Advances in Preparation, Application in Contaminant Removal, and Environmental Risks of Biochar-Based Catalysts: A Review

Yang et al.
Biochar (2022) 4:51

https://doi.org/10.1007/s42773-022-00169-8 Biochar
REVIEW Open Access
Advances in preparation, application

in contaminant removal, and environmental
risks of biochar‑based catalysts: a review
Bowen Yang1, Jiawei Dai1, Yuan Zhao2, Jingwei Wu1, Caiya Ji2 and Yuhu Zhang1*
Abstract
As a carbon-rich material produced by pyrolysis of biomass, biochar features low cost, large specific surface area, and
widely available feedstocks based on the functional diversity and environmental-friendly properties, it has received
increasing attention in the fields of pollutant removal due to three win–win effects of water remediation, carbon
sequestration and reutilization of wastes. To design excellent biochar-based catalysts for environmental applications,
one must understand recent advances in the catalysts for contaminant removal. This review focuses on the current
application of biochar-based catalysts in redox systems, Fenton-like systems, sonocatalytic systems and photocata-
lytic systems. Besides in-depth discussion in effects of preparation conditions on physicochemical characteristics
of biochars, the review supplements new preparation technologies of biochar and biochar-based catalysts. Most
importantly, the advantages/shortcomings, catalysis mechanisms, as well as the pollutant removal ability of different
types of biochar-based catalysts are discussed. The environmental risks of the catalyst applications are also elaborated
on. Future research on biochar-based catalyst production and its environmental applications is discussed. The review
provides a good overview of the current advances of biochar-based catalysts in pollutant control and the future
research directions.
Article Highlights
• Biomass type and thermochemical conversion temperature significantly affect biochar physicochemical proper-
ties.
• Biochar-based catalysts applied in Fenton-like system exhibited better performance for refractory emerging pol-
lutants.
• Biochar-matrix, metal nanoparticles of catalysts, as well as intermediates are the main risks.
Keywords: Biochar-based catalysts, Sonocatalysts, Fenton-like catalysts, Photocatalysts, Pollutant removal,

Environmental risks
*Correspondence: [email protected]
1
College of Resource Environment and Tourism, Capital Normal University,
Beijing 100048, China
Full list of author information is available at the end of the article
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permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the
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Yang et al. Biochar (2022) 4:51 Page 2 of 31
Graphical Abstract
1 Introduction sewage sludges, manures, algas, wood chips and so on,

Nowadays, with the development of industrialization can be used to produce biochars (Lopes and Astruc 2021;
and urbanization, various contaminants, including heavy Shaheen et al. 2019). Besides feedstock, the physico-
metals, antibiotics, polychlorinated biphenyls, pesticides, chemical properties of biochars are largely determined
endocrine disruptors, volatile organic compounds, and by thermochemical decomposition conditions including
polycyclic aromatic hydrocarbons are released into the temperature, residence time and heating rate (Xiang et al.
air, water and soil environment (Kwon et al. 2020; Lu 2020; Zhao et al. 2018). Whereas the adsorption process
et al. 2020). These pollutants could pose a serious threat could not completely decontaminate contaminants, com-
to the ecosystem and public health. Various green reme- pared to adsorption, catalysis technology can eliminate
diation technologies have been developed for the removal contamination by redox reaction. Recently, increasing
of these pollutants from the environment. Based on the attention has been paid to the applications of biochars
concept of green restoration, biochar (BC), as a promis- in the field of pollutant catalytic oxidation–reduction
ing multifunctional porous carbon material, has gathered (Fang et al. 2017; Lyu et al. 2020; Wang et al. 2019a). Eas-
much more attention (Wang et al. 2019a). The abundant ily tunable functional groups, chemical stability and elec-
feedstocks, huge specific surface area, abundant func- trical conductivity also make biochars act as a platform
tional groups, porous structure, and low cost endow bio- for supporting various catalytic nanoparticles (Ahmaru-
char with enormous potential for application in the field zzaman 2021; Kwon et al. 2018). The biochars with
transfer, which reduce the recombination of the e‒/h+

of pollutant remediation (Issaka et al. 2022; Liang et al. excellent electron-conductivity contribute to electron
2021), energy shortage (Bolan et al. 2022; Chen et al.
2019b) and climate change reversal (Tam et al. 2020). pair of semiconductor photocatalysts (Zhai et al. 2020).
Biochar is a porous carbonaceous product obtained Moreover, the incorporation of biochar can modify the
from the thermochemical decomposition of bio- weak visible light sensitivity, low adsorption capacity
mass under an oxygen-limited atmosphere (Aller and easy agglomeration of the photocatalysts (Ye et al.
2016). Almost all biomass, including organic munici- 2019). Besides photocatalytic system, many researchers
pal solid wastes, food wastes, agricultural residues, used biochar-based catalysts for peroxide activation to
induce the generation of reactive oxygen species (ROS) 2.1 Conventional production technologies
(Gholami et al. 2020b; Liu et al. 2020c; Luo et al. 2021; The biochar conventional production technologies
Wang et al. 2022). However, some defects such as light include pyrolysis, gasification and hydrothermal carboni-
dissolution and harmful metal ions release limited the zation. Recently, the conventional pyrolysis and hydro-
larger-scale application of these catalysts. Based on the thermal carbonization are still the most widely used
special surface structure and redox-active moieties (Chen methods to prepare biochars.
et al. 2015, 2017; Fang et al. 2015, 2017; Li et al. 2020; Liu
et al. 2019b), such as oxygen functional groups (OFGs), 2.1.1 Pyrolysis
mineral components, dissolved organic matter (DOM) In general, pyrolysis proceeds under oxygen-free condi-
and persistent free radicals (PFRs), attentions have been tions at temperatures ranging from 300 to 900 °C. Fig-
paid to direct generation of ROS for the degradation of ure 1 shows the effects of temperature on properties of
contaminants by using biochar-based catalysts (El-Nag- biochars. The most rapid decrease in yield occurs at
gar et al. 2020; Wu et al. 2021). 200–400 °C, and yields at least 30% could be obtained
Few reviews have systematically reviewed the advance under 800 °C. It could be found that the pH increased
of biochar-based catalysts for the removal of contami- with increasing temperature due to the detachment of
nants. Consequently, the overarching objective of this the acidic functional groups, which led to an increase
work is to present a comprehensive review on the appli- in alkalinity. Additionally, the relative content of the ash
cations of biochar catalytic technology in pollutant con- and the surface area follow the same rule (Weber and
trol. Besides the detailed description of conventional Quicker 2018), but it is not possible to estimate the sur-
preparation methods of biochar, the review supplements face area based on the temperature alone, and the surface
new technologies on the preparation of biochar and area may decrease after a further increase of temperature
biochar-based catalysts, and the correlation of biochar (Weber and Quicker 2018). Figure 1e shows the decrease
properties with catalysis. Comparatively, the two parts rate of O/C ratios is higher than that ofH/C ratios with
of the content are important but were overlooked in the the increase in temperature, indicating decreased polar-
previous review. After that, this review digests current ity and increased aromaticity. Obviously, the decrease in
applications of biochar-based catalysts in redox, Fenton- atomic ratios does not occur linearly with the pyrolysis
like, sonocatalytic, and photocatalytic systems. Most temperature. Figure 1d shows that the biochar trans-
importantly, the advantages/shortcomings, catalysis formed from volatile matter to fixed C as temperature
mechanisms, as well as the pollutant removal ability of increased. Besides, a longer residence time can increase
different types of biochar-based catalysts are discussed. biochar yield and fixed carbon content due to the repo-
Moreover, as an environmental function material, eco- lymerization of char constituents and decrease the vola-
friendly is an extremely important property to evaluate, tile matter content, at the same pyrolysis temperature
hence the environmental risks of the catalyst applica- (Zhao et al. 2018). The surface area and morphology are
tions are also elaborated. Finally, the perspectives and more significantly influenced by residence time, which is
future research directions of biochar-based catalysts are often overlooked in previous literature (Zhao et al. 2018).
discussed.
2.1.2 Gasification
2 Recent progress of biochar production Gasification could produce syngas, tars and char via
technologies the gaseous media (nitrogen, air, oxygen, steam etc.) to
Biochar, is the precursor of biochar-based catalysts, and partially oxidize the feedstock, hence, it requires high
its synthesis and properties greatly affect the catalysis temperatures ranging from 700 to 900 °C (Tam et al.
performance of catalysts. Nowadays, conventional pyrol- 2020). The low O/C ratio of feedstock used in this pro-
ysis methods are widely used to prepare biochars, and cess usually leads to efficient gasification (Kim et al.
emerging advanced pyrolysis techniques are developing 2020). Similarly, the product depends on the reaction
boomingly. The yield, surface area, pH, ash, and fixed car- temperature, pressure, and temperature rising rate. The
bon, volatile matter, polarity and aromaticity with their temperature is the most important parameter directly
according pyrolysis temperatures are important to design affecting the gasification reactions, and a higher tem-
useful biochar catalysts as they indicate the success of the perature can increase the yield of H2 and CO, carbon
pyrolysis process. Therefore, the relationship between conversion and cold gas efficiency, while reducing the
preparation conditions and performance of materials contents of CO2, C H4, hydrocarbons and tar contents
should be taken into consideration. Table 1 summarizes (Cha et al. 2016; Han and Kim 2008; Taba et al. 2012).
different technologies for the preparation of biochars In addition, the types of gasification agents significantly
with advantages and shortcomings. affect the characteristics of the biochar. It was reported
Yang et al. Biochar
Table 1 Technologies for production of biochars with advantages and shortcomings

Method of preparation Preparation temperature Retention time Biochar yield Advantages Shortcomings References
Pyrolysis 300–900°C Minutes to days 30–60% Simple and direct technology, low Reduced acidic functional groups, Jiao et al. (2021)
(2022) 4:51
cost, porous structure, high SBET low adsorption capacity due to the
partial oxidation of feedstock, poor
properties
Gasification 700–900°C 10–20 s 10–20% Low residence time and cost, high High temperature, less quantity of Murtaza et al. (2021)
gas yield biochar as a by-product, the genera-
tion of greenhouse gases
Hydrothermal carbonization 180–350°C 1–12 h 60–90% Easy to decompose biomass in an The feedstock limited by simple Cheng and Li (2018)
aqueous medium, no need to dry carbohydrates
biomass, convenient for coating
pre-formed nanostructures with
carbonaceous shells
Catalytic pyrolysis 300–600°C Minutes to hours 40–60% Low temperature due to catalysts, Contamination caused by catalysts Sekar et al. (2021)
high yield, improved product quality
Co-pyrolysis 250–600°C Several hours 30–60% The thermal degradation of a mixture Same with pyrolysis Fakayode et al. (2020)
of two or more biomass feedstocks
develops multiple properties of bio-
chars through synergistic effects
Microwave-assisted pyrolysis 300–700°C Hours to days 20–50% Uniform heating, high power conver- Restrictions on the reaction condi- Zhang et al. (2022)
sion efficiency, low thermal inertia, tions, the power and life of the
reduced energy consumption magnetron, microwave leakage
Calcination 300–700°C Several hours 30–60% Two or multifarious solid phase mat- High calcination temperature Baig et al. (2016)
ters are closely bound together destroys the structure of biochar and
decreases SBET
Hydrothermal treatment 90–220°C 2–24 h – More OFGs, high S BET and Vt, mild Poor stability, secondary pollution Wang et al. (2020d)
safety conditions
Sol–gel Water bath heating Hours to days – Easy to uniformly and quantitatively High cost of raw metal alkoxide, Xie et al. (2019)
incorporate some elements to toxic organic solvents, long process,
improve performance, easy reaction volatile gas
process, low temperature
Impregnation – Hours to days – Simple operation, good stability, less Secondary pollution Panwar and Pawar (2022)
metal leaching
Page 4 of 31
Fig. 1 Percent yields (a), pH (b), Van Krevelen diagram (e), surface area (f) of biochar from different feedstocks at different pyrolysis temperatures;
Biochar total carbon content (% w/w) changes with peak pyrolysis temperature and ash content (c); Biochar ash, volatile matter, and fixed carbon
proportions expressed as weight % in a ternary graph for each biochar type (d). [Data are from reference (Cha et al. 2016; Chandra and Bhattacharya
2019; Das et al. 2021; Liu et al. 2017b; Sun et al. 2017; Tomczyk et al. 2020; Xie et al. 2015; Zhao et al. 2018)]
that the ratio of the aromatic ring structure of the aro- could accumulate radicals on the char surface, form-
matic compounds composing the char was lower and ing some additional structures (such as hydroxides or
the contents of alkaline metals, such as Mg and Ca, oxides), which prohibited the formation of carbonates
were higher when H2O was used, the presence of steam or their agglomerates (Tay et al. 2013).
2.1.3 Hydrothermal carbonization as promising catalysts. For example, a previous study

Hydrothermal carbonization (HTC) based on the reac- showed that the co-production of bio-oil and MgO-
tion medium of water at relatively lower temperatures impregnated biochar from catalytic pyrolysis of Mg-
and higher pressures can convert biomass with moisture loaded biomass favored the thermal degradation process
content into biochar with higher carbon content (Gale due to the weakened hydrogen-bonding networks and
et al. 2021). In HTC process, the biomass needs not to disrupted the crystalline structures. The relative contents
achieve the drying step, and the product yield is higher of ketones and furans increased, and the relative contents
(up to 88%) than that from pyrolysis and gasification (less of phenols and sugars decreased for Mg-loaded sam-
than 60%), hence HTC is more energy efficient to obtain ples (Zhang et al. 2020c). Therefore, the use of catalysts
the same quality biochars (Cha et al. 2016; Meyer et al. is relatively promising due to lower energy requirement,
2011; Parmar et al. 2014). The effects of the tempera- pyrolysis temperature and enhancement of product
ture on properties of hydrochar are shown in Fig. 2. In selectivity (Lee et al. 2020). Because some catalysts may
HTC process, the hydrochar products are usually gen- be expensive, poisoned or ineffective, a proper selec-
erated below 250 °C (Fernandez-Sanroman et al. 2021), tion of catalysts is extremely necessary during the pro-
and temperature is a vital factor, which initiates an ionic cess of catalytic pyrolysis (Gholizadeh et al. 2021; Kabir
reaction in the subcritical regions (Khan et al. 2019). In and Hameed 2017; Zheng et al. 2017). It was noted that
terms of pH, even with an increasing trend along with although the derived cobalt-impregnated biochar exerted
temperature, hydrochars exhibited slightly acidic or excellent catalytic activity to activate peroxymonosulfate
mildly basic with pH-values ranging between 6 and 8 due (PMS) for atrazine degradation, all transformation by-
to the formation of organic acids during the hydrother- products and parent atrazine were still classified as very
mal process, which is different significantly from pyroly- toxic compounds to aquatic organisms (Liu et al. 2020a).
sis biochars (Vassilev et al. 2010). The proximate analysis Fredriksson used olivine as an active bed material for
indicated hydrochars have higher volatile matter content catalytic cracking of tars during gasification of biomass,
while lower ash content than pyrolysis biochars. Car- the carbon deposition observed after exposing olivine
bon content (C) correlates well with the ash content (A) to reducing conditions can result in significant catalyst
and pyrolysis temperature (T) (R2 = 0.9447, Fig. 2c), so it deactivation (Fredriksson et al. 2013).
is possible to accurately prepare hydrochars with desir-
able carbon and ash content by adjusting the hydrother- 2.2.2 Co‑pyrolysis
mal temperature. Figure 2e indicates that an increase in Compared to conventional pyrolysis, co-pyrolysis is a
hydrothermal temperature instigates a reduction in H/C process that entails the thermal degradation of a mix-
and O/C ratios, resulting from the degree of the conden- ture of two or more biomass feedstocks through the
sation reaction (Sevilla and Fuertes 2009). Note that the generation of synergistic effects, hence it could improve
decrease in atomic ratios occurs linearly with pyrolysis the pyrolysis method for the development of multiple
temperature (R2 = 0.9022, Fig. 2e), proposing an estima- properties of biochar used in applications (Ahmed and
tion of atomic ratios based on the temperature alone Hameed 2020). Depending on the synergistic effects and
could be possible. interactions of multifarious biomass materials, co-pyrol-
ysis can significantly improve the quality of the product.
2.2 Advanced pyrolysis techniques Many studies indicated that the yield of biochar, pore
Conventional pyrolysis may not be promising for the structure, ash content, and heating value would have an
development of multiple properties of biochars. Based on improvement by co-pyrolysis (Fakayode et al. 2020; Li
the shortcomings of conventional techniques, advanced et al. 2021). It demonstrated that the surface area and
pyrolysis methods are developed to improve the yields, higher heating value of biochar derived from co-pyroly-
qualities, characteristics and properties of products. sis of rice husk-pine sawdust and seaweed are 3.83 and
Currently, advanced pyrolysis techniques involve several 1.16 times higher than those of seaweed-derived biochar
approaches, including catalytic pyrolysis, co-pyrolysis, (De Bhowmick et al. 2018). Some studies also indicated
microwave-assisted pyrolysis and combination of multi- that co-pyrolysis could enhance adsorption performance
ple technologies. toward a variety of pollutants. Kwon reported that Cu(II)
adsorption capacity of co-pyrolysis biochar derived from
2.2.1 Catalytic pyrolysis chitin and oyster shell had a promotion and synergistic
Catalytic pyrolysis is usually used to prepare high value- effects enhanced the properties of biochar (Kwon et al.
added chemical energy products. The use of proper 2022). A review summarized that merging lignocellu-
catalysts can improve the pyrolysis process and charac- losic and macroalgae biomass feedstocks can be suc-
teristics of the products. Biochar materials can be used cessfully employed for biochar production in the energy
Fig. 2 Percent yields (a), pH (b), Van Krevelen diagram (e) of hydrochar from different feedstocks at different pyrolysis temperatures; Hydrochar total
carbon content (% w/w) changes with peak pyrolysis temperature and ash content (c); Hydrochar ash, volatile matter, and fixed carbon proportions
expressed as weight % in a ternary graph for each biochar type (d). [Data are from reference (Ghanim et al. 2016; Liu et al. 2017b; Raheem et al. 2022;
Saqib et al. 2018; Wang et al. 2018c; Yao et al. 2016; Zhang et al. 2020b; Zhou et al. 2019; Zhu et al. 2015)]
biorefinery (Fakayode et al. 2020). While co-pyrolysis is be taken into consideration and most of the studies
a developing technology that is being keenly explored regarding catalytic pyrolysis are still in the lab scale, and
at present, more considerable attention, such as tem- attention should be paid to this aspect in future studies
perature, heating rates and feedstock types and blend- (Yang et al. 2022). Gasification is often performed at large
ing ratio, pretreatment and economic analysis should be scales thus producing several tons of biochar per day as a
given to it considering the various benefits derived from co-product. The cost of $380 per ton and large volumes
its utilization (Fakayode et al. 2020). of gas make gasification an incidental method to produce
biochars, and interestingly, it was found a higher heat-
2.2.3 Microwave‑assisted pyrolysis ing value of 18.9 MJ for gasification biochars (Low and
Microwave-assisted pyrolysis has boomed over the past Yee 2021; Meyer et al. 2011; Norgate and Langberg 2009).
5 years (Lee et al. 2020). In microwave pyrolysis of bio- However, the cost will increase greatly if biomass mois-
mass, the heat transfer is more efficient as the heat is gen- ture content is high. HTC is a suitable method that could
erated within the core of material by the interaction of convert biomass with any moisture content into biochars
microwaves with biomass (Foong et al. 2020), hence lead- with higher carbon content, and it was reported that the
ing to energy saving. The microwave power and inter- yield could reach 20 kilotons per year with $190.15 per
action of heating time and microwave power positively ton production cost by HTC (Nizamuddin et al. 2017;
affected the maximum yield of biochar (Sahoo and Remya Pacheco Antero et al. 2020). Microwave-assisted pyroly-
2020). The pyrolysis heating rate greatly depends on the sis is another method to handle biomass with high mois-
temperature, power of the microwave, microwave absorb ture content, and the water in biomass has been shown
ability and pyrolysis feedstock (Lee et al. 2020). The to increase the rate in a microwave pyrolysis reactor,
induction of additives, such as the absorber or catalysts, thereby increasing the heating efficiency (Hadiya et al.
can further promote microwave-assisted pyrolysis, and 2022). Therefore, the microwave pyrolysis of biomass is
the properties of biochars obtained through microwave profitable when biochar pyrolysis oil and non-condensa-
pyrolysis are significantly different from those of conven- ble gas are considered. Co-pyrolysis is similar to pyroly-
tional pyrolysis. Biochar is also an excellent additive for sis on economic feasibility, and the difference lies in the
biomass pyrolysis due to its high microwave absorbabil- selection of raw materials, but rare references investi-
ity (Wang et al. 2020a). In a previous study (Haeldermans gated the co-pyrolysis costs. Note that the high value
et al. 2019), an increasing microwave power without the applications of the remaining co-pyrolysis products will
use of absorbers led to a higher degree of aromaticity greatly improve the economics of biochar production
and a more open surface of biochar (Jiao et al. 2021). The (Fakayode et al. 2020).
microwave-assisted pyrolysis can be considered as a new
form of development, however, the lack of excellent reac- 3 Recent progress of biochar‑based catalyst
tor design can be a main obstacle that impedes the com- synthesis
mercialization of biomass recycling (Foong et al. 2020). Several approaches have been developed for biochar-
based catalyst synthesis from different feedstocks.
2.3 Cost factor Among them, calcination, hydrothermal treatment,
The cost is a non-negligible factor when preparing bio- sol–gel, and impregnation are by far the most important
chars. Pyrolysis is a so important technology in the technologies (Table 2).
biomass energy industry development with simplic-
ity in design and operation. More importantly, it allows 3.1 Calcination
to input almost all types of biomasses at various sizes Calcination usually proceeds under N 2 or air conditions
(Low and Yee 2021). Many researches have investigated at temperatures ranging from 300 to 700 °C, which is
the cost of pyrolysis. Jenny found that the conventional similar to pyrolysis. Calcination is one of the most com-
pyrolysis of biochar and methanol yields the minimum mon methods for preparing biochar based-catalysts, by
carbon price of $642.40 per Mg, while fast pyrolysis bio- which two or multifarious solid phase matters are closely
chars achieve the minimum carbon price of $61.38 per bound together to achieve composite multi-function-
Mg (Meyer et al. 2011; Raheem et al. 2022), but research- alization. Compared with pyrolysis, calcination could
ers should make a promotion on the property and yield increase the hardness of materials, prevent their break-
of biochar by pyrolysis to improve this method. Catalytic age, and change material textural and mineralogical char-
pyrolysis could reduce the production cost by reducing acteristics (Baig et al. 2016). Just as its name implies, the
energy input. The introduction of catalysts could obtain temperature, gas phase composition, and thermal stabil-
the product with higher yields and better quality at lower ity of the compound significantly affect the calcination
temperatures. Nevertheless, the cost of catalysts should process. A series of TiO2/pBC composites were prepared
Table 2 Synthesis parameters and characteristics of various biochar-based catalysts
Biomass types Preparation Preparation Catalysts Characteristics Active moiety References
methods conditions
Yang et al. Biochar
C (wt %) O (wt %) Metal (wt %) BET (m2·g−1) Vt (cm3·g−1)
Pine needles Pyrolysis 300°C; 10°C·min−1; Pine needle 65.1 26.2 – 5.24 – OFGs; Fang et al. (2015)
6h biochar [FRs] = 5.38 × 1018
spins·g−1;
[·OH] = 75 μM
(2022) 4:51
Cotton straw Pyrolysis; activation 350°C; 10°C·min−1; Cotton straw – – – 39.005 0.03514 N, Si elements; Wang et al. (2019c)
2 h; NH2Cl treatment biochar [FRs] = 8.25 × 1016
spins·g−1
Red mud and lignin Pyrolysis 700°C; 10°C·min−1; Mixed metal-bio- 32.0 35.0 27.2 100.8 – Metal oxides; Cho et al. (2019)
1 h; N2 flow rate char composites metallic Fe
500 mL·min−1
Fir sawdust Adsorption; fast 773 K; N2 Ag@biochar 86.2 10.7 1.1 27.8 – Ag NPs Liu et al. (2016)
pyrolysis
Rice straw Impregnation; Salt solution impreg- N-biochar @ 76.4 20.2 – 150.7 0.081 Hydroxyl groups; Liu et al. (2019a)
pyrolysis nation; 800°C for 4 h; CoFe2O4 Co3+; phenolic and
5°C·min−1 quinone moieties;
graphitic N
Camellia seed husks Impregnation; 400°C for 2 h; oxidation biochar- 29 36.8 31.29 – – OFGs; Fe3O4 Pi et al. (2019)
pyrolysis; co- HNO3(68%) + H2SO4 Fe3O4 particles; carbon
precipitation (70%) soaking 1 h hybridization;
defective sites; PFRs
Wheat husks, paper Pyrolysis; impregna- BC: pyrolysis at ZnO-biochar 26.15 35.93 31.09 119.15 0.16 Functional groups; Gholami et al.
sludge tion; hydrothermal 500°C for 20 min; porous particles; (2019a)
treatment Zn(NO3)2 solution; ZnO; metals like Si
hydrothermal: 90°C and Al that exist in
for 2 h biochar gallery
Biochar Oxidation; hydro- Oxidation by H2SO4, Fe-Cu-LDH / 28.93 6.32 64.75 91.35 0.89 Fe-Cu LDH Gholami et al.
thermal method HNO3; hydrothermal biochar (2020a)
method at 90°C for
24 h
Platanus orientalis Sonication; 650°C for 2 h; sonica- FeBC 81.86 3.31 7.34 – – Fe-loaded biochar Wen et al. (2021)
linn branches pyrolysis tion with F eCl3 at could increase the
25°C for 1 h; 650°C immobilization of
for 1 h potentially toxic
elements through
(co)precipitation
Paper waste, wheat Pyrolysis; hydro- 500°C for 20 min; CeO2H@biochar 23.67 31.28 36.6 59 0.19 Biochar trap Khataee et al. (2018)
straw thermal method; 90°C for 24 h; 500°C electrons in CB of
calcine for 2 h with air CeO2; metals in the
BC galleries act as π
acceptor metals
Page 9 of 31
Table 2 (continued)
methods conditions 2 −1 3 −1
Yang et al. Biochar
C (wt %) O (wt %) Metal (wt %) BET (m ·g ) Vt (cm ·g )
Pine pollen Hydrothermal; in- 180°C for 12 h biochar@ – – – 21.848 0.059 Biochars assist e− Zhai et al. (2020)
situ precipitation CoFe2O4/Ag3PO4 to move; Z-scheme
heterojunction
between MB and
Ag3PO4
(2022) 4:51
Glucose Hydrothermal; 180°C for 10 h; 600°C Fe3O4 hydrochar – – 9.17 1072 0.3979 Fe(II); magnetic Wang et al. (2020d)
activation for 90 min hydrochar
Hog fuel, demoli- Pyrolysis; hydro- 600°C for 30 min; Cu2O-CuO @ 18.19 44.17 37.64 32.91 0.37 Biochar; Cu2O-CuO Khataee et al. (2019)
tion waste thermal 180°C for 3 h biochar
Hemp stems Sol–gel; calcine 500°C for 2 h in N2 TiO2-CuO/HSC – – – 17.35 0.064 HSC; CuO; TiO2 Peng et al. (2019)
Wheat husks, paper Pyrolysis; modifica- 500°C for 20 min; Zn-Co LDH-@ 21.73 30.16 37.26 95.76 0.11 Zn−Co—LDH; Gholami et al.
sludge tion; hydrothermal H2SO4 + HNO3; 90°C biochar biochar (2020b)
for 24 h
Walnut shells Pyrolysis; hydrolysis 500–800°C for 2 h; TiO2/biochar 11.7 86.92 – – – Biochar transfer Lu et al. (2019)
calcined at 500°C electrons and acted
for 1 h as acceptor
Reed straw Pyrolysis; sol–gel 500°C for 6 h TiO2/pBC – – – 102.160 0.0122 TiO2 Zhang et al. (2017)
Activated carbon Sol–gel; calcine 80°C for 4 h; 500°C AC-TiO2 47.7 30.2 22.1 360.4 0.0348 Lignocellulosic Djellabi et al. (2019b)
Olive pits for 2 h OP-TiO2 23.1 39.1 37.8 55.13 0.0147 materials collect
and transfer elec-
Wood shaving WS-TiO2 31.4 35.7 32.9 30.04 0.0147 tron–hole charges;
C=O and O=C–OH
as electron accep-
tor
Chicken feather Hydrothermal Air dry at 200/220°C TINCs 75.14 15.14 5.91 64.10 – Ti–O–C; Ti–O–Ti Li et al. (2018)
cross-link for 8 h; argon at and Ti-N bonds
450°C for 1 h
Reed straw Pyrolysis; sol–gel; 500°C for 6 h; 300°C Zn-TiO2/biochar 40.44 31.31 26.78 169.158 0.0159 Zn; TiO2 Xie et al. (2019)
calcined for 2 h
Olive pits Sol–gel; hydrother- 500°C; 180°C for 6 h TiO2-OP @Fe3O4 – – – 104.7 0.175 Ti–O–C bridge; OP Djellabi et al. (2019a)
mal; magnetization act as a photosen-
sitizer for TiO2 or
electrons acceptor
Sewage sludge Impregnation; 800°C for 1 h; TiO2/Fe/Fe3C- – – – 267.3 0.33 Mesoporous Mian and Liu (2019)
thermal decompo- 10°C·min−1 under N2 biochar surface; Ti3+; Fe3C
sition and Fe0
Page 10 of 31
Yang et al. Biochar
Table 2 (continued)
(2022) 4:51

methods conditions
C (wt %) O (wt %) Metal (wt %) BET (m2·g−1) Vt (cm3·g−1)
Chestnut leaves Pyrolysis; thermal 900°C for 2 h; 300°C g-C3N4 modified 61.2 – 38.8 (N) 8.05 – Biochar mainly Pi et al. (2015)
poly-condensation for 2 h; 520°C for 2 h biochar acts as adsorbent;
electron-transfer
channels and
acceptors
Bamboo Hydrothermal; cal- 180–200°C; 550°C for Biochar@g-C3N4 – – – 34 – Biochar spheres Wang et al. (2018b)
cine; impregnation 4 h; 70°C for 60 min core–shell catalysts acted both as
a reservoir and
sensitizer
α-D-glucose One-pot HTC 180°C for 12 h Fe3O4/C/g-C3N4 – – – 79.9 – Carbon and Fe3O4 Ding et al. (2018)
with superior
electron transfer
ability
Biochar Hydrolysis method Room temperature Biochar/BiOX – – – – – Biochar acted as an Li et al. (2016)
for 12 h (X = Br, Cl) electron reservoir
Lotus-leaf Calcinate 300°C for 1 h; N2 CdS@LAC-800 39.0 29.41 23.6 1245 – Excellent light Huang et al. (2018b)
harvesting ability
Rice straw Hydrothermal treat- 180°C for 24 h g-MoS2/ PGBC 50.87 3.96 22.81 266.8 0.126 PGBC with good Ye et al. (2019)
ment conductivity; PGBC-
OOH; PGBC-OH
Cornstalk Pyrolysis; impregna- 600°C for 6 h; stirred Biochar/natur-al 84.72 10.25 2.79 240.6 0.062 Minerals serve Yang et al. (2021a)
tion for 4 h; 600°C for 6 h manganese ore as an electron
medium to facili-
tate the electron
transfer and redox
Page 11 of 31
by calcination (Zhang et al. 2017). The composites have and it is similar to the hydrothermal method. A biochar@
a lower SBET (specific surface area) (102.16 m2·g−1) than ZnFe2O4/BiOBr heterojunction was prepared via the
that of raw biochar (125.04 m2·g−1). This phenomenon simple solvothermal method at 160 °C for 12 h (Chen
may be attributed to the reason that semiconductors et al. 2019a). The heterojunction has a lower SBET and V t
cover a proportion of the biochar’s surface, hence result- of 27.16 m 2·g−1, 0.069 cm3·g−1 and 30.28 m2·g−1, 0.056
ing in a decrease in surface area. Moreover, a higher cal- cm3·g−1 than pure BiOBr, due to the BiOBr microspheres
cination temperature of 500 °C can destroy the structure grown on the surface of biochar causing pore blockage.
of biochar, hence resulting in significantly decreased S
BET
(0.4035 m2·g−1) of the composite. In contrast, the BET 3.3 Sol–gel
surface area of the Lotus-Leaf-Derived Activated-Car- Sol–gel means that the colloidal suspension or sol is
bon-Supported Nano-CdS increased from 734.6 m2·g−1 formed from a precursor, such as inorganic metal salts or
to 1245 m2·g−1 with calcination temperatures that varied metal–organic compounds, followed by hydrolysis and
from 600 °C to 800 °C (Huang et al. 2018b). It could be polymerization of the precursor (Cui et al. 2021; Silvestri
assumed that a higher calcination temperature is favora- and Goncalves 2019). Tailored properties of the material
ble for woody biomass rather than herbaceous biomass are advantages of the sol–gel method by controlling the
feedstock when preparing catalysts. Consequently, it is morphology and distribution of the generated inorganic
critical to reasonably select the feedstock and calcination nanomaterials within the polymer matrix. The sol–gel
temperature during the process of catalyst preparation by method is mainly used to synthesize biochar-decorated
the calcination method. Moreover, thermal polyconden- TiO2 catalysts (Liu et al. 2019c). In TiO2-decorated bio-
sation is usually used to produce g-C3N4 based catalysts, char-based catalyst, the TiO2 nanoparticles are agglom-
which is actually similar to calcination. For example, bio- erated on the surface of biochar, and the crystal phase
char@C3N4 composites were obtained by a thermal poly- structure, average size, and dispersion of TiO2 upon the
condensation process (Pi et al. 2015). Typically, melamine biochar greatly depend on the sol–gel decomposition
was firstly mixed with biochar and ground for 1 h, the temperature (Mian and Liu 2018). After the solution
mixture was then heated to 300 °C for 2 h, and the fur- reaction step, it is easy to uniformly and quantitatively
ther condensation treatment was performed at 520 °C for incorporate some elements to improve catalyst perfor-
2 h. mance. It is generally believed that the diffusion of the
components in the sol–gel system is in the nanometer
range, and the reaction is easier to proceed and the tem-
3.2 Hydrothermal treatment perature is low compared with the solid phase calcination
Compared with pyrolysis chars, hydrochars possess reaction. For example, Xie (Xie et al. 2019) used absolute
more OFGs, making it more suitable for being used as ethanol and acetic acid as the solvent to prepare Zn dop-
an excellent catalyst (Wang et al. 2020d). The hydrother- ing TiO2/BC catalyst with SBET of 169.1579 m 2·g−1 by
mal treatment process for the synthesis of biochar-based simple sol–gel method at room temperature. The result
catalysts usually proceeds at the temperature ranging indicated that the doping of zinc elements via the sol–gel
from 90 to 220 °C and a retention time of 2 to 24 h. A method may make TiO2 easier to load on biochar, and
ZnO-biochar nanocomposite with high S BET (119.15 effectively reduce the agglomeration of TiO2 and crystal
m2·g−1) and Vt (pore volume) (0.16 m3·g−1) was synthesize. However, sol–gel is just a critical step to prepare
sized by the hydrothermal method at 90 °C for a duration catalysts, and it needs to conduct a further calcination
of 2 h (Gholami et al. 2019a). The material with a nano- after the process of depositing catalytic nanoparticles
sized structure can be easily prepared via hydrothermal on the biochar surface (Zhang et al. 2017). Moreover,
techniques. The biochar-incorporated Zn-Co-layered there are some shortcomings involved with the sol–gel
double hydroxide (LDH) nanocomposite exhibited good method. For example, the cost of raw metal alkoxide is
incorporation of Zn-Co-LDH nanostructures into the relatively high, and organic solvents might be toxic, the
biochar lattice, and the integration of Zn-Co-LDH nano- entire sol–gel process usually takes a long time, and gas
flakes with biochar matrix resulted in the formation of a and organic matter will escape and shrinkage during the
regular-shaped nanocomposite with an improved S BET drying process.
(95.76 m2·g−1) compared with the pristine biochar (68.19
m2·g−1) (Gholami et al. 2020b). Compared with calcina-
tion, hydrothermal treatment is more cost-efficient due 3.4 Impregnation
to milder safety conditions and simple processes with- 3.4.1 Metal (oxides)
out the process of desiccation. The solvothermal method In this method, active metallic species are incorporated
is usually used to prepare T iO2 or BiOX based catalysts, into biochar structures by mixing feedstock with metal
precursors, forming active interfaces and binding sites biochar-based catalysts for the catalytic activity recently
(Tam et al. 2020). This method could have a great enhance- (Wan et al. 2022). Due to the different atomic radi-
ment for biochar-based catalysts on the adsorption capac- uses, atomic orbitals and electronegativity of these ele-
ity, catalytic performance and magnetism (Pan et al. 2021). ments, this method could promote the electron density,
The magnetic nitrogen doped biochar catalysts were pre- reactive-active moieties, defective sites and reusability
pared through impregnating biochar with mixtures of by chemically modifying and modulating the inherent
Co(NO3)2 and F eSO4 under an oxygen-limited condition, carbon configuration (Tam et al. 2020; Wan et al. 2020;
followed by calcination at a desired temperature (400– Yu et al. 2020), and it shows the superiority over many
800 °C) for 4 h (Liu et al. 2019a). The composite calcined other methods. N-doped biochar-based catalysts could
at a higher temperature had higher SBET (150.7 m 2·g−1) form pyridinic-N, pyrrolic-N, quaternary-N, and pyri-
3 −1
and Vt (0.081 cm ·g ) than that calcined at compara- done-N-oxide through the polymerization reaction with
tively low temperatures, which is not consistent with the oxygen- containing functional groups on the surface
previous study (Zhang et al. 2017), despite this identical of biochars, which increase the surface sorption sites,
biomass feedstock. This phenomenon can be attributed basicity and positive charges (Chen et al. 2018; Huang
to the formation of a large number of CoFe2O4 crystals et al. 2022; Kasera et al. 2022). It was reported that the
on the surface of biochar by impregnation, which could CO2 uptake of the N-doped hickory biochar was 31.6%-
contribute to the stability of the biochar pore structure. 55.2% higher than that of the corresponding pristine
Moreover, a higher calcination temperature can obtain a and ball-milled biochars. Chen found that N-doped bio-
high graphitization degree structure, which is conductive chars show a synergetic effect on the formation of phe-
to the charge transfer process and helpful for promoting nols by combining the advantages of activated carbon,
electron transfer (Wang et al. 2018a). A TiO2/Fe/Fe3C-bio- active functional groups, and N H3, and it also inhibits the
char composite was synthesized by impregnating sewage generation of O-species and acetic acid while promotes
sludge and different ratios of nanoparticles with chitosan, the formation of aromatics (Chen et al. 2020). Biochar-
subsequently thermal decomposition at 800 °C (Mian and based catalysts doping S could improve the persulfate
Liu 2019). NPs (nanoparticles) ratio and chitosan support activation capacity of sludge biochar-based catalysts via
have significant influence on the properties and catalytic enhancing the electron shuttling capacity in nonradi-
activity of catalysts,and high content of Fe impregnation cal pathways (Yun et al. 2018). Wang prepared sewage
reduces surface area and active site due to F e0 agglom- sludge biochars incorporating zigzag-edge sulfur (SSB),
eration. Nevertheless, impregnation often produces com- and it effectively activated the sp2-hybridized graphene
posites rather than carbonaceous biochar, demanding lattice, which generated more Lewis acid and basic sites.
scrutiny comparison among bare biochar, impregnated 93.6% of bisphenol A (BPA) removal was achieved by
composites, and the exhausted catalysts (Tam et al. 2020). SSB/PMS within 60 min (Wang et al. 2020b). The dop-
The precipitation method can be classified as one of the ing of P could introduce functionality onto biochars to
impregnation methods, and the difference is that pre- realize chemical activation based on the low electronega-
cipitates are formed and deposited on the biochar surface tivity and the large atomic radius of P (Suo et al. 2019;
when caring out the impregnation process. The biochar@ Zhou et al. 2022a). Zhou prepared the P-doped biochar
CoFe2O4/Ag3PO4 was synthesized by a facile in-situ pre- composites with high specific surface area, mesoporous
cipitation process via using ethylene glycol as the solvent, ratio and abundant P-containing functional groups, and
followed by impregnating biochar@CoFe2O4 with mix- P-O-Caromatic and Caromatic-PO3/C2aromatic-PO2 groups
tures of AgNO3 and Na2HPO4 (Zhai et al. 2020). Similarly, are the active sites for chemical adsorption of methylene
the composite exhibited a lower SBET (21.85 m2·g−1) and blue (Zhou et al. 2022b). B dopants could modulate the
Vt (0.059 cm3·g−1) than raw magnetic biochar, the intro- electron distribution and physicochemical properties of
duction of magnetic biochar had little effect on the crys- sp2-hybridized carbons, and it was found that the biochar
tal structure of Ag3PO4 by impregnation process, and the materials introduced B, which acts as the Lewis acid site,
intensity of crystal characteristic peaks of the photocata- enhanced the surface affinity towards peroxydisulfate
lysts varies with the change of loading ratio. (PDS) and modulated the electronic structure of cata-
lysts, and evidently resulted in superior electron transfer
3.4.2 Non‑metallic rate long-term durability and catalytic capacity owing to
Attention has been increasingly paid to incorporat- the high stability boron sites (Liu et al. 2020b; Sun et al.
ing non metallic elements (such as N, S, P, B) into 2018).
Fig. 3 A proposed mechanism for pollutant degradation by the pure biochar at light radiation (a); biochar-based catalysts by Fenton-like reaction
(b); biochar-based catalysts by photocatalysis reaction (c); biochar-based catalysts by sonocatalysis reaction (d)
4 Biochar‑based catalyst applications in pollution a critical factor affecting the generation of PFRs, which
control further affects the degradation of organic pollutants. In
Biochar-based catalysts have been widely used for the a previous study, the rice husk-derived biochars exhib-
removal of contaminants in water and soil. Moreover, ited the degradation rate for 1,3-dichloropropene ini-
biochar-based catalysts have been widely used in differ- tially decreased from 0.00152 h−1 to 0.00073 h−1 and
ent systems, including redox systems, Fenton-like sys- subsequently increased to 0.00305 h−1 with an increas-
tems, sonocatalytic systems and photocatalytic systems ing pyrolysis temperature range from 300 to 700 °C (Qin
(Fig. 3) (Table 3). et al. 2017). A certain high temperature promotes the
formation of PFRs, but excessively high temperatures
4.1 Biochar composite for redox systems may cause the cracking and reorganization of the organic
Organic contaminants can be directly degraded by bio- structure, resulting in the elimination of PFRs (Fang et al.
char without the addition of oxidants (Lyu et al. 2020). 2015). Besides, DOM with abundant PFRs derived from a
PFRs in biochar can transfer electrons to O2 to pro- sugar beet tailing and Brazilian pepper biochars, serving
duce the superoxide radical anion and hydrogen per- as both electron donor and electron acceptor, exhibited
oxide, which react further with PFRs to produce ·OH 100% reduction of Cr(VI) (Dong et al. 2014). Moreover,
(Fang et al. 2015). Biochar carbonization temperature is the introduction of metal could significantly improve
Table 3 Applications of various biochar-based catalysts in pollutant control
Catalysts Reaction conditions Removal performance Influence factors Driving mechanisms References
Redox system Fe@biochar [As(III)/Cr(VI)] = 0.03 M; 91.3% for As(III); 85.9% for Temperature; O-function- Fe@biochar generated more Xu et al. (2022)
[catalyst] = 1 g·L−1; t = 48 h; Cr(VI) ality; amorphous ferrous reactive ·OH by reducing
Yang et al. Biochar
T = 323 K; pH = 6.5 mineral; minerals (e.g., Ca, the O2 and enhanced the
Mg, K) redox-related transformation
of As(III)/Cr(VI)
Cotton straw biochar [E2]0 = [EE2]0 = 10 μM; 95% of E2 and EE2; 87% of Cl– inhibits but N
H4+ and Nitrogen and silicon ele- Wang et al. (2019c)
[NH2Cl] ∼0.15 mM, 24 h; E2 and 75% of EE2 within H
CO3− promote removal ments of biochar activated
24 h NH2Cl to generate ·NO for
(2022) 4:51
[Cot350]0 = 1 g·L−1;
[NH4Cl]0 = 0.30 mM; the degradation of the EDCs
[FAC]0 = 0.15 mM; T = 25°C;
[phosphate buffer]0 = 5 mM;
pH = 9
Co3O4@ biochar [catalyst] = 4.0 mg; 100% after 10 cycles Pyrolysis atmosphere; tem- The catalytic performance (Kwon et al. 2018)
[NaBH4] = 1 mL 250 mM; perature of biochar is contingent on
[p-nitrophenol] = 1 mL both pore structure and
0.68 mM Co9S8
Ag@biochar [Cr (VI)] = 0.02 M; T = 323 K; 100% within 20 min; 93% Particle size of Ag; depend- Follows a CO reduction Liu et al. (2016)
t = 20 min; [Ag@bio- after 2 cycles ent on temperature; miner- mechanism
char] = 1 g·L−1 and HCOOH als (e.g., Ca, Mg, K)
(95% v/v; 3.97 mL)
Pine needles biochar [diethyl phtha- 100% High oxygen concentration FRs in biochar transfer elec- Fang et al. (2015)
late] = 5 mg·L−1; [oxy- enhances removal trons to O2 to form O2·− and
gen] = 0.2 mL·min−1; H2O2, which reacts with FRs
[P300] = 1 g·L−1; to produce ·OH
[ethanol]0 = 10 mM;
T = 25°C; pH = 7.4
Fenton-like system Biochar/natural manganese [BPA] = 20 mg·L−1; 95.9% within 2 h Catalysts dosage; HCO3‒ PMS activated via a nonradi- Yang et al. (2021a)
ore [PMS] = 1.0 mM; [cata- cal mechanism to metasta-
lyst] = 1.0 g·L−1; pH = 6.5; ble state, BPA transferred
t=2 h electrons to the metastable
PMS through the catalyst
Sch@biochar [SMX] = 10 mg·L−1; 100% Catalysts dosage; pollutant Hydroxylation; the oxidation Yang et al. (2021b)
[H2O2] = 2.0 mM; [cata- concentration; pH of the amino groups; the
lyst] = 1.0 g·L−1; pH = 3.0; cleavage of the S–N bonds
t = 60 min; ultrasonic
power = 300 W
Oxidation biochar-Fe3O4 [tetracycline] = 20 mg·L−1; 92.3% within 2 h pH; H2PO4‒ Involving generation of Pi et al. (2019)
[PS] = 10 mM; [cata- SO4·‒, ·OH and 1O2
lyst] = 0.4 g·L−1; pH = 3.0;
t=2 h
N-biochar @CoFe2O4 [MET] = 10 mg·L−1; 3cycles, > 80% Temperature; pH-dependent SO4·−,·OH and 1O2 partici- (Liu et al. 2019a)
t = 360 min [cata- and favorable at neutral and pated into degradation
lyst] = 200 mg·L−1; weak basic conditions
[PMS] = 0.5 mM; pH = 3–11
Page 15 of 31
Table 3 (continued)
Sonocatalytic system Ti-BC hydrogel beads 62% after four cycles Na3PO4 inhibits removal; pH; Cavitation, nucleation, Afzal et al. (2022)
Yang et al. Biochar
[CIP] = 30 mg·L−1; [cata-

lyst] = 1 g·L−1 t = 120 min; minerals; ultrasonic power; growth, and implosion of
ultrasonic power = 300 W catalyst amount; tempera- microbubbles
ture
(Fe-Cu-LDH) /biochar [cefazolin sodium] = 0.1 mM; 97.6% during 80 min; 9% Ultrasonic power; pH; h+ reacts with H2O, OH− to (Gholami et al. 2020a)
[catalyst] = 1 g·L−1; drop after five cycles dissolved gases; oxidants; generate ·OH, e‒ reacts with
(2022) 4:51
ultrasonic power = 300 W; organic/inorganic scaven- O2 to form O2‒·, which reacts
t = 80 min; pH = 6.5 gers with h+ to generate ·OOH
ZnO-biochar [GMF]0 = 20 mg·L−1; [cata- 83.7% COD removal within Pollutant concentra- h+ reacts with OH− and H2O Gholami et al. (2019a)
lyst] = 1.5 g·L−1; pH = 5.5; 90 min; 10% loss of degradation; solution turbulence; to generate ·OH, hot spots
ultrasonic power = 300 W tion after five runs catalysts dosage; ultrasonic product ·OH
irradiation powers; gas
addition
CeO2-H@biochar [RR84] = 10 mg·L−1; [cata- 98.5% within 60 min; 87.1% Initial RR84 concentration; Sonication generates Khataee et al. (2018)
lyst] = 1 g·L−1; t = 360 min; after five cycles pH; catalyst amount; ultra- OH and H radicals, and
pH = 6.5; ultrasonic sonic power enhances redox/ electronic
power = 300 W properties and peculiar
ceria-BC synergistic effect
Photocatalytic system Biochar@CoFe2O4/Ag3PO4 [BPA] = 20 mg·L−1; 80.23% mineral-ization in Mass ratio of magnetic Z-scheme photocatalytic Zhai et al. (2020)
visible-light irradiation; [cata- 60 min; 58.96% after 4 cycles biochar in catalysts mechanism, h+ and ·O2‒ are
lyst] = 0.5 g·L−1; t = 60 min active species
Fe3O4 based glucose mag- VL irradiation; Completely treat 8.0 log E. pH; dissolved O2 PS activation by ≡Fe(II) of Wang et al. (2020d)
netic hydrochar [Cell] = 8.0 log cfu·mL−1; coli cells, 40 min Fe3O4 and photo-generated
[MHC] = 200 mg·L−1; electron captured by PS
[PS] = 2 mM; T = 25°C; were major processes
pH = 3 ~ 9
Cu2O-CuO@biochar [RO29] = 20 mg·L−1; [cata- 94.12% in 90 min; 79.62% BC content; scavengers; h+, O2·− and ·OH are major Khataee et al. (2019)
lyst] = 1 g·L−1; pH = 8.7; UV COD removal in 180 min enhancers; dosage of cata- reactive agents
light irradiation lysts and pollutants
Biochar carbon-doped TiO2/ [ammonia] = 100 mg·L−1; 99.7% under UV light while Calcine temperature; pH; h+, ·O2− and ·OH are main Peng et al. (2019)
CuO 25°C for 24 h; sunlight and 60.7% under sunlight photocatalyst dosage active species
UV light irradiation
Zn-Co-LDH@biochar [catalyst] = 0.75 g·L−1; 92.7% in 130 min; < 10% Solute concentration; photo- ·OH is major reactive agents Gholami et al.
[GMF]0 = 15 mg·L−1; drop after five runs; 80% catalyst dosage (2020b)
pH = 2.5; UV light irradiation COD removal in 200 min
TiO2/biochar [MO] = 20 mg·L−1; [cata- 83.23% mineral-ization, Weight ratio of biochar to Ti h+, ·O2−, ·OH as active Lu et al. (2019)
lyst] = 0.25 g·L−1; UV irradia- 76.56% after 5 runs species
tion time; 150 min
TiO2/BC pH = 8.71; [KN- 99.71% within 60min when Illuminant; pH; catalysts dos- h+, ·O2−, ·OH as active Zhang and Lu (2018)
R] = 30 mg·L−1; [cata- PH=1; 73.98 ± 0.13% until age; KN-R concentration; species
lyst] = 6.0 g·L−1; UV high fifth cycle
pressure xenon lamp
Page 16 of 31
Table 3 (continued)
Activated carbon-TiO2 Completely reduced after Surface area and porosity of Photoreduction by e-, sensi- Djellabi et al. (2019b)
Yang et al. Biochar
Visible lights; pH = 3;
[CrVI] = 10 ppm; [cata- 30 min, 50 min and 130 min catalysts; composite tized mechanism, carboxyl-
Olive pits-TiO2 lyst] = 0.5 g·L−1; [Tartaric TiO2 surface-complex
mediated, charge transfer
Wood shaving-TiO2 acid] = 10 mg·L−1
TiO2/pBC [SMX] = 10 mg·L−1; pH = 4; 91.27% in 3 h; 57.44% of Calcination condition; inor- · − ·

O2 , OH are major reactive Zhang et al. (2017)
COD ganic anions; pH agents
(2022) 4:51
[photocatalyst] = 1.25 g·L−1

Ti-coupled N biochar [RhB] = 20 mg·L−1; [cata- 52.53% TOC removal Amount of Ti precursor – Li et al. (2018)
lyst] = 1 g·L−1; 20°C; visible-
light irritation
Zn-TiO2/biochar [catalyst] = 1.25 g·L−1; 81.21% in 3 h Zn content; solution pH; ·
O2−, ·OH as reactive oxygen Xie et al. (2019)
[SMX] = 10 mg·L−1; T = 25°C; catalyst dosage; anions species
pH = 5.03; visible light
irritation
TiO2-lignocellulosic bio- visible light; [dyes and 100, 75 and 81% in 1 h Pollutant; catalyst; Tert-butyl Dyes are oxidized by ·OH, Djellabi et al. (2019a)
mass@Fe3O4 Cr(VI)] = 10 ppm; [photo- for MB, RhB and CR; 100% alcohol concentration; pH; Cr(VI) is reduced
catalyst] = 0.25 g·L−1 within 40 min for Cr(VI) metallic cations
TiO2/Fe/Fe3C-biochar pH = Not adjusted (6.7); 376.9 mg·L−1 in 300 min Ratio of sludge; chitosan; ·
OH and some O2·‒perform Mian and Liu (2019)
[catalyst] = 1 g·L−1; Ti(OBu)4; glutaraldehyde; in degradation and miner-
[H2O2] = 0.57 M; FeCl3; H2O2; pH alization
[MB] = 200 mg·L−1
g-C3N4 modified biochar [MB] = 5.4 mg·L−1; 91% decoloriza-tion Biochar/melamine mass h+ and O2·‒ are the primary Pi et al. (2015)
[MO] = 16 mg·L−1; ratios; pH oxidative species
[p-nitrophenol] = 32 mg·L−1;
[catalyst] = 0.45 g·L−1; 18 W
LED light
Biochar@g-C3N4 core–shell [catalyst] = 0.5 g·L−1; ~ 55%, no evident activity Amounts of g-C3N4 h+ and ·O2− play main roles Wang et al. (2018b)
photocatalysts [TC] = 10 mg·L−1; light loss after 4 cycles as the active species
irradiation
Fe3O4/C/g-C3N4 Visible light; pH = 2; 100%, 20.9-fold that over pH Reduced mainly by the Ding et al. (2018)
[catalyst] = 0.2 g·L−1; g-C3N4 for Cr(VI) e− directly, subordinately
[Cr(VI)] = 20 mg·L−1 reduced by ·O2−
Magnetic biochar supported pH = 5.5; T = 30°C; 98.4% of MeP and 90.7% of Solar; ozone; pH; scavengers h+, ·O2−, ·OH as active Kumar et al. (2017)
g-C3N4/FeVO4 [catalyst] = 0.5 g·L−1; [methyl 2-CP in 60 min species
paraben and 2-cholrophe-
nol] = 20 mg·L−1
Page 17 of 31
Yang et al. Biochar
(2022) 4:51
Table 3 (continued)
Biochar@Bi2O2CO3/g-C3N4/ [catalyst] = 0.5 mg·mL−1; 99.3% under visible light in pH, H2O2, anions, ozone and SO4·− and ·OH are main Kumar et al. (2018)
CoFe2O4 [PQT] = 20 ppm; pH = 7.2; 90 min PMS active species
T = 30 ± 0.5°C
[4-NP] = 10 mM; N2; Complete conversion
[NaBH4] = 0.05 M; BCBF: in < 5 min
4-NP: NaBH4 = 1: 10:700;
[catalyst] = 100 g·L−1; t = 1 h; CH4 (∼ 119 μmol g−1), CO h+ reacts with H2O to gener-
[CO2] = 0.5 ml; Xe arc lamp (∼ 131 μmol g−1) and O2 ate H+ and O2, H+ reacts
880 W (∼ 242 μmol g−1) with CO2 and e− to generate
CH4
Biochar/BiOX (X = Br, Cl) [catalyst] = 1 g·L−1; 82% for 2.5 h Ratio of C/BiOX h+, ·OH and ·O2− function as Li et al. (2016)
[MO] = 0.6 M; t = 2.5 h; vis- active species
ible light irritation
CdSe/HTC composites [TC] = 20 mg·L−1; 35.86% mineralization Water substrates; pH; salt; TC e− produces ·O2−, which Men et al. (2019)
concentration; catalyst dos- reacts with h+ to generate
1
T = 25 ± 1°C; [cata-
lyst] = 0.5 g·L−1; t = 80 min; age; co-existing ions O2; ·O2−, h+, 1O2 are main
visible light irradiation active species
CdS@LAC-800 [organic dyes] = 40 mg·L−1; 97.8% in 60 min for MO; Activated carbon; produc- Efficient light harvesting; h+, Huang et al. (2018b)
[catalyst] = 100 mg·L−1; 96.3% at 150 min for MB tion temperatures O2·−, ·OH and H2O2 are main
visible light active species
g-MoS2/PGBC [TC] = 20 mg·L−1 50 mL; vis- > 40% TOC removal after Graphitization degree and h+ and ·OH are predominant Ye et al. (2019)
ible light irradiation 60 min conductivity of biochar; pH; active species
coexisting anions
Page 18 of 31
the oxidation–reduction activity of pure biochars. For contributor for MS-400/600 while CM took the absolute
instance, biochar-coated Fe(0) composite exhibited more dominance for MS-800, ASS and CM took the respon-
than 90% removal of 2,4,6-Trinitrotoluene in 5 h, and the O4·− and ·OH in MS-800/
sibility for the generation of S
biochar of the composite may act as an electron transfer PDS system (Yu et al. 2019).
mediator (Oh et al. 2017). An Ag nanoparticle-embed-
ded biochar hybrid material can completely catalytically 4.2.2 Transition metals‑based biochar catalysts
reduce Cr(VI) using formic acid as a reducing agent, and Transition metals, such as iron, copper, cobalt and so on,
the particle size of Ag plays an important role in this can efficiently activate oxidants to generate ROS. Due to
process (Liu et al. 2016). Obviously, pure biochar or bio- the excellent performance and low toxicity, iron-based
char-coated metal composites can efficiently achieve an catalysts have attracted extensive attention. Nanoscale
almost complete reduction of Cr(VI). The properties of zero valent iron (nZVI) and magnetite (Fe3O4), as two
pure biochar need to be adjusted to enhance its catalysis- common potential alternative sources of F e2+, can be
reaction. The cost and risks of heavy metal release of the used to activate oxidants for pollutant degradation. More
biochar-coated metal composite may be high, due to the than 70% of ciprofloxacin was removed, using BC/nZVI
introduction of metal. Biochar catalyst selection for the activating H2O2 (20 mM) in acidic conditions, and ·OH
pollutant oxidation and reduction should be based on the oxidation was the primary pathway in the process (Mao
biochar characteristics, cost, and environmental risks. et al. 2019). Similarly, the pyrolysis temperature signifi-
cantly affects the catalytic properties of magnetic biochar
4.2 Biochar‑based catalysts for Fenton‑like systems by affecting the size distribution of iron oxides, especially
4.2.1 Pure biochar Fe (II) content in these composites. In a study, metroni-
The biochars can effectively catalyze H 2O2 to form ROS, dazole was rapidly and completely degraded by the mag-
resulting in the degradation of pollutants. The pyrolysis netic biochar at the temperature of 400 °C (SMBC400)
temperature of biochar influenced •OH generation in the activating H2O2, and the rate of which was higher than
a ·SO4‒ mediated photocatalysis associated with a Fen-

presence of H
2O2. It was reported that wheat-derived bio- that of SMBC300 and SMBC500 (Yi et al. 2020). Recently,
chars at higher temperatures led to a higher yield of •OH
during H2O2 activation, and the degradation efficiency of ton-like system was used for bacterial inactivation. In
sulfamethazine (13.7 μM) went up from 93.4% to 100% this study, F e3O4-based magnetic hydrochar (MHC) was
with the increase of pyrolysis temperature, and the draw- used for persulfate (PS) activation under visible light.
back is that reactivity was inhibited by the adsorption of Complete treatment of 8.0 log E. coli cells was reached
sulfamethazine on their surface (Huang et al. 2016). within 40 min in visible light /PS/MHC system, suggest-
The peroxide could be effectively catalyzed by OFGs ing higher removal than that of PS/MHC system (Wang
and PFRs of biochars to form ROS or sulfate radicals for et al. 2020d). As a result, photo-Fenton-like systems may
pollutant degradation (Xia et al. 2020). The sewage sludge be a promising water disinfection technology. The Cu
biochar was proven to be an efficient persulfate activator and Co-based biochar catalysts were also used to acti-
for pollutant degradation, a high mineralization efficiency vate peroxide or hydrogen peroxide for organic pollutant
of ∼ 80% for BPA could be achieved by PMS at a biochar degradation. A solid digestate-biochar-Cu NP composite
dosage of 0.2 g·L−1 within 30 min, and 1O2 was the main (0.5 g·L−1) exhibited a tetracycline (TC) (200 mg·L−1)
reactive species (Huang et al. 2018a). The pyrolysis tem- degradation of 97.8% in the presence of H 2O2 within 6 h
perature significantly affects the activity of the activation of reaction time, which was mainly attributed to Cu(II)/
reaction. In a study, N-doped graphitic biochars (N-BCs) Cu(I) redox reaction and the electron-transfer process of
were used as catalysts for PDS activation. In particular, FRs in biochars (Fu et al. 2017). The degradation capac-
N-BC derived at 900 °C (N-BC900) exhibited the highest ity for TC is well above that of almost all other photo-
degradation rate, and it could completely degrade phe- catalysts. It was reported that nearly complete removal
nol, sulfamethoxazole (SMX) and BPA in 20 min, and of chloramphenicol (30 mg·L−1) was achieved in a
Orange G in 60 min at 20 ppm, which was 39-fold of that Co3O4-BC/PMS system within 10 min, the outstanding
on N-BC400 (Zhu et al. 2018). Different from the radical- performance of which mainly stems from the synergis-
based oxidation in N-BC400/PDS via the PFRs, 1O2 and tic effect of the conducting BC and the Co3+/Co2+ redox
nonradical pathways dominate the process. Besides, the reaction (Xu et al. 2020). In addition, non-metal, such as
contributions made by organic matter, acid-soluble sub- S and N doping can further promote the activity perfor-
stance (ASS), carbon matrix (CM), and basal part (BSP) mance of Co-based biochar catalysts. It was reported that
in a magnetic nitrogen-doped sludge-derived biochar the dinotefuran decomposition of S-doped C o3O4 com-
(MS) for activation reaction were significantly different, posite increased by 1.71 times as compared to the S-free
and it was reported that ASS was the most important sample, which was attributed to the enhanced generation
of 1O2 and various radicals by S incorporation (Du et al. (0.1 mM) at an ultrasonic power of 300 W within 80 min
2020). Similarly, a higher pyrolysis temperature of bio- (Gholami et al. 2020a). In a study, two types of hierarchi-
char could improve PDS activation reaction. A N-doped cally structured manganese dioxide/biochar nanocom-
graphitic biochar (SDBC-900) showed a faster degrada- posites (MnO2/BCs) were prepared for BPA degradation
tion with complete SMX removal compared with 33.0% in an ultrasound-assisted heterogeneous Fenton-like
and 84.9% on the biochar pyrolyzed at 400 and 700 °C in system. In this process, the crystalline properties of the
45 min (Ho et al. 2019). During this process, the SDBC nanocomposites affected their catalytic activity, and the
900-acid played versatile roles in PDS activation. While S α-MnO2/biochar exhibited complete removal of BPA
doping is not always positive for PMS activation, accord- (100 μM) in the presence of H2O2 (10 mM) by using an
ing to a previous study, a heteroatom (N and S) doping ultrasonic power of 130 W within 20 min (Jung et al.
biochar was used for the catalytic degradation of meto- 2019). Cerium oxide (CeO2) and Z rO2, as oxides of the
lachlor through activating PMS, N-doping positively lanthanide metal, have been widely used to couple with
whilst S-doping negatively influenced the degradation biochars as heterogeneous catalysts. The prepared
process (Ding et al. 2020). In conclusion, the biochar- CeO2-H@BC nanocomposites exhibited the best Reac-
based catalysts exhibited better degradation performance tive Red 84 degradation efficiency, which was enhanced
in the Fenton-like system than that of photocatalysis sys- with the increase in ultrasonic power. In this process,
tem for refractory emerging organic pollutants, such as a 98.5% degradation was obtained with an ultrasonic
TC, SMX, ciprofloxacin and so on. However, pollutants power of 450 W and an initial Reactive Red 84 concentra-
degraded by biochar-based catalysts in the Fenton-like tion of 10 mg·L−1 (Khataee et al. 2018). A ZrO2-biochar
system might generate high-cost and ecotoxicity risks, exhibited 96.8% degradation efficiency with an initial
due to the induction of peroxide (Li et al. 2022). Based on Reactive Yellow 39 concentration of 20 mg·L−1 and ultra-
the cost-effectiveness, photo-Fenton-like systems may be sonic power of 300 W (Khataee et al. 2017b). The high
a promising development direction in degradation-resist- sonocatalytic activity could be explained by sonolumi-
ant wastewater treatment. nescence and hot spot mechanisms. Interestingly, the
TiO2-biochar nanocomposites could be used as sono-
4.3 Biochar‑based catalysts for sonocatalytic systems catalyst for dye degradation, the mechanisms of which
The application of ultrasound as a primary source to are similar to those of Z rO2-biochar, and degradation
stimulate chemical reactions has received increas- efficiency of 97.5% was observed at initial Reactive Blue
ing attention. However, there are some disadvantages, 69 concentration of 20 mg·L−1 and ultrasonic power of
including long treatment time and huge consumption 300 W after 80 min (Khataee et al. 2017a). In conclu-
of energy, biochar-based materials can act as suitable sion, biochar-based composite catalysts could efficiently
sonocatalysts to counter these deficiencies (Wang et al. degrade (almost 100%) cationic dyes, and the perfor-
2019a). As the name implies, the ultrasonic frequency mance increased with the increase of ultrasonic power,
had a substantial effect on the sonocatalytic reaction whereas the tendency was opposite to pure biochar. To
(Gholami et al. 2019b). Recently, a series of biochar- develop new biochar-based composite and ultrasound-
based composite catalysts, including pure biochar, transi- assisted heterogeneous Fenton-like system for the
tion metals, lanthanide metal and semiconductor-based removal of emerging persistent organic pollutants may be
biochar composites were synthesized. currently an important development direction.
Biochar, as a sonocatalyst, is more useful in low-fre-
quency ultrasound systems for organic pollutant degra- 4.4 Biochar‑based catalysts for photocatalytic systems
dation. In a previous study, a peat-moss derived biochar 4.4.1 Pure biochar
exhibited higher removal efficiency for rhodamine B Pure biochar can directly generate ROS without oxi-
(100 mg·L−1) at 40 kHz (51.8%) than that at 300 kHz dants for organic pollutant degradation under UV light
(26.2%) after 1 h, due to less dispersion of the biochar in irradiation. It was reported that 100%, 95% and 89% of
the solution at 300 kHz, and stronger sonophysical effects 5.0 mg·L−1 diethyl phthalate were degraded in pine nee-
at 40 kHz, which significantly enhanced the sonochemi- dles, wheat and maize straw biochar (pyrolysis at 300 °C)
cal oxidation reactions on the surface of the biochar (Kim suspensions in the presence of O2, respectively, with the
et al. 2018). Similarly, Fe, Cu, Mn and Zn, as common reaction time of 24 h (Fang et al. 2015). In this process,
O2 to produce the ·O2‒ and H

transition metals, are usually used to prepare catalysts Free radicals (FRs) in biochar transferred electrons to
owing to the characters of high efficiency, non-toxicity, 2O2, which reacted further
low cost and environmental friendliness. For instance, with FRs to produce ·OH. Biochar carbon matrix (BCM)
Fe-Cu layered double hydroxide/biochar exhibited a high and DOM can induce the generation of ROS under solar
sonocatalytic efficiency of 97.6% for cefazolin sodium irradiation. In a previous study, the photogeneration of
ROS from biochar suspension was investigated, and the which can transfer electrons or serve as acceptor, and the
results indicated that BCM accounted for 63.6–74.6% of absorbance in the visible light band with the increase of
·
OH and 10–44.7% of 1O2 formation, while DOM derived the ratio of biochar to T iO2. In addition, early work on
from biochar generated 46.7–86.3% of 1O2 and 3.7–12.5% doped TiO2 employed transition metals (e.g., Cr, Mn, Fe,
of •OH, and almost 59–72% diethyl phthalate degrada- Zn and Cu) introduced as substitutional atoms inside the
tions were achieved within 120 min under UV light by crystalline habit to generate 3d electronic states lying in
pine needle and wheat straw biochars (Fang et al. 2017). the range 0.5–1.5 eV below the conduction band (CB) of
Moreover, it was reported that DOM strongly influences TiO2, thus providing visible light absorption, for example,
the photodegradation of organic pollutants, which var- the TiO2/Fe/Fe3C-biochar obtained a rising adsorption in
ies depending on the structure of DOM. After exposure the visible-light region due to the charge transfer of Ti3+,
to UV light, the aromaticity and molecular weight of the Si, Al, and Fe, and the methylene blue removal capacity
DOM declined due to photo transformation, and signifi- evaluated as 376.9 mg·L−1 (Mian and Liu 2019). How-
cant enhancement was observed in imidacloprid photo- ever, metal doping may show an unfavorable trade-off
degradation (almost 90% in 90 min) in the presence of between absorption and photocatalytic activity, result-
biochar-derived DOM (Zhang et al. 2020a). It is noted ing in increased charge recombination via newly formed
that the biochars exhibited different performance, due deep electronic levels (Naldoni et al. 2019). For instance,
to differences in biochar pyrolysis temperature. Besides, Zn-TiO2/biochar exhibited a lower degradation (81.21%)
the pyrolysis temperature affects the photocatalytic activ- (Xie et al. 2019) than that of T iO2/biochar (91.27%)
ity of dissolved state biochar (DSB). It was found that (Zhang et al. 2017) for SMX in 3 h. In contrast, the non-
the photocatalytic efficiency of DSB increased with the metal (e.g., N, C, and S) doping can form 2p electronic
decrease of pyrolysis temperature, and DSB300 had the states above the valence band (VB) capable of producing
greatest gradation of 60% for atorvastatin (10 μM) in 5 h efficient charge transfer electronic transition to the 3d
under sunlight. The greatest performance could be attrib- CB of TiO2 and thus providing high photocatalytic activi-
uted to the dual role of DSB, the mineral and organic ties (Naldoni et al. 2019). Among these, nitrogen and sul-
carbon components of which can act as heterogeneous fur have provided better and similar band gap narrowing,
photocatalysts and photosensitizers to synergistically but the large ionic radius of sulfur requires much higher
enhance electron–hole separation, and contribute to the formation energy, hence nitrogen doping has proved to
formation of 1O2 and triplet-excited state (3DSB*) (Shi be more promising for visible-light-driven photocataly-
et al. 2020). Consequently, FRs, BCM, DOM, and DSB sis (Kumar et al. 2019a). For example, in the previous
play a critical part in enabling biochars to participate in study, the incorporation of nitrogen into the crystalline
photocatalytic reactions. To manufacture biochars with TiO2 lattice may modify the electronic band structure of
targeted photocatalytic performance, it is essential to TiO2, then a new substitutional N 2p band was formed
define the correlation of photochemical reactivity with above the O 2p valance band, which narrowed the TiO2
the structure and moieties of biochars. band gap, and shifted the optical absorption to the vis-
ible light region, resulting in a better performance of
4.4.2 Titanium dioxide N-TiO2@SiO2@Fe3O4 photocatalyst (Kumar et al. 2019a).
Titanium dioxide, as the most commonly used photo- The results showed that 93% of benzophenone-3 within
catalyst, provides a set of beneficial redox properties (Hu 5 h and 71% of carbamazepine within 9 h were degraded
et al. 2020). However, the photocatalytic activity is ham- under visible light. A Ti-coupled N-embedded chicken
pered by limited light absorption and the high recom- feather biochar also presented a 90.91% degradation rate
bination of charge carriers (Naldoni et al. 2019). To of Rhodamine B under visible light after 240 min (Li et al.
mitigate this limit, different approaches have been 2018). The direct contact of F e3O4 and T iO2 may enhance
explored for the material’s assembly, such as nanocrys- the visible light response a little, whereas it brings an
tals’ shape and facet engineering, heterojunction con- unfavorable heterojunction, resulting in lower photo-
struction, and metal co-catalyst deposition (Chen et al. catalytic performance. Obviously, the oxidation rate for
2010). The previous researches had indicated that bio- Rhodamine B degradation (75% in 1 h) using TiO2-olive
chars can serve as a support for T iO2 to remedy the pits@Fe3O4 is faster than that of Ti-coupled N-embedded
above shortcomings. The TiO2/biochar composite exhib- chicken feather biochar, due to the presence of olive pit
ited a higher decolorization efficiency of 96.88% than biomass, which can enhance adsorption capacity and
that of single T
iO2 for methyl orange (Lu et al. 2019). An serve as a charge acceptor via Ti–O–C bridge and inhibit
obvious enhancement of absorption in the visible light the transfer of electron/hole charges from T iO2 to F
e3O4
band was obtained owing to the presence of biochar, (Djellabi et al. 2019a).
4.4.3 Graphite carbon nitride 4.4.4 Bismuth oxyhalide

Graphitic C3N4, as a nonmetal photocatalyst, possesses As a common semiconductor with a special layered
a comparatively narrower bandgap of ca. 2.7 eV, good structure, BiOX is composed of [Bi2O2] slabs interleaved
thermal chemical stability and cheaper cost than T iO2. with double halogen atoms labs, which can effectively
Unfortunately, bulk g‐C3N4 exhibits poor electronic separate electrons and holes (Li et al. 2016). However, the
properties, small specific surface area and low quantum inherent large band gaps of BiOCl (∼ 3.4 eV) and BiOBr
yield due to structural defects of stacking of the layers, (∼ 2.6 eV) still restricted their applications in solar con-
and tremendous efforts have been made to improve version, various strategies such as heterojunction forma-
the photocatalytic efficiency through design strate- tion, doping, interface modification, enhancement in Bi
gies, including band-gap engineering, defect control, content, inner coupling between different BiOX pho-
pore texture tailoring, dimensionality tuning, surface tocatalysts, use of sensitizers and creation of oxygen
sensitization, heterojunction construction, co-catalyst vacancies can improve photocatalytic performance
and nanocarbon loading (Wen et al. 2017). Similarly, (Sharma et al. 2019). Li developed biochar/BiOBr com-
biochar can play an important role in enhancing the posite photocatalysts, and the visible-light absorption
photocatalytic activity of g‐C3N4. A simple biochar@g- of BiOX catalysts can be exceedingly enhanced by bio-
C3N4 composite initially was used to degrade cationic char, which mainly stems from the profoundly improved
dye, exhibiting a more desirable decolorization rate of charge separation and delivery efficiency (Li et al. 2016).
91% for methylene blue than that of C 3N4 in 3 h, due to And the catalysis ability is affected by the mass ratio
enhanced methylene blue adsorption (Pi et al. 2015). It between biochar and BiOX, and for10% biochar/BiOBr,
can be found that the cationic dye methylene blue decol- the degradation efficiency of methyl orange reaches 82%
orization capacity of biochar@g-C3N4 is lower than under visible-light irradiation within 2.5 h, which is much
that of TiO2-Lignocellulosic Biomass@Fe3O4 (Djellabi higher than that of pure BiOBr. Obviously, the biochar/
et al. 2019a) and TiO2/Fe/Fe3C-biochar (Mian and Liu BiOBr exhibited slightly lower degradation efficiency of
2019). However, biochar@g-C3N4 catalyst may be more methyl orange than that of T iO2/biochar (Lu et al. 2019),
practical in the application of cationic dye decoloriza- while biochar/BiOBr had a better practical application
tion, due to better visible light absorption. Recently, the prospect in decolorization of cationic dyes, due to the
antibiotic TC degradation is still a challenge, due to its wide visible-light adsorption.
recalcitrance. It was reported the biochar spheres acted
both as a reservoir and a sensitizer in biochar@g-C3N4 4.4.5 Other photocatalysts
core–shell photocatalyst to enhance light absorption Other photocatalysts were also used to couple with bio-
in nearly the entire wavelength range due to the nar- chars. Liu prepared Ag/Ag3PO4 support amino-modified
rower gap of the sp2 carbon cluster and large amounts biochar composite, which exhibited greatly enhanced
of carbon clusters (Wang et al. 2018b). The core–shell photocatalytic performance, and almost 80% amoxicil-
non-metallic photocatalyst exhibited a degradation rate lin was decomposed in 120 min, whereas only 65% with
of 55% for TC (10 mg·L−1) in 80 min under visible light pure Ag3PO4 (Liu et al. 2017a). The CdS load activated
irradiation, which was 4 times as high as that of the biomass carbon composite displayed excellent photo-
g-C3N4. The degradation of TC using biochar@g-C3N4 catalytic ability toward methyl orange and methylene
in photocatalysis system is far below that of biochar- blue degradation with the efficiency of 97.8% at 60 min
based catalyst using in Fenton-like system. An oxidation and 96.3% at 150 min, respectively (Huang et al. 2018b).
biochar supported magnetite particles (OBC-Fe3O4) CuWO4, a n-type semiconductor, was supported on bio-
exhibited better catalytic performance for PS activa- char to construct a Biochar-CuWO4 composite with deg-
tion due to its abundant oxygen-containing groups on radation up to 97% of ciprofloxacin after 90 min of visible
the surface and F e3O4 particles, which resulted in 92.3% light irradiation (Thiruppathi et al. 2020). Besides, the
of TC (20 mg·L−1) removal within 2 h (Pi et al. 2019). nanocomposites exhibited complete photodegradation of
Even so, the degradation performance of TC is not good methylene blue and Rhodamine B solutions after 80 min
enough, using either the biochar@g-C3N4 composite of light irradiation. In a work, an N-modified biochar,
in catalysis system or biochar-based catalysts in the with great conductivity and a special 2D sheet platform
Fenton-like system. To design a photo-Fenton system structure, was used as a platform for supporting Bi2WO6,
via taking advantage of photocatalysis and Fenton-like causing a narrower band gap of the composites than that
reactions may be a promising way to further enhance of Bi2WO6 (Wang et al. 2020c). The composites exhibited
the degradation of TC. excellent photocatalytic activity for the degradation of
10 mg·L−1 Rhodamine B (99.1%, 45 min) and reduction lead to the transference of the electrons on the CuO and
of Cr(VI) (96.7%, 30 min) under visible light irradiation. Cu2O CB and the hole from CuO to the VB of Cu2O,
In conclusion, it could be found that the new biochar- hence 94.12% degradation efficiency of Reactive Orange
based CdS, C uWO4, Bi2WO6 composites can very effi- 29 was obtained by the composite at the initial concen-
ciently (nearly 100% within 2.5 h) degrade cationic dyes, tration of 20 mg·L−1 after 90 min under UV-B light irra-
such as Rhodamine B, methyl orange, methylene blue and diation (Khataee et al. 2019). By the utilization of g-C3N4,
so on, under visible light, the performance of which is polyaniline (PANI), reduced graphene oxide (RGO) and
better than that of biochar/BiOX. Compared to conven- biochar, a Z-scheme photocatalyst g-C3N4/ACN/RGO@
tional TiO2 or g-C3N4 based catalysts, the new catalysts, biochar was synthesized and exhibited a high degrada-
such as g-MoS2, Bi4Ti3O12 based catalysts and so on, tion of 99.7% and 98.4% for 2,4-Dichlorophenoxy acetic
have better performance for TC degradation. A porous acid and ibuprofen (20 mg·L−1) under visible light expo-
graphite biochar self-assembled with g-MoS2 nanosheets sure in 50 min (Kumar et al. 2019b). Similarly, Ag3PO4 is
is observed to have enhanced visible light harvesting, a visible light-responsive photocatalyst with a higher
accelerated charge transfer, efficient carrier’s separa- quantum efficiency (90%) but susceptible to photo cor-
tion, and excellent performance for TC degradation, and rosion caused by Ag+ reduction, which could be solved
more than 40% of the total organic carbon (TOC) could by constructing Z-scheme heterojunctions with C oFe2O4,
be removed after 60 min under visible light irradiation hence a biochar@CoFe2O4/Ag3PO4 Z-scheme composite
(Ye et al. 2019). Similarly, the metal doping can further was prepared, and exhibited the high photocatalytic and
improve photocatalytic performance. Wang reported Ag mineralization ability of 91.12% and 80.23% for bisphe-
can be applied as excited electron–hole pairs in biochar nol under visible-light within 60 min (Zhai et al. 2020).
quantum-dot/Bi4Ti3O12 nanosheets by transferring the In conclusion, the heterojunctions, especially Z-scheme
plasmonic energy from the metal to the semiconductor, composite, exhibited higher photocatalytic efficiency
and the 2D Ag/carbon quantum dots/bismuth titanate than that of biochar coupled single photocatalyst, and
exhibited a high degradation efficiency of almost 90% the mass ratio between biochar and catalysts significantly
for TC (10 mg·g−1) under visible-light irradiation after affected the performance of the composite. However, the
90 min (Wang et al. 2019b). The surface plasmon reso- cost of heterojunction photocatalysts is comparatively
nance of Ag can promote the electron transfer properties higher, due to the multistep synthetic process and induc-
of the biochar quantum-dots, meanwhile, it can act as an tion of some precious metals, such as Ag. Consequently,
electron buffer to decrease the recombination rate of the as illustrated in previous studies, the heterojunction pho-
electron hole, and provide a chemical group to enhance tocatalysts may be more applicable to the degradation
the electron transfer and connection. of toxic and refractory organic contaminants, such as
methyl paraben, bisphenol, chlorophenol, ciprofloxacin
4.4.6 Heterojunctions and so on.
Among these strategies, the construction of heterojunc-
tions has seen a recent explosion of interest due to fur- 5 Environmental concern of biochar‑based
ther improvement in photocatalytic efficiency of biochar catalysts
coupled single photocatalysts. According to the hetero- The excellent performance of biochar-based catalysts
junction energy band theory, when different semicon- applied to water and soil pollution control had accepted
ductors with the difference in energy band structure widely attention, but potential environmental effects
are combined, the semiconductors can absorb the radi- remain largely unexplored and poorly understood. Gen-
ant energy and be excited to generate electron–hole erally speaking, the potential risk of biochar-based cata-
pairs, and with a heterojunction, the band gap energy lysts toward the environment mainly stems from the
can be significantly reduced and therefore light absorp- release of toxic contaminants during the production and
tion as well as charge transfer will be increased (Wen application in environmental modifications.
et al. 2017). Recently, the biochar coupled heterojunc-
tion composites were prepared, and exhibited superior 5.1 Impacts of biochar‑matrix on environment
photocatalytic performance, due to the narrow band gap, The pyrolysis of biomass can generate some toxic con-
high surface area, broader solar spectrum response and taminants (such as aromatic hydrocarbons, aldehydes
reduced charge carrier recombination. Among oxide- and ketone), which are usually highly toxic, with high
based semiconductors, Cu2O and CuO as the p-type volatility and low water solubility, particularly high
semiconducting materials have a relatively narrow band environmental mobility (Raclavska et al. 2018; Shaheen
gap of 1.8–2.2 eV and 1.2–1.8 eV, respectively. The poten- et al. 2019). In general, the pyrolysis at a low tempera-
tial difference in the VB or CB of Cu2O and CuO could ture can produce biochar with high toxicity owing to
the inadequate combustion (Lyu et al. 2016). Polycyclic deemed as toxic (Zhang et al. 2018), but iron oxide parti-
aromatic hydrocarbons (PAHs), as a highly toxic per- cles including Fe3O4 and Fe2O3 are nontoxic or low-toxic
sistent organic pollutant, are generated as temperatures matter (Lei et al. 2018). For example, nano-TiO2 has vari-
approach 1000 °C (Nakajima et al. 2007). PAHs might ous negative impacts on the health of a variety of verte-
be toxic to organisms, such as crustaceans, while there brate animals, and it could cause damage to the cardiac
is no evidence of the existence of a correlation between and reproductive systems, and pose a significant threat
PAHs content and the ecotoxicity of biochar to terrestrial to the recruitment of broadcast spawning invertebrates
flora and fauna (Oleszczuk et al. 2013). This phenomenon (Han et al. 2019). Particle size and shape are important
might be explained by the synergetic impacts of various factors affecting toxicity (Suresh et al. 2013). Generally,
contaminants, and the interactions between biochars and toxicity increases with the decrease of particle size, and
contaminants (Liu et al. 2018). The persistent free radicals the particles with sharp edges and corners are chemi-
(PFRs), generated during biomass pyrolysis, could induce cally and biologically reactive, and small spherical parti-
the formation of reactive oxygen species, which pose cles are more toxic than rod-like particles because they
huge agro-environmental and human health risks, due to can damage the cell membrane more easily (Zhuang et al.
their half-lives and persistence in both biochar residues 2017, 2019). Due to the complexity of environmental fac-
and the atmosphere (Odinga et al. 2020). In addition, bio- tors, metal oxide nanoparticles may undergo structural
char matrixes may release heavy metals when applied to changes, which may further strengthen the toxicity of
environmental remediation. For example, the most toxic nanoparticles (Zhang et al. 2018). For example, in the
chemicals dioxins (Hale et al. 2012) and potentially toxic presence of phosphate, ZnO nanoparticles change from
elements, such as Pb, Cd, Cr, Cu, Ni, Zn, and As, have uniform spherical particles into larger anomalous porous
also been detected in biochar (Freddo et al. 2012), which particles that are more toxic to mammalian cells than the
might be released into the environment. A study showed initial nanospheres (Lv et al. 2012). Most of the toxicity
that corn cob biochars inhibited urease activity due to studies only focused on the raw nanoparticles, which
the release of heavy metals and polyaromatic hydrocar- overlooked the potential harm of nanoparticles under
bons (Liu et al. 2018). Carbon nanoparticles are difficult complex natural environmental conditions (Zhuang et al.
to degrade under natural conditions and are harmful to 2019). In future researches, it is necessary to understand
living organisms, and the toxicity mechanism includes the potential toxicity effects of particles relating to their
oxidative stress response, mechanical damage and effects possible nanostructure changes. The fabrication process
on biological enzymes (Peng et al. 2020). Moreover, the of the biochar-based materials should be optimized to
·
OH stemming from biochar and biochar-based cata- improve their stability before and after use, so as to mini-
lysts in the aqueous phase may cause significant inhibi- mize or eliminate the potential release of these toxic con-
tory effects on seed germination, seedling root and shoot taminants to the environment (Lu et al. 2020).
growth, and the damage of plasma membranes in corn,
wheat, and rice (Liao et al. 2014). However, some stud- 5.3 The toxicity of reactive intermediates
ies reported that carbon nanoparticles can act as a plant The intermediates with higher biochemical toxicity
growth inducer causing enhanced plant dry biomass than that of the original pollutants might be generated
and root/shoot lengths, hence are transpiring as a nano- when using biochar-based catalysts to degrade con-
carbon fertilizer in soil (Vithanage et al. 2017). And the taminants (Wang et al. 2018d). In most cases, organic
accumulation of carbon nanoparticles in the soil can pollutants are not completely mineralized by UV-AOPs
further modify the balance among plant-toxic metals in but are partially oxidized into transformation products
soil, thereby enhancing the translocation of heavy metals (TPs), which could increase the complexity of the water
(loids) into the plant system (Vithanage et al. 2017). remediation. Although present at low concentrations,
TPs might threaten the health of humans, living organ-
5.2 Impacts of metal nanoparticles of biochar‑based isms and eco-systems (Wang et al. 2018d). Fortunately,
catalysts in environment in most cases, the results are optimistic, the degrada-
The preparation process of biochar-based catalysts tion usually causes the reduction of contaminant toxicity
involves acid/alkali/oxidant, hence might be a pollut- (Liang et al. 2021). For example, the toxicity of Cr (III)
ant source (Wang et al. 2018e), the toxic elements or obtained by the photocatalytic reduction of Cr (VI) is
metal nanoparticles in biochar-based materials are also so far below that of Cr (VI). During the process of TC
non-negligible risks. When applied in environmental photocatalysis degradation, the acute toxicity of inter-
modification, these metal compositions may be released mediates was lower than that of TC. Worryingly, the
into the environment, leading to secondary pollution. bio-accumulative of the TC intermediates increased sig-
Semiconductors such as T iO2, CuO and ZnO are usually nificantly (Wang et al. 2020e).
6 Conclusions and future perspective Author contributions

BY: conceptualization, methodology, writing—original draft. JD: methodology,
This work reviews recent advances in biochar-based formal analysis, data curation. YZ: conceptualization, resources, supervision.
catalyst preparation, application in contaminant JW: validation, data curation. CJ: formal analysis, validation. YZ: supervision,
removal, and environmental risks. The physicochemi- funding acquisition, project administration, writing—review and editing. All
authors read and approved the final manuscript.
cal properties of biochar are significantly affected by
temperature, and hydrochar with desirable carbon and Funding
ash content could be accurately prepared by adjusting This work is funded by the National Natural Science Foundation of China
under Grant 41671331, the Innovative Approaches Special Project of the
the temperature. The choice of the preparation method Ministry of Science and Technology of China under Grant (2020IM020300),
for catalysts is based on raw materials and desirable the Beijing–Tianjin–Hebei Collaborative Innovation Promotion Project, China
catalysts. The enhanced performance of biochar cata- (Z201100006720001) and the National Key Research and Development
Program of China under Grant 2016YFA0600103. We want to acknowledge
lysts is mainly attributed to the unique physicochemi- anonymous reviewers for their valuable comments.
cal properties of biochars, which could be used both as
support and electron reservoir, resulting in the increase Availability of data and materials
All date generated during the current study are available from the corre-
in adsorption capacity, catalytic active sites and charge sponding author on reasonable request.
separation of catalysts. Nearly complete removal of
cationic dyes and hexavalent chromium could be Declarations
achieved by simple biochar catalysts in photocatalysis,
sonocatalytic and redox systems. Biochar heterojunc- Ethics approval and consent to participate
Not applicable.
tion catalysts are especially suitable for the removal of
refractory emerging organic pollutants, due to the bet- Competing interests
ter performance but significantly complex preparation The authors declare that they have no known competing financial interests
or personal relationships that could have appeared to influence the work
process. Emerging organic pollutants could be more reported in this paper.
efficiently removed by biochar catalysts in a Fenton-like
system than those in the other three systems. The toxic Author details
1
College of Resource Environment and Tourism, Capital Normal University,
contaminants of biochar-matrix, metal nanoparticles Beijing 100048, China. 2 School of Environmental and Safety Engineering,
of catalysts and intermediates stemming from the reac- Changzhou University, Changzhou 213164, China.
tion process of pollutants are the main risks when using
Received: 12 February 2022 Accepted: 27 June 2022
biochar-based catalysts.
Despite considerable progress made in preparation,
and application in contaminant removal of biochar-
based catalysts, further research still needs to be done
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Yang et al.

Biochar (2022) 4:51

REVIEW Open Access

Advances in preparation, application

Keywords: Biochar-based catalysts, Sonocatalysts, Fenton-like catalysts, Photocatalysts, Pollutant removal,

1 Introduction sewage sludges, manures, algas, wood chips and so on,

transfer, which reduce the recombination of the ­e‒/h+

Table 1 Technologies for production of biochars with advantages and shortcomings

2.1.3 Hydrothermal carbonization as promising catalysts. For example, a previous study

C (wt %) O (wt %) Metal (wt %) BET ­(m2·g−1) Vt ­(cm3·g−1)

C (wt %) O (wt %) Metal (wt %) BET ­(m ·g ) Vt ­(cm ·g )

Biomass types Preparation Preparation Catalysts Characteristics Active moiety References

[CIP] = 30 mg·L−1; [cata-

TiO2/pBC [SMX] = 10 mg·L−1; pH = 4; 91.27% in 3 h; 57.44% of Calcination condition; inor- · − ·

[photocatalyst] = 1.25 g·L−1

a ·SO4‒ mediated photocatalysis associated with a Fen-

­O2 to produce the ·O2‒ and H

4.4.3 Graphite carbon nitride 4.4.4 Bismuth oxyhalide

6 Conclusions and future perspective Author contributions

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transfer, which reduce the recombination of the e‒/h+

2.1.3 Hydrothermal carbonization as promising catalysts. For example, a previous study

C (wt %) O (wt %) Metal (wt %) BET (m2·g−1) Vt (cm3·g−1)

C (wt %) O (wt %) Metal (wt %) BET (m ·g ) Vt (cm ·g )

O2 to produce the ·O2‒ and H

4.4.3 Graphite carbon nitride 4.4.4 Bismuth oxyhalide

6 Conclusions and future perspective Author contributions