene-COOH@(polyethylene polyimide/poly
complete activation of the adsorbent (Wei et al., 2018). acrylic acid)10 followed the Langmuir isotherm model, indicating
The adsorption of three kinds of dye compounds by MXene- that the reaction was a monolayer adsorption and the adsorbent
based nanocomposites modified by layer-by-layer strategy was had homogeneous adsorption sites (Li et al., 2018).
investigated (Li et al., 2018). Pristine MXene was first treated with
chloroacetic acid to obtain a COOH-modified surface, and then
immersed in polyethylene polyimide and poly acrylic acid solutions 4.2. Effects of water quality
separately for multiple times in order to have several layers of
polyethylene polyimide and poly acrylic acid molecules obtaining 4.2.1. pH
3-dimensional formation. The schematic illustration of the fabri- The pH greatly affects the performance of MXene-based adsor-
cation process is shown in Fig. 4c. The fabricated material, MXene- bent in regard to the removal of organic compound. Basically, since
COOH@(polyethylene polyimide/poly acrylic acid)10, was utilized, the dominant mechanism of adsorption is electrostatic interaction,
as well as the pristine MXene and MXene-COOH, to examine and regardless of whether the contaminant is an organic or inorganic
compare the adsorption of methylene blue, safranin t, and neutral compound, the charges on the adsorbent and adsorbate are very
red. The result showed that MXene-COOH@(polyethylene important (Jun et al., 2020a; Lei et al., 2019). The pKa value of the
adsorbate and the pHpzc of the adsorbent can affect the adsorption
process, depending on the solution pH, and considering the general NaCl, CaCl2, and Na2SO4, were conducted, and in the experiments
trend, adsorption performance is enhanced as pH value increases. the concentrations of the reagents were varied (Jun et al., 2020a).
Under acidic conditions, MXene cannot be negatively charged The reagents were selected such that the different effects between
enough to attract positively charged adsorbates, since there is monovalent ions and divalent ions, if any, would be highlighted. As
competition for the MXene ions between the Hþ and adsorbate the concentration of NaCl increased from 300 to 1200 mS cm1, the
ions, such as methylene blue. Under alkaline conditions, owing to adsorption capacity of MXene and its removal rate of methylene
the sufficient negative charge of the adsorbent, more adsorption blue decreased, and this phenomenon might be attributed to
can be expected (Jun et al., 2020a; Lei et al., 2019). screening effect, which reduced the electrostatic attraction be-
The effect of solution pH on adsorption by MXene was examined tween the adsorbate and MXene. The divalent ions of CaCl2 and
using Ti3C2Tx as an adsorbent and methylene blue as an adsorbate Na2SO4 in this study showed a slightly different trend of result,
(Jun et al., 2020a). The experiments were conducted at solution pH depending on how the ions and adsorbate were charged. Due to the
of 3.5, 7, and 9.5, and it was observed that as the solution pH effect of the divalent cations, Ca2þ in this case, which was as a result
increased, the adsorption capacity and removal rate increased. This of the competition for MXene between the cations and methylene
demonstrates that the dominant mechanism was electrostatic blue, a decrease in the adsorption capacity and removal rate was
interaction, affected by pKa value of methylene blue and pHpzc of observed. On the other hand, the divalent anions, which are
Ti3C2Tx. Since methylene blue is positively charged at pH 3.1 and oppositely charged to the adsorbate, rarely affected the adsorption
has Cl, it can be attracted by a negatively charged adsorbent at the (Jun et al., 2020a).
same pH. And the pHpzc of the MXene was approximately pH 3, The effect of NOM was also evaluated in the same study; the
which led to the adsorption of methylene blue on the adsorbent in effect of humic acid on adsorption was explored (Jun et al., 2020a).
this study (Jun et al., 2020a). The effect of pH on adsorption was also Experiments were conducted in the presence of humic acid at
investigated, and the study employed Ti3C2eSO3H as an adsorbent concentrations of 0, 2.5, and 10 mg L1, and changes in the
and methylene blue as an adsorbate in water (Lei et al., 2019). The adsorption capacity and removal rate due to the varying concen-
investigation was conducted at pH 2 to 12, and the lowest trations of humic acid were observed. As the concentration of hu-
adsorption capacity of 49 mg g1 was achieved at pH 2 and the mic acid increased, the adsorption capacity of MXene and the rate
highest capacity of 145 mg g1 at pH 11. This relationship between of removal of methylene blue increased. The result may be
adsorption capacity and pH could be explained by the adsorption explained with the aid of the bridge effect, as mentioned in Section
mechanism applied in this reaction, which is electrostatic interac- 3.2.2., where the effect of humic acid on the adsorption of inorganic
tion. At low pH, in the abundance of H ions, there would be contaminants has been treated (Jun et al., 2020b; Liu et al., 2018b).
competition for the adsorbent ions between the hydrogen ions and Since humic acid has aromatic structure and carboxylic acid, which
adsorbate ions, leading to less adsorption capacity. On the other makes it likely to act as a multivalent anion, the effect of humic acid
hand, at high pH, the MXene-based adsorbent would be more on adsorption could be similar to the effect of background ions,
negatively charged due to more SO 3 on the surface, leading to its divalent anions in particular (Jun et al., 2020a).
higher attraction for the positively charged methylene blue in water
(Lei et al., 2019). 4.2.3. Temperature
An interesting study on the pH effect of methylene blue The effect of temperature on adsorption in water by MXene, like
adsorption by MXene was carried out (Zhang et al., 2019b). pH other factors, has been investigated and found to be substantial.
value was varied from pH 3 to 11 and the adsorption capacity at When temperature increases, the viscosity of water generally de-
each pH level was noted. Around 10 mg g1 of adsorption capacity creases, leading to greater diffusion in the system and, thus,
was achieved at pH 3 and 11, unlike in other studies. The adsorption increased possibility for adsorption (Lei et al., 2019; Zhu et al.,
capacity decreased from pH 3 until pH 7 and increased from pH 7 to 2019). Also, temperature can influence thermodynamic parame-
11; that is to say, the minimum adsorption capacity of around ters, including enthalpy, entropy, and Gibbs free energy. Increased
2 mg g1 was obtained at pH 7. Since high adsorption capacity was temperature results in a positive value of enthalpy change before
obtained below the pHpzc, which was pH 5.1 in this study, it is likely and after reaction, which indicates that the reaction is endo-
that the main adsorption mechanism at pH 3 was not electrostatic thermic. Furthermore, by evaluating values of entropy change and
interaction but hydrogen bonding. And the increasing trend of the Gibbs free energy change, it can be predicted if the reaction would
adsorption capacity from pH 7 may imply that the negatively be spontaneous or not (Jun et al., 2020a; Lei et al., 2019; Zhang et al.,
charged MXene, confirmed by the zeta potential analysis, attracted 2019b; Zhu et al., 2019).
the positively charged adsorbate. However, due to the possibility of The effect of temperature on the adsorption of contaminants in
hydrolysis of methylene blue at high pH, adsorption performance at water was evaluated, using Ti3C2Tx for the removal of methylene
high pH was slightly lower than at low pH (Zhang et al., 2019b). blue at the specific temperatures 293, 303, and 313 K (Jun et al.,
2020a). Analyzing for the adsorption capacity, it was found that
4.2.2. Background ions and NOM the adsorption process was enhanced and removal rate increased as
There is need to examine the interaction of adsorbate, adsor- temperature increased. This relationship was demonstrated by the
bent, and pre-existing ions in water for practical application. This is thermodynamic parameters: positive values of enthalpy and en-
because, in untreated water, including municipal and industrial tropy changes and negative value of Gibbs free energy change. The
wastewater, adsorption might be inhibited by pre-existing ions and positive value of enthalpy showed that the reaction was endo-
NOM, a typical example being humic acid (Jun et al., 2020b). As a thermic, and the positive value of entropy change referred to the
result, several studies have explored the effect of background ions, increased randomness. As the temperature increased from 293 to
related to ion strength, and NOM on adsorption reaction (Lian et al., 313 K, Gibbs free energy decreased e 8.99 kJ mol1 at
2015; Xu et al., 2008). The effect of background ions may vary 293 K, 9.79 kJ mol1 at 303 K, and 10.51 kJ mol1 at 313 K e
depending on their charges, and it has been found that the presence showing that higher temperature yielded better adsorption per-
of pre-existing ions can enhance or worsen the performance of formance (Jun et al., 2020a).
adsorbents (Jun et al., 2020a). The effect of temperature on methylene blue adsorption by
In order to investigate the effect of background ions, adsorption Ti3C2eSO3H was investigated (Lei et al., 2019), who conducted ex-
experiments in the presence of background ions, such as those from periments at various temperatures, from 320 to 360 K. The
adsorption capacity was first analyzed and it was concluded that concentration of H ions increased and there was competition be-
higher temperatures yielded greater adsorption capacity; there was tween the adsorbed target contaminant and H ion for accessible
a 16 mg g1 increase in qe when temperature increased from 318 to surface sites on the Ti3C2Tx, causing the desorption of the
358 K. Owing to the increased mobility due to increase in tem- contaminant from the MXene. Also, under highly acidic environ-
perature, diffusion was increased, enhancing the adsorption pro- ment, desorption of the adsorbate may be accelerated since MXene
cess. On the thermodynamic parameters: the positive value of tends to become positively charged due to protonation. In this
enthalpy indicates that the reaction was endothermic; the negative study, the removal rate of the adsorbent remained over 90% after 5
value of Gibbs free energy change indicates that the reaction was regenerations and its morphology was hardly changed. However,
spontaneous, and as the temperature increased, the value of Gibbs there was a slight decrease in the removal rate with more re-
free energy change became more negative, showing the positive generations, which may be attributed to the decrease in the num-
influence of temperature on the adsorption process (Lei et al., ber of functional groups on the surface of the adsorbent (Khan et al.,
2019). 2019). The effect of the concentration of regenerant was investi-
Adsorption experiments were conducted using 2D-MX@Fe3O4 gated using different concentrations of HCl solution: 2, 4, 5, and 8 M
as an adsorbent and methylene blue as an adsorbate at specific (Shahzad et al., 2019a). They conducted experiments to investigate
temperatures: 298, 313, and 328 K (Zhu et al., 2019). According to the reusability of MX-SA4:20, which had been used in the adsorptive
the adsorption result, maximum adsorption capacity (qm) increased removal of Hg(II), and almost 80% of desorption of the Hg(II) ions
as temperature increased, achieving almost 92% removal of meth- was achieved by 2 M of HCl. Furthermore, as the concentration of
ylene blue at 328 K. The possible reasons for the increased HCl solution increased, the desorption rate of Hg2þ increased, until
adsorption capacity due to increased temperature were explained: approximately 100% of desorption was achieved by 8 M of HCl
such as the weak binding force at increased temperature, reduced (Shahzad et al., 2019a). A previous study on the recyclability of
viscosity of the solution, and expanded free volume of the system. MXene-based nanocomposites had been conducted as part of the
Thermodynamic analysis was also explored, and it turned out that study on the removal of Hg(II) (Shahzad et al., 2018). They also used
positive values of enthalpy, entropy and Gibb’s free energy change 1 M of HCl solution as regenerant for the exhausted MGMX in order
were obtained. In particular, the value of enthalpy change, to desorb the adsorbed mercury ions. The achieved desorption rate
42.8 kJ mol1, was considered high, over 40 kJ mol1, which also was approximately 90%, showing fairly constant values, but the
means that chemical interactions were involved in the adsorption removal rate of the adsorbent decreased from almost 100%e81.0%
process between the adsorbent and methylene blue (Zhou et al., after five recycles. This decrease may be explained by the loss of
2017). As temperature increased, the change in free energy surface functional groups and the decreased specific surface area
decreased, reaching almost 0 kJ mol1 at 328 K, and considering the caused by partial oxidation of the adsorbent to TiO2 (Shahzad et al.,
positive values of entropy and free energy change, this demon- 2018).
strates that the spontaneity of the adsorption reaction was affected Another widely used regenerant is HNO3 or/and Ca(NO3)2, and
by temperature (Zhu et al., 2019). A similar study demonstrated the being an acidic solution, similar effects as HCl solution can be
importance of the effect of temperature to the adsorption perfor- achieved. A study on the regeneration of used MXene by HNO3 or/
mance of MXene@Fe3O4 (Zhang et al., 2019b). In the study, exper- and Ca(NO3)2 was conducted, in which exhausted DL-Ti3C2Tx was
iments at temperatures of 298, 308, 318, and 328 K were conducted. regenerated by HNO3 and Ca(NO3)2 (Shahzad et al., 2017). The
The adsorption reactions at high temperatures yielded higher adsorbent was used to remove Cu(II) in water and recycled by the
adsorption capacities; in other words, the adsorption process was acidic solution of nitric acid and calcium nitrate. The adsorption
endothermic. Furthermore, thermodynamic analysis was carried rate of the adsorbent after the first regeneration cycle was 80%, and
out by examining the three parameters e entropy change, enthalpy a declining trend in the adsorption rate after the second and third
change and Gibbs free energy change. A positive value of enthalpy cycles was observed, reaching 47 and 30%, respectively, which are
change was obtained, indicating that the reaction was endothermic, steep decrease compared to the results of similar studies. The
a result which corroborated the results obtained from the analysis decrease might be due to imperfect desorption of copper ions,
of the adsorption capacity. As temperature increased, Gibbs free oxidation of the adsorbent, and reduction of Cu(II) to Cu(I)
energy decreased, demonstrating that higher temperature resulted (Shahzad et al., 2017). Nitric acid alone may be a good regenerant,
in better reaction performance. The positive values of the entropy and recycle experiments of synthesized adsorbents were con-
and Gibbs free energy implies that the adsorption reaction was ducted to compare the crosslinked MXene/alginate composite,
spontaneous, although this depends also on the reaction temper- prepared with calcium nitrate, and the un-crosslinked one (Dong
ature (Zhang et al., 2019b). et al., 2019b). A 0.1 M of nitric acid was used and the re-
generations of the adsorbents after the removal of Pb(II) and Cu(II)
5. Regeneration of MXene nanomaterials were conducted on 10 occasions in order to achieve the adsorption
rate for each cycle. Since the structure of the crosslinked MXene/
Recyclability of an adsorbent is a key factor to be considered alginate composite was mechanically more beneficial than the un-
when determining its effectiveness and economical advantage crosslinked composite, the adsorption rates of the former for each
(Khan et al., 2019). Several studies have explored the regeneration of the 10 cycles were higher than the ones of the latter. By
of MXene-based adsorbents, showing their high reusability. The increasing the stability of the structure by crosslinking with cal-
regenerants commonly used in these studies are HCl (Dong et al., cium nitrate, a higher adsorption rate was achieved compared to
2019a; Fard et al., 2017; Khan et al., 2019; Shahzad et al., 2018, the un-crosslinked composite (Dong et al., 2019b).
2019a), HNO3 and/or Ca(NO3)2 (Dong et al., 2019b; Peng et al., 2014;
Shahzad et al., 2017; Wang et al., 2017a), and other regenerants, 6. Conclusions and areas of future study
such as ethanol (Li et al., 2018; Zhang et al., 2019b), NaOH (Zou
et al., 2016), and thiourea (Mu et al., 2019), were also used. In the various studies covered in this review paper, there are two
Table 3 presents the summary of regeneration methods of mechanisms of adsorption for the removal of both inorganic and
exhausted MXene-based adsorbents. The recyclability of used organic compounds which are mentioned the most: electrostatic
Ti3C2Tx for the removal of Cs ions was examined using 0.2 M of HCl interaction and ion exchange. Large surface areas and an abun-
to desorb the ions (Khan et al., 2019). By adding HCl solution, the dance of surface functional groups can lead to higher adsorption,
Table 3
Summary of regeneration methods of exhausted MXene-based adsorbents.
MXene Species Regenerant Experimental condition Main finding Ref.
Ti3C2Tx Ba 69% HCl pH < 3 Regeneration of MXene could be influenced by pH since Fard et al. (2017)
importantly less adsorption occurred in the pH below
pHpzc of MXene owing to the accordingly increased zeta
potential value.
MX-SA4:20 Hg 2, 4, 6 and 8 M HCl Contact time ¼ 5 h (agitation) The regeneration using 8 M HCl achieved 99% of Shahzad et al.
desorption of Hg2þ adsorbed on the sample, therefore (2019a)
causing that desorption of Hg2þ from MX-SA4:20, should
be performed under very high acidic condition for
improved result.
DL-Ti3C2Tx Cu HNO3, Contact time ¼ 5 h The adsorption efficiency of regenerated DL-Ti3C2Tx was Shahzad et al.
Ca(NO3)2 80% in the first cycle, 47% and 30% in the second and (2017)
third cycle which could be owing to imperfect
desorption of Cu2þ and the partial oxidation changing
Ti3C2Tx into TiO2.
MGMX Hg 1 M HCl Contact time ¼ 5 h (incubator shaker) The adsorption efficiencies of recycled MGMX were Shahzad et al.
important which were higher than 90% until the fourth (2018)
cycle and there was a slight decrease in the fifth cycle:
81%, attributed to the stability of MGMX.
Glu@TNFs-3 Cd(II) 0.2 M HCl Contact time ¼ 9 h (stirring) By the adsorption capacity of the recycled Glu@TNFs-3 Dong et al.
which was 61 mg g1, high reusability of the adsorbent (2019a)
was exhibited. Under acidic condition, the used
adsorbent was protonated by Hþ, causing the adsorbed
heavy metals to be desorbed.
MXene-COOH@(PEI/ Methylene C2H5OH Temp. ¼ RT The removal rate was 85% after the first cycle and Li et al. (2018)
PAA)10 blue constantly decreased to 64% in the eighth cycle. The
possible reasons for the decrease could be due to
multiple surface washing and the loss of surface
functional groups.
Alk-MXene Pb(II) 0.1% HNO3 þ 5% Contact time ¼ 5 h (incubator shaker, By using the regenerant HNO3 and Ca(NO3)2, the used Peng et al.
Ca(NO3)2 200 rpm) adsorbent could be efficiently recycled and the removal (2014)
of Pb(II) after regeneration was 95%.
urchin-like rutile Cr(VI) 5% NaOH Temp. ¼ 298 K After regeneration of u-RTC using NaOH solution, the Zou et al. (2016)
TiO2eC adsorbed Cr(VI) was well desorbed and the according
adsorption efficiencies of Cr(VI) were over 90% until
fifth cycle.
Ti3C2Tx-DMSO- U(VI) 0.01, 0.1 and 0.2 M Contact time ¼ 0.5 h The regeneration experiments were conducted with Wang et al.
hydrated HNO3 different concentration of the regenerant. The (2017a)
desorption efficiency of 0.01 M HNO3 was
approximately 86% which is the smallest rate among
the results. By increasing the concentration of the
regenerant, the efficiency also increased, specifically
96% for 0.1 M and 98% for 0.2 M.
Ti3C2Tx Cs 0.2 M HCl Contact time ¼ 0.5 h (rocking mixer) The removal efficiency after the first regeneration cycle Khan et al.
m/V ¼ 5 g L1 was 98% and the percentage decreased until the fifth (2019)
temp. ¼ 293 K cycle down to 91%. The possibility of the decrease could
be loss of functional groups on surface and the integrity
of the adsorbent.
Ti3C2Tx Methylene 0.1 N HCl, Contact timeHCl ¼ 4 h The regeneration tests were conducted 4 times and Jun et al. (2020a)
blue 0.1 N NaOH Contact timeNaOH ¼ 4 h there was a slight decrease in the removal rate of MB,
probably due to incomplete desorption. However, the
fourth regenerated adsorbent still had a qe over
50 mg g1.
MXene-45 Pd 0.5 M HNO3, Among the regenerants, 0.5 M Thiourea was the most Mu et al. (2019)
0.5 M HCl, efficient eluent with the efficiency of 99%. And, also,
0.5 M Thiourea using 0.5 M Thiourea, the adsorption capacity was
(CH4N2S), decreased from 185 mg g1 to 167 mg g1 but, still, the
0.5 M HCl þ removal efficiencies were approximately over 90% until
0.5 M Thiourea the fifth cycle.
MXene@Fe3O4 Methylene C2H5OH The exhausted adsorbent was washed thoroughly with Zhang et al.
blue ethanol and dried at 343 K. The removal efficiency was (2019b)
over 80% in the first cycle and there was a slightly
decreasing trend of the removal efficiency down to 77%
in the fifth cycle.
Sodium alginate/ Pb 0.1 M nitric acid The regeneration result was different compared to Dong et al.
Ti3C2Tx Cu solution cross-linked processing and uncross-linked processing. (2019b)
Since the cross-linking improves the mechanical
properties of alginate, it showed better adsorption
efficiency compared to the other.
MGMX ¼ magnetic Ti3C2Tx MXene; TNFs ¼ Ti3AlC2-derived nanofibers.

and the adsorptive performance of MXene-based materials can be thoroughly investigated before application. If found efficient in the
highly influenced by water quality. The main determinants of water aforementioned areas, MXene would prove its practicality as a
quality that influence the adsorption performance of MXene are pH powerful adsorbent even more and could be employed in various
value, temperature, and background ions/NOM. Under acidic con- fields as well, not only in water treatment.
ditions, adsorption capacity, in general, decreases due to competi-
tion for MXene ions between abundant hydrogen ions and target Declaration of competing interest
compounds. On the other hand, as pH value increases, adsorption
capacity also increases since surface charges become more nega- The authors declare that they have no known competing
tive, confirmed by the zeta potential value. At very high pH, how- financial interests or personal relationships that could have
ever, decrease in adsorption capacity is observed, since abundant appeared to influence the work reported in this paper.
OH reacts with the target compound to form a hydroxide. How-
ever, there are still several studies in which the results were con- Acknowledgements
trary to the general trend above, such as exhibiting adsorption
almost independently of pH value. Higher temperatures generally This research was funded by the Korea Ministry of Environment
enhance adsorption, and MXenes show higher adsorption capacity (The SEM projects; 2018002470005, South Korea) and the U.S.
in such conditions. Confirmed by the thermodynamic parameters, National Science Foundation (OIA-1632824). This study was also
the adsorption process tends to be endothermic and spontaneous, supported by the University of South Carolina ASPIRE program.
thus raising the feasibility of the adsorption reaction in regard to
the increased temperature. The effect of background ions and NOM References
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Contents lists available at ScienceDirect

A review on MXene-based nanomaterials as adsorbents in aqueous

Removal of inorganic and organic contaminants by MXene-based nanomaterials was reviewed.

2.3. Delamination method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1. Introduction attracted great attention as emerging adsorbents for the effective

3.3.3. Temperature 4. Removal of organic contaminants by MXene nanomaterials

MXene Species Regenerant Experimental condition Main ﬁnding Ref.

MGMX ¼ magnetic Ti3C2Tx MXene; TNFs ¼ Ti3AlC2-derived nanoﬁbers.

capacitance. Nature 516 (7529), 78e81. (6153), 1502e1505.

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