Liu et al.

Carbon Research (2022) 1:8

https://doi.org/10.1007/s44246-022-00007-3

REVIEW Open Access

Modified biochar: synthesis and mechanism

for removal of environmental heavy metals
Zhixin Liu1,2, Ziyi Xu2, Linfeng Xu2, Faeiza Buyong1*, Tay Chia Chay1, Zhuang Li3, Yawen Cai2, Baowei Hu2,
Yuling Zhu2 and Xiangke Wang2,3*

Abstract
With social progress and industrial development, heavy metal pollution in water and soils environment is becoming
more serious. Although biochar is a low-cost and environmentally friendly adsorbent for heavy metal ions, its adsorp-
tion and immobilization efficiency still need to be improved. As an upgraded version of biochar, modified biochar
has attracted extensive attention in the scientific community. This review summarized the recent research progress
on the treatment methods on heavy metal pollutants in water and soils using biochar. The features and advantages
of biochar modification techniques such as physical modification, chemical modification, biological modification and
other categories of biochar were discussed. The mechanism of removing heavy metals from soil and water by modi-
fied biochar was summarized. It was found that biochar had better performance after modification, which provided
higher surface areas and more functional groups, and had enough binding sites to combine heavy metal ions. Biochar
is a very promising candidate for removing heavy metals in environment. Furthermore, some high valent metal ions
could be reduced to low valent metals, such as Cr(VI) reduction to Cr(III), and form precipitates on biochar by in-situ
sorption-reduction-precipitation strategy. However, it is still the direction of efforts to develop high-efficiency modi-
fied biochar with low-cost, high sorption capacity, high photocatalytic performance, environmentally friendly and no
secondary pollution in future.

Highlights
1. Efficient elimination of heavy metal ions by biochar from wastewater was summarized.
2. Immobilization of heavy metal ions in soil by biochar through sorption-reduction-precipitation was reviewed.
3. The interaction mechanism of heavy metal ions with biochar was discussed in details.
Keywords: Modified biochar, Environmental heavy metals, Synthesis, Mechanism, Pollution management

1 Introduction fertilizers has become increasingly serious. The pollu-

With the rapid development of industry and the increase tion by heavy metals is a serious threat to environmental
in the types and quantities of agricultural chemical ecosystem and human health because of its persistence
products, the pollution of heavy metals in natural water and concealment. Therefore, the efficient elimination of
and soils caused by industrial wastes, pesticides, and heavy metals from water and soil has been a hot issue
of the public for many years (Wang et al. 2019a; Zhang
et al. 2021a; Yu et al. 2021; Liu et al. 2021). Because
*Correspondence: [email protected]; [email protected] heavy metals are difficult to be biodegraded or trans-
1
Faculty of Applied Sciences, University Technology MARA​, 40450 Shah Alam, formed, adsorption and immobilization have become
Malaysia
2
School of Life Science, Shaoxing University, Shaoxing 312000, China
the focus of researchers as the most promising treatment
Full list of author information is available at the end of the article methods in recent years (Liu et al. 2022a). Under the

© The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which
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Liu et al. Carbon Research (2022) 1:8 Page 2 of 21

dual pressure of social development and environmental In the database of Web of Science (SCIE only, from
protection, biochar has attracted great attention because 2008), papers with the topic of "modified biochar"
of its wide application in environmental pollution con- or "biochar modification" or "engineered biochar" or
trol and its environmental and economic benefits (Liang "designer biochar" were searched on April 22, 2022, and
et al. 2021). a total of 3310 papers were found. The retrieved arti-
Biochar is a kind of solid biofuel with high carbon cles were saved as plain text files, including full records
and hydrogen contents and large specific surface areas. and cited references, and were converted into execut-
It usually refers to converting biomass (e.g., plants, able formats using Citespace’s "Data/Import/Export"
industrial wastes, agricultural wastes, sludge and live- function to visualize the retrieval records (Panahi
stock manure, etc.) in anoxic or anaerobic environment et al. 2020; Chen et al. 2012). After statistical analysis
and pyrolyzed at a temperature not higher than 1000 of the publication years of the papers, it is found that
°C (Wardle et al. 2008; Amusat et al. 2021), as shown the related papers have been increased year-by-year
in Fig. 1. Waste-based biochar is considered an environ- since 2009, and have shown a rapid growth especially
mentally friendly material, and it’s easy to be obtained in recent five years (2017 to present), as shown in Fig. 2.
with low cost. Biochar can adsorb and fix organic con- Hence, modification of biochar for its removal ability
taminants and heavy metals in water and soils (Gao et al. improvement is a hot research issue at present. Cites-
2019; He et al. 2019), and has a wide application in envi- pace was used to analyze the keyword co-occurrence of
ronmental protection, agricultural production and other the articles, setting the time slicing from January 2009
fields. to April 2022, one year per slice, choosing "Keyword"
Biochar is rich in stable carbon and contains a large as the node type, setting the selection criteria to TOP
number of nutrient elements. It is widely used in car- 5.0% and the maximum number of selected items per
bon sequestration and soil improvement due to its rich slice to 50. It is found that 12 keywords co-occurrence
surface micropore structures and the resulting huge sur- more than 300 times are as follows: sorption/sorption
face areas, as well as rich functional groups. Biochar can (1312), aqueous solution (838), removal (779), activated
be used as adsorbents and passivators to remove heavy carbon (559), biochar (502), water/waste water (836),
metals from water and fixed heavy metals in soils (Qiu heavy metal (425), soil (344), carbon (343), and mecha-
et al. 2022). This is a win–win strategy for the recycling nism (320). Therefore, it can be inferred that the study
and utilization of biomass waste as well as environmen- on modified biochar is closely related to the treatment
tal remediation. However, the removal and fixation effi- of heavy metal pollution in soils and water, and the
ciency in water and soils of biochar to heavy metals is researches are focusing on the mechanisms of sorption
relatively limited. The modification of biochar is a suit- and removal, as shown in Fig. 3.
able method to improve its removal efficiency of heavy
metals.

Fig. 1 Raw materials and pyrolysis products of biochar

Liu et al. Carbon Research (2022) 1:8 Page 3 of 21

Fig. 2 The number of papers with the topic of "modified biochar" in 2008–2022

Fig. 3 Keywords co-occurrence analysis of the articles on "modified biochar", the font size corresponds to the number of co-occurrence times
Liu et al. Carbon Research (2022) 1:8 Page 4 of 21

1.1 Heavy metals and Marmiroli 2011). Therefore, it is urgent to explore

Heavy metals generally refer to metals whose density is low-cost and efficient methods to remove arsenic from
greater than 5.0 g·cm−3, and there are about 45 kinds of the environment.
heavy metals in a general sense. According to the World
Health Organization (WHO), common toxic and harm- 1.1.3 Cadmium
ful "heavy metals" in environmental pollution include Cadmium is a toxic trace element of heavy metals and is
chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), arse- a non-essential element for humans, animals and plants,
nic (As), cadmium (Cd), mercury (Hg) and lead (Pb), etc. but it is very important in the metallurgy, plastics, elec-
(WHO, Adverse Health Effects of Heavy Metals in Chil- tronics and other industries (Cuypers et al. 2010). Cad-
dren 2011, Wan Ngah and Hanafiah 2008). Among them, mium usually enters the soil through the exhaust gas,
Cr(VI), As(III), Cd(II), and Hg(II) are the most impor- wastewater and residue discharged from the industrial
tant heavy metal pollutants, which are found in water production process. Cadmium mainly exists in soils in
and soils that need attention. At the same time, due to water-soluble, exchangeable, carbonate, silicate, organi-
the development of nuclear energy industry, uranium cally bonded, iron and managanese oxidized forms. Cad-
(U(VI)) as; a radioactive heavy metal has also attracted mium is soluble and exchangeable in water, and can be
great research interest (Chen et al. 2022). absorbed by plants and enriched in animals and human
body through food chain (Jarup and Akesson 2009).
1.1.1 Chromium Cadmium enrichment in animals and plants to a certain
Chromium (Cr) is mainly produced in leather tanning, extent will cause serious harm to animal and plant health,
metal electroplating, metal finishing, textile dyeing and resulting in various diseases and even death of animals,
other industrial processes, and is widely distributed in plants and human body (Satarug et al. 2010; Singh et al.
wastewater, surface water and groundwater. In nature, 2011). The damage caused by cadmium accumulation
chromium occurs mainly in trivalent (III) and hexavalent has the characteristics of long-term, concealment and
(VI) forms. Cr(III) is an essential trace element for organ- irreversibility. Therefore, research on the removal of cad-
isms with low solubility because it can easily form stable mium in water and soils is of great importance for the
and insoluble precipitates (hydroxides, oxides or hydrox- protection of the environmental ecosystem and human
ides). However, Cr(VI) is more toxic, and chronic expo- health (Cuypers et al. 2010; Satarug et al. 2010).
sure to Cr(VI) can lead to cellular mutations that lead to
cancer and other diseases (Su et al. 2021). 1.1.4 Mercury
As a toxic heavy metal, mercury is listed as one of "Top
1.1.2 Arsenic 10 Major Chemicals of Concern" by WHO. Mercury pol-
Arsenic is a kind of heavy metal, which is widely dis- lution mainly comes from coal burning, mining or met-
tributed in natural environment. In the natural environ- allurgy, chlor-alkali processing, chemical production and
ment, arsenic rarely exists in the form of elementary other industries. The United Nations Environment Pro-
substance, but mostly exists in the form of compounds. gramme estimates that anthropogenic releases of mer-
The classification of arsenic in nature is mainly divided cury into the environment are about 2 gigatons per year,
into organic arsenic (mainly include MMA, DMA and and that surface soil mercury pollution has increased by
TMA), which is less toxic, and inorganic arsenic (mainly about 86 gigatons due to human activities. Soil pollution
include ­AsH3, arsenate and arsenite), which is more toxic causes mercury to be adsorbed by crops, including rice,
but less mobile (Srivastav et al. 2022; Nguyen et al. 2019). and mercury is found in human hair. The Minamata Con-
Arsenic has closely relationship with human life, and is vention on mercury was launched by the United Nations
used widely in more than 50 industries such as medicine in 2013 to protect human health and the environment,
and health, metallurgy, pesticide, silicate industry, semi- and 128 countries have so far signed the convention.
conductor, for processing, feed, anticorrosion, cosmetics However, while atmospheric mercury levels may decline
and military. In the agricultural production, in addition rapidly after emissions stop, it will take decades for mer-
to the widely used defoliants, arsenic-containing herbi- cury-contaminated soils to reach harmless levels. There-
cides, arsenic-containing pesticides, male insecticides fore, it is necessary to study the effective remediation
in hybrid rice have been widely used. Meanwhile, arse- technology of mercury contaminated soil (O’Connor
nic is also the most serious carcinogenic pollutant that et al. 2018).
threatens human health. The arsenic pollution can cause
chronic and subacute acute arsenic poisoning, and can 1.1.5 Uranium
also induce lung cancer, skin cancer and bladder cancer Uranium is the heaviest element found in nature and is
(Asere et al. 2019; Wu et al. 2020a; Yu et al. 2022; Beesley radioactive. After the fission reaction of uranium atoms,
Liu et al. Carbon Research (2022) 1:8 Page 5 of 21

large amounts of energy are released which can be used

for nuclear weapons, power generation, and other fields.
As a common radioactive pollutant, U(VI) has metabolic
toxicity and chemical toxicity to different organisms
including human beings. With the continuous develop-
ment and utilization of nuclear energy, uranium (U(VI))
is inevitably discharged into natural water bodies. With
the announcement of Japan’s Fukushima nuclear efflu-
ent into the sea plan, nuclear pollution in the world has
been concerned. Nowadays, nuclear pollution, which
poses a serious threat to soil and water, is now common
around the world. In order to restore the polluted water
bodies and reduce its environmental risk, the efficient
removal of U(VI) technology has attracted the attention
of researchers (Wang et al. 2020a).

1.2 Preparation and modification of biochar

Biochar is extensively used as an adsorbent for the
removal of heavy metals from water (Gao et al. 2019) Fig. 4 Modification methods of biochar
and as a passivator for the heavy metals in soils (He et al.
2019). In addition, the raw biochar materials could be
found from variety of sources, the preparation method
is simple, and the waste recycling can be realized. There- for 2 h. The yield of corn cob biochar was 24.43 ± 5.28%.
fore, the application of biochar for environmental heavy It was found that without any chemical treatment, the
metal remediation is a win-win strategy. However, the maximum sorption ability of methylene blue by the bio-
fixation ability of original biochar for heavy metals is rel- char was 16.50 mg·g−1 at 25°C. The physical properties
atively limited. In order to enhance the fixation ability of and chemical compositions of the biochar were meas-
biochar for heavy metals and to promote the real appli- ured by elemental analysis, N ­ 2 adsorption-desorption,
cation of biochar in environmental heavy metal remedia- FT-IR and SEM images, and it was found that the biochar
tion, modification of biochar through different methods yield and volatile substance composition were higher for
(acid-base modification, nano-material loading/compos- low temperature pyrolysis at 400-500°C compared with
ite, etc.) have been studied all over the world (Ahmed high temperature pyrolysis. It was found that the pyroly-
et al. 2016; Liu et al. 2020a). sis temperature was inversely proportional to the biochar
Currently, the commonly used biochar modification yield and volatile substance content. Ammonia ambi-
techniques mainly include physical, chemical and biolog- ance pyrolysis can make efficiently surface modification,
ical modifications, as shown in (Figs. 4 and 5) Rajapaksha increase magnetism and activate N-functional groups.
et al. 2016). Generally, physical method is more suitable Mian et al. (2018) prepared nitrogen-mixed magnetic
for real applications as it is easy to operate on large scale. biochar containing agar biomass under N ­ H3 ambiance
Chemical modification could change the surface proper- pyrolysis, and found that the product had the maximum
ties according to the application of biochar, but it may sorption capacity of Cr(VI) up to 142.9 mg·g−1, higher
need chemicals which are pollutants themselves, or are than magnetic biochar and other reported materials.
costly. Biological method can be applied on large scale, Ammonia environmental pyrolysis improved the mag-
but it generally needs relative long contact time to change netism of the biochar, making it easy to separate from
the structures and surface properties. the solution and collect after Cr(VI) treatment. Pyrolyti-
cally modified urban organic waste (UOW) biochar was
1.2.1 Physical methods considered carbon sink for long-term immobilization of
heavy metals in soil (Nair et al. 2020).
Internally modified pyrolysis Internally modified pyrol-
ysis can significantly increase the porosities and surface Microwave pyrolysis is one widely used technique in
areas of biochar, thereby enhancing the sorption ability the last decade. Microwave heating can increase the
of biochar. Suwunwong et al. (2020) synthesized corn heating rate and reduce energy consumption without
cob biochar using internally modified pyrolysis under the direct contact with the heated material. This technique
heating rate of 10 °C·min−1 and maintained it at 500 °C is more environmentally friendly than traditional heating
Liu et al. Carbon Research (2022) 1:8 Page 6 of 21

methods and has become the most commonly used con-

ventional pyrolysis method. Using ­K3PO4 and clinoptilo-
lite or bentonite as microwave absorbers and catalysts,
C + H2 O = H2 + CO (1)
the low microwave absorption rate and the quality of bio-
char can be improved during switchgrass pyrolysis. The
microwave heating of 10 wt.% ­K3PO4 + 10 wt.% bentonite C + 2H2 O = 2H2 + CO2 (2)
reached 400°C after 2.8 min, while the conventional heat- The advantage of water vapor modification is that it is
ing was 28.8 min, the heating time of adding microwave environmentally friendly and does not produce second-
was reduced to less than 1/10 of the conventional heating ary pollution, but it also has the disadvantages of high
time. Compared with the specific surface area of biochar temperature and energy requirements and relatively low
prepared by conventional heating method (0.33 m ­ 2·g−1), carbon yield, which limit the wide application of this
the specific surface area of biochar prepared by micro- method (Amusat et al. 2021).
wave heating method (76.3 m ­ 2·g−1) increased by more
than 230 times (Mohamed et al. 2016). Song et al. (2020) In addition, water vapor modification can remove the
developed a nano-magnetite-modified biochar mate- particles or volatile gases trapped on the surface of bio-
rial (m-biochar) using microwave in-situ rapid synthesis char, thus increasing the pore volume of biochar and
method, and systematically studied the removal ability making the internal pores of biochar develop (Rajapaksha
and mechanism of Cr(VI) from polluted groundwater by et al. 2014). Rajapaksha et al. (2015) studied the effects
m-biochar. The maximum sorption capacity of m-biochar of invasive plant Sicyos Angulatus L. biochar that was
was 9.92 mg·g−1, which was significantly higher than that steam modified on enhancing the removal of sulfameth-
of the original biochar (8.03 mg·g−1). It can be concluded azine (SMT) from water, and found that steam activated
that the surface modification of biochar can increase the biochar produced at 700 °C showed the highest sorp-
amount of surface functional groups and make them tion capacity at pH 3 (37.7 mg·g−1), increasing sorption
combine with metal ions, thus improving the sorption capacity by 55% compared to non-activated biochar pro-
capacity of biochar. duced at the same temperature.

Gasification Gasification is the partial oxidation of Steam modified biochar also performed well in the
raw materials by gasification agents (air, oxygen, steam, removal of heavy metals. Wang et al. (2020b) treated
etc.), and the temperature of the gasification process is biochar by steam activation (SBC) at the temperature of
usually higher than 700 °C and a small amount of steam 500 °C for 45 min, and applied it to the effective elimi-
and oxygen is required (Hansen et al. 2016). The biochar nation of ­Cu2+ and tetracycline (TC). The pyrolytic bio-
can form solid, liquid and gas products, but the yield of char of wood chips, rapeseed, manure particles and
biochar is lower than that of pyrolysis because gasifica- wheat straw at 300, 500 and 700 °C was studied, and the
tion tends to focus more on gaseous products (Wang difference between steam-activated biochar and non-
and Wang 2019). The main purpose of steam modified activated biochar was compared. It was found that steam
biochar is to increase the specific surface areas, pore vol- activation increased Pb(II) sorption capacity of most
umes and surface morphologies of biochar by reducing biochars, mainly due to the increase in surface area. The
the aromatics and polarity of biochar. The surface areas Pb(II) sorption capacity of rapeseed straw biochar was
of biochar by steam-modification were increased, which 195 mg·g−1 at 700 °C, nearly 2 times compared with the
was attributed to corrosion of the biochar surface and uptake of wheat straw–based and non–steam activated
the release of additional syngas (mainly in the form of canola biochars with 109 mg·g−1 and 108 mg·g−1, respec-
hydrogen) (Vijayaraghavan 2019). The basic mechanism tively (Kwak et al. 2019). The effect of steam modified
of ­H2O vapor modification is described in Eqs. (1) and (2) biochar on the removal of drug compounds in water was
(Amusat et al. 2021): studied. Chakraborty et al. (2018) studied the sorption

(See figure on next page.)

Fig. 5 A. The process for biochar without and with treatment in descriptive manner. The diagram for different bioreactor types. (Sutar et al. 2022)
"Reproduced with permission from Elsevier, Copyright ©2022." B. N-doped magnetic biochar preparation via one-step under NH3 environment.
(Mian et al. 2018) "Reproduced with permission from Elsevier, Copyright ©2018." C. Thiol-modified RS biochar prepared with β-mercaptoethanol for
Cd and Pb remediation from polluted soils. (Fan et al. 2020) "Reproduced with permission from Elsevier, Copyright ©2020." D. Schematic illustration
of fabrication for ZnO/biochar composites. (Chen et al. 2019b) "Reproduced with permission from Elsevier, Copyright ©2019." E. Description of
various synthesis methods for NMOBCs preparation. (Zhao et al. 2021) "Reproduced with permission from Elsevier, Copyright ©2021." F. Schematic
diagram of magnetic biochar embedded g-C3N4 nanosheets. (Karpuraranjith et al. 2021) "Reproduced with permission from Elsevier, Copyright
©2021."
Liu et al. Carbon Research (2022) 1:8 Page 7 of 21

Fig. 5 (See legend on previous page.)

Liu et al. Carbon Research (2022) 1:8 Page 8 of 21

capacities of ibuprofen by protobiochar and steam acti- (π-EDA) interaction (Fig. 6) (Amusat et al. 2021), just the
vated biochar made from Aegle marmelos shell from same as unmodified biochar.
aqueous solution. Under the optimal removal conditions,
Aegle marmelos biochar (WAB) and Aegle marmelos Ball-milling modified biochar has a good performance in
steam activated biochar (WASAB) showed the removal removing environmental heavy metals. Cui et al. (2021)
efficiencies of 90% and 95%, respectively. Morphological prepared Ball-milling LDHs-biochar composites
analysis showed that the active adhesion sites increased (B-LDHS-BC) with Ball-milling technique for sorption
after biochar modification. In addition, they compared of Cd(II), studied the influence of Ball-milling on the
the sorption abilities of physically (using steam) acti- structures and properties of LDHS-BC, and found that
vated Cocos biochar (CPBC) and chemically (using the removal of Cd(II) by B-LDHs-BC included physi-
­H3PO4) activated Cocos biochar (CCBC) to remove IBP cal adsorption and chemical sorption processes. It was
from simulated water, and found that the sorption capac- proved that BM successfully removed LDHs from the
ities of IBP by CCBC and CPBC were 12.2 mg·g−1 and surface of B-LDHs-BC. Although the N ­ 2-BET surface
9.7 mg·g-1, respectively. The total pore volumes of CCBC area (226 m ­ 3 ·g−1) of B-LDHs-BC was a little lower than
and CPBC were calculated to be 0.552 ­cm3·g−1 and 0.417 that of Ball-milling BC, the B-LDHs-BC contained much
­cm3·g−1, respectively. CCBC had higher pore volume and more oxygen-containing groups and much higher sorp-
surface area than CPBC, which confirmed that CCBC tion capacity (119 mg ·g−1). The Cd(II) sorption perfor-
had higher sorption ability and microporous charac- mance of B-LDHS-BC was enhanced by inducing more
teristics. This may be due to the coconut shell chemical active sorption sites and acidic groups (Fig. 7 A and B)
activation by H­ 3PO4, which formed porous structures on (Cui et al. 2021).
the surface of the adsorbent (Chakraborty et al. 2019).
The conditions of gasification could provide different Meanwhile, Ball-milling magnetic modified biochar
kinds of active species, which can interact with biochar can synergistically remove heavy metal ions and drug
and thereby change the surface functional groups, pore compounds in aqueous solution. Li et al. (2020) stud-
volumes and surface areas. According to the application ied the sorption of TC and Hg(II) from aqueous solu-
requirement, one can select different gasification system tion using Ball-milled magnetic nanobiochars (BMBCs)
to change the biochar surface properties and structures, (Fig. 6b). This demonstrated a significant improvement
which is helpful to improve the sorption selectivity and in the removal efficiency of TC and Hg(II) by BMBCs. It
ability. was shown that ≥ 99% of TC and Hg(II) were adsorbed
to BMBCs at optimal preparation (700 °C, 12 h). The
Ball‑milling Ball-milling (solid-phase synthesis) is a sorption efficiency was negatively correlated with the
common synthesis process of nanomaterials, which has ionic strength of the solution, but positively correlated
been widely used in industry. As a kind of solvent-free with the solution temperature in the temperature range
technique, it has widely been used to construct biochar- of 25°C ~ 45°C. The results showed that the sorption of
based materials with well dispersion and high porosities TC was mainly dominated by electrostatic interaction,
to enhance the environmental pollution treatments. The hydrogen bond and Cπ-Cπ interaction, whereas the sorp-
Ball-milling process produces nanoparticles as small as tion of Hg(II) ions was mainly controlled by the elec-
10 microns in size and can be operated continuously. trostatic attraction, the formation of Hg–Cπ bond and
Ball-milling of carbon-based composites is a new low- surface complexation. In addition to excellent removal
cost method to prepare nano-composites with good capability, BMBC700 also showed good recyclability and
surface properties. The physicochemical properties of magnetic separation advantages (Li et al. 2020).
biochar and its nanocomposites are improved by Ball-
milling, such as the total pore surfaces and micropore In addition, Ball-milling modified biochar can improve
surfaces of biochar, thus enhancing the sorption capaci- the removal ability of dyes and organic pollutants in
ties of biochar. Due to the interaction of biochar and aqueous solution. In the work of Zhang et al. (2021b),
nanoparticles, biochar nanocomposites can effectively ­BMHCH2O2 was modified by Ball-milling and 10%
adsorb heavy metals, dyes and emerging organic pol- hydrogen peroxide (­ H2O2) solution in two steps at differ-
lutants in water. The sorption capacity of the origi- ent pyrolysis temperatures. It was found that the specific
nal biochar can be improved in the range from several surface area (SSA) of biochar significantly increased after
times to more than 200 times. The sorption mechanisms Ball-milling, and the hydroxyl groups and carboxyl groups
of biochar modified by Ball-milling include physical on biochar further increased after the ­H2O2 modification.
adsorption, chemical sorption, ion exchange, pore fill- Therefore, the sorption efficiency of MB on biochar was
ing, hydrophobic effect and π-π electron donor-acceptor further improved by two steps of modification. Among
Liu et al. Carbon Research (2022) 1:8 Page 9 of 21

Fig. 6 Preparation and adsorption mechanism of Ball-milling biochar. A. A real–world example (a), the impact of forces (b) and the types of motion
of grinding balls in a Ball mill: (c) rolling over; (d) falling; (e) rolling. (Amusat et al. 2021) "Reproduced with permission from Elsevier, Copyright
©2021." B. Schematic illustration of BMBC preparation (Li et al. 2020) "Reproduced with permission from Elsevier, Copyright ©2020." C. Ball-milling
of pristine wheat stalk biochar for adsorption of tetracycline hydrochloride (TCH) (Xiang et al. 2020) "Reproduced with permission from Elsevier,
Copyright ©2020."

the tested adsorbents, B ­ MHCH2O2-450 had the larg- ­ a+, ­K+, ­Mg2+ and TCH in the solution produces com-
N
est sorption capacity for MB (310 mg·g−1) (Zhang et al. petitive sorption, while the presence of ­Ca2+ promotes
2021b). Xiang et al. (2020) investigated the sorption the sorption of TCH by forming tetracycline-Ca2+ com-
property of tetracycline hydrochloride (TCH) by pyro- plexes. BM-biochar pyrolyzed at 600°C has the best
lytic straw raw and Ball-milled biochar (BM-biochar) at adsorption performance, and TCH sorption capacity is
300 °C, 450 °C and 600 °C. The surface properties of BM- 84.54 mg·g−1 at pH = 6-8 (Xiang et al. 2020).
biochar were obviously improved as compared with the
original biochar. TCH sorption occurred mainly on the In conclusion, Ball-milling modified biochar has the
outer spherical surface of biochar and was carried out potential to improve the sorption capacity of bio-
by filling holes. The sorption capacity was positively cor- char because the surface areas and the surface sites are
related with external surface areas, total microporous or increased after Ball-milling, thereby improving the
mesoporous volumes of biochar (Fig. 6c). The presence of removal of pollutants from aqueous solutions. The study
Liu et al. Carbon Research (2022) 1:8 Page 10 of 21

Fig. 7 A. SEM images of (a) BC, (b) B-BC, (c) B-LDHs-BC, and (d) B-LDHs-BC (Cd(II))."Reproduced with permission from Elsevier, Copyright
©2021." B. High resolution XPS spectra for C 1 s, O 1 s, Mg 1 s, Al 2p of B-LDHs-BC (a-d) and M-BLDHs-BBC (a´–d´). (Cui et al. 2021) "Reproduced
with permission from Elsevier, Copyright ©2021." C. The SEM analysis of SCG (a) and NaOH-SCG (b); The TEM images of SCG (c) and NaOH-SCG
(d)."Reproduced with permission from Elsevier, Copyright ©2021." D. (a) N2 adsorption–desorption isotherms, (b) FTIR spectra, (c) TGA curve, and (d)
PAHs concentration of SCG and NaOH-SCG. (Nguyen et al. 2021) "Reproduced with permission from Elsevier, Copyright ©2021."
Liu et al. Carbon Research (2022) 1:8 Page 11 of 21

of biochar modified by Ball-milling is of great signifi- textile wastewater (Liu et al. 2019). Walnut shell bio-
cance for the elimination of heavy metals from wastewa- char (WSC) and wood powder biochar (WPC) pre-
ter. Ball-milling is the most commonly used method to pared by limited oxygen pyrolysis were modified by
modify biochar in really applications because it is easy to ­ZnCl2, KOH, ­H2SO4, and ­H3PO4. Experimental results
operate on large scale. More importantly, the Ball-milling showed that the specific surface area of modified bio-
modification could be finished in short time. There are char after KOH treatment was the highest. Acid modi-
also some disadvantages on this kind of biochar as it only fication increased a large number of oxygen-containing
has efficiency on increasing the surface areas, and does functional groups on biochar. These functional groups
not change other functions. Therefore, the combination provided more sorption sites for pollutants, which are
of Ball-milling method with chemical or biological meth- conducive to bind the pollutant molecules. The sorption
ods will have a wider application prospect. capacities of MB on different treatment reagents were
­ZnCl2 > KOH > ­H3PO4 > ­H2SO4. The maximum sorption
capacities of WPC and WSC by the two biomass treat-
1.3 Chemical methods ments were 850.9 mg·g−1 and 701.3 mg·g−1, respectively
Chemical technique is one most commonly used method (Liu et al. 2020b). He et al. (2021) prepared rice straw
at present, usually includes acid, alkaline, oxidizing- biochar by anaerobic pyrolysis and modified the biochar
agents, metal salts or metal oxides, and other modifica- with 15% H ­ 2O2 and 1:1 H­ NO3/H2SO4 mixed acid, respec-
tions, etc. (Wang and Wang 2019). Using different kinds tively. The results showed that the oxidation modification
of chemicals, the surface properties such as the concen- with 15% ­H2O2 and 1:1 H ­ NO3/H2SO4 acid significantly
trations of functional groups, the kinds of functional increased the carboxyl functional groups on the biochar
groups, the surface defects etc. could be changed, which surface. The carboxyl functional groups on the surface of
is helpful to change the sorption property of biochar. biochar were enhanced more effectively by acid modifi-
cation than by oxidant modification. Cd(II) forms sur-
1.3.1 Acid modification
face complexes through coordination between functional
The improvement of biochar by acid treatment includes groups and biochar, which is the main mechanism of
removing metals and other impurities on biochar sur- Cd(II) specific sorption on biochar surface. After modi-
face, and increasing acid functional groups on biochar fication, the number of carboxyl groups on the surface of
surface. Meanwhile, acid treatment can also change the rice straw biochar increased significantly, thus improving
surface areas of biochar, and the effect varies with types the specific sorption capacity of Cd(II) on biochar (He
and concentrations of acids (Wang and Wang 2019). et al. 2021). In conclusion, the surface charge and func-
Acidified biochar is the most suitable soil improver (Pan- tional groups could be changed obviously after acid mod-
war and Pawar 2020). Wibowo et al. (2007) modified bio- ification. The point of zero charge is decreased and the
char with ­HNO3, after the modification, a large number surface purity is increased. The change of surface proper-
of oxygen-containing acidic surface groups were intro- ties is critical for the application of biochar.
duced on the surface of biochar, and the specific surface
areas were increased. Compared with the biochar before 1.3.2 Alkali modification
oxidation, the O/C ratio of biochar after oxidation with The main purpose of alkali modification is to increase
concentrated ­HNO3/H2SO4 and 30% H ­ NO3 increased surface area, pore volume and oxygen-containing func-
by 10 times (flax), 5 times (CH800), 7 times (flax) and tional groups. Common alkali modification reagents are
4 times (CH800), respectively. The total acidities of flax potassium hydroxide and sodium hydroxide (Wang and
increased from 0 to 3.3 (­HNO3/H2SO4) and 1.2 (30% Wang 2019). Potassium hydroxide modification increases
­HNO3) after oxidation. The CH800 had a similar trend the surface area of biochar prepared by pyrolysis from
(Table 1). Therefore, acid oxidation of biochar increases 14.4 to 49.1 ­m2·g−1, and increases the oxygen-containing
the O/C ratio and total acidities of biochar (Uchimiya functional groups, thus enhancing the sorption capac-
et al. 2012). Liu et al. (2020a) obtained primitive bio- ity of As(V) from 24.49 mg·g−1 for the original biochar
char (CSBC) from pyrolysis of corn straw in a finite oxy- to 30.98 mg·g-1 (Jin et al. 2014). Sodium hydroxide is
gen condition and modified it with H ­ 3PO4-CSBC and less corrosive and less costly than potassium hydroxide
KOH, respectively. The sorption capacities of CSBC, (Cazetta et al. 2011). NaOH modified coconut biochar
­H3PO4-CSBC and KOH-CSBC to MB were 43.1 mg·g−1, increased its surface area significantly from 1940 ­m2·g−1
230.4 mg·g−1, and 406.4 mg·g-1, respectively. The chemi- to 2885 m­ 2·g−1 compared with KOH modified coconut
cal treatment significantly improved the sorption ability (Cazetta et al. 2011; Tan et al. 2008).
of MB on biochar, especially for KOH-CSBC. Therefore, Nguyen et al. investigated the feasibility of TC removal
the KOH-CSBC has the potential to remove dyes from from different aqueous solutions using alkaline treated
Table 1 Raw materials, modification methods and removal effect of heavy metals of modified biochar
Liu et al. Carbon Research

Adsorbent Pyrolysis Modification method Target contaminant Main results Reference

temperature
(°C)

Reed residues 650°C Nano-magnetite + microwave Cr(VI) Synthesized m-biochar enhanced Cr(VI) Song et al. 2020
(2022) 1:8

removal ability from contaminated ground-

water as compared to pristine biochar
Sawdust and switchgrass 650°C Triple superphosphate (TSP) and bone Pb(II), Cu(II), Cd(II) The biochar copyrolysized with phosphate Zhao et al. 2016
meal (BM) fertilizers had high metals stabilization in
soils
MgCl2 400–600°C Fast pyrolysis Pb(II), Cd(II) and tetracycline The MgO@N-biochar had high ability for Ling et al. 2017
binding Pb(II) with high sorption capacity
of 893 mg·g−1 and short equilibrium
time (< 10 min)
Broiler litter manure 350°C, 700°C Pyrolysis, steam-activated Cu(II), Ni(II), Cd(II), Pb(II) Both in soils and water, the addition of Wang et al. 2019b
biochar increased pH and enhanced heavy
metals immobilization
β-cyclodextrin functionalized 500 °C Pyrolysis + mixing Heavy metals and dye β-BC possessed the ability to promote the Wu et al. 2020b
biochar (β-BC) removal of antibiotic resistance genes in
wastewater treatment
Pine bark waste 950°C Magnetic(CoFe2O4) Pb(II) and Cd(II) MBC showed efficient ability for Cd(II) and Reddy and Lee 2014
Pb(II) removal from aqueous solutions
Waste marine macro-algae 500°C Iron oxide particles (e.g., magnetite, magh- Heavy metals Magnetic biochar had high sorption ability Son et al. 2018
emite) for heavy metals than other reported bio-
char
Walnut shells 249.85°C Nano FeS and starch (or chitosan) Pb(II) Biochar loaded with nano-FeS, starch or Liu et al. 2022b
chitosan showed much higher sorption
ability for Pb(II) than the bare biochar
Microcystis biomass 200°C Fe3O4 U(VI) The ­Fe3O4/biochar had high sorption ability Wang et al. 2020a
in the removal of U(VI)
Cottonseed hull and flax shive 700 °C Concentrated ­H2SO4/HNO3 and 30% ­HNO3 Pb, Cu, and Zn Oxidized biochar has rich carboxyl groups Uchimiya et al. 2012
which enhanced the sorption ability for
Pb, Zn and Cu as compared to unoxidized
biochar
Page 12 of 21
Liu et al. Carbon Research (2022) 1:8 Page 13 of 21

biochar (NaOH-SCG) prepared by pyrolysis of coffee metals or metal oxides are mainly as follows: (1) the met-
grounds. The results showed that the sorption capacity of als or metal oxides are firstly mixed with raw materials
NaOH-SCG biochar (113.6 mg·g−1) was 2.9 times higher and then pyrolyzed to synthesize biochar; (2) biochar is
than that of unmodified SCG (39.2 mg·g−1). The alkaline prepared by pyrolysis of raw materials, and then soaked
treated biochar has high sorption capacity for TC and has with metal ions or metal oxides under certain conditions
broad application prospect in the separation of hazard- (Tan et al. 2016). After medication with metals or metal
ous chemicals in different wastewater (Fig. 7 C and D) oxides, the properties of biochar could be changed obvi-
(Nguyen et al. 2021). Tang et al. (2022) used alkali-modi- ously, such as photocatalytic ability, magnetic property,
fied straw biochar to remove the emerging contaminants oxidation/reduction property, etc.
(ECs) in kitchen wastewater, such as bisphenol A (BPA), Karimnezhad et al. (2014) studied the modifica-
TC and ofloxacin (OFL). They found that the alkali- tion of walnut shell biochar with different concentra-
modified straw biochar had larger specific surface area, tions of ­ZnCl2, and found that the specific surface area
stronger hydrophobicity and higher sorption capacity, of the modified biochar increased with the increase
and the removal rate of ECs reached 95%-100%. Under of impregnation ratio. Wang et al. (2015) studied the
static operation mode, the maximum sorption capaci- effect of biochar modified by hematite at 600°C on the
ties of alkali-modified biochar for BPA, TC and OFL were removal of As(V) in the soil, and found that the maxi-
71.43, 101.01 and 54.05 mg·g−1, respectively (Tang et al. mum sorption capacity of modified biochar for As(V)
2022). Chen et al. (2021) used KOH to modify N-enriched could reach 429 mg·kg−1 due to the effect of electrostatic
biochar (KNB) from waste chicken feathers. They found sorption and surface functional groups. However, the
that the sorption rates of Cd(II) (2 h to reach equilib- removal of heavy metals by the original biochar was only
rium) and Pb(II) (1 h to reach equilibrium) by KNB were 265 mg·kg−1, and the difference was about 2 times before
fast. The sorption capacities of Cd(II) and Pb(II) by KNB and after modification. O ’Connor et al. (2018) found that
were 22.32 mg∙g-1 (Cd(II)) and 119.65 mg∙g-1 (Pb(II)), sulfur modified rice husk biochar had a higher removal
which increased by 7.07 and 26.52 times compared with rate of Hg(II) from soil than unmodified biochar, and the
the original biochar, respectively. The main sorption removal rate increased with the increase of sulfur addi-
mechanisms of KNB for Cd(II) and Pb(II) included elec- tion amount. Wan et al. (2018) impregnated hydrated
trostatic interactions, cation-π interactions, complexa- manganese oxide (HMO) nanoparticles into a peanut
tion and ­K+ exchange (Chen et al. 2021). Hafizuddin et al. shell-derived biochar (BC), and obtained a nanocompos-
(2021) used sodium hydroxide (NaOH) to modify palm ite adsorbent HMO-BC, which showed better sorption
kernel shell (PKS) and coconut shell (CS), and found that capacity than bare BC in actual heavy metal containing
the surface modified biochar had high specific surface wastewater treatment. HMO-BC can effectively remove
areas (CS: 356.9 ­m2·g−1, PKS: 427.6 m ­ 2·g−1), small pore Pb(II) from the actual lead plating wastewater to the
sizes (CS: 2.2 nm, PKS: 2.0 nm) and large pore volumes discharge limit (0.2 mg·L−1), the treatment volume of
(CS: 0.34 ­cm3·g−1 (Yu et al. 2021), PKS: 0.30 c­ m3·g−1 (Yu 525BV, much higher than bare BC (60BV), as shown in
et al. 2021). The results indicated that NaOH modifica- Fig. 8. Furthermore, the HMO-BC can be reused and has
tion could effectively improve the surface characteristics no observed capacity loss. Nitrogen-mixed biochar was
of biochar. In addition, the surface modification of 25% modified with magnesium oxide nanoparticles (MgO@n-
NaOH greatly increased the active functional groups of biochar), and it was found that the MgO@n-biochar had
biochar, which directly improved the sorption capacity a large sorption capacity for Pb(II) (893 mg·g−1), a short
of biochar (CS: 527.4 mg·g−1, PKS: 627.0 mg·g−1). Com- balance time (< 10 min), and a large handling volume
pared to acid modification, the alkali modification can (~ 4450BV). Meanwhile, this excellent sorption perfor-
also change surface areas, pore volumes and functional mance can be maintained with various environmentally
groups. After alkali modification, the point of zero charge relevant interferences, such as pH, natural organic matter
and oxygen-containing groups are generally increased as and others. It is interesting to note that the material may
compared with the pretreated biochar. be suitable for the treatment of wastewater, natural water
and even drinking water (Ling et al. 2017).
1.3.3 Metal ions and metal oxides‑modified biochar A method to produce zinc-biochar nanocomposites
The sorption, catalytic performance and magnetic prop- from bagasse was studied, and the removal of Cr(VI) was
erty of biochar can be changed by modification with 1.2 ~ 2.0 times higher than that of original biochar (Gan
metals or metal oxides. Metal modification can improve et al. 2015). New types of biochar, namely FeS@WNS,
the biochar sorption capacity for heavy metals and their Chitosan-FeS@WNS, and Starch-FeS@WNS were con-
oxides by increasing the exchange of ions and nitrogen- structed by loading FeS, starch or chitosan with WNS.
containing functional groups. The modification with FeS nanoparticles can effectively improve the removal of
Liu et al. Carbon Research (2022) 1:8 Page 14 of 21

Fig. 8 A. Schematic illustration of the enhanced heavy metal sequestration by HMO-BC. B. Influence of competitive ions, Ca(II), Mg(II) and Na(I)
on sorption of Pb(II) and Cd(II) onto HMO-BC and BC. Conditions: C0 (Pb(II)) = 10 mg L−1, C0 (Cd(II)) = 5 mg L−1, Sorbent dose = 0.2 g L−1,
pH = 6.0 ± 0.2, and Temperature = 298 K. Lower Pb(II) and Cd(II) concentrations were chosen to better show the adsorption preference of HMO-BC
toward target metals. (Wan et al. 2018)"Reproduced with permission from Elsevier, Copyright ©2018."

Pb(II), while chitosan or starch can improve the stability as montmorillonite, superphosphate, etc.) (Zhao et al.
and easy agglomeration of FeS. The removal mechanisms 2016), organic compounds (mercaptan (Lyu et al. 2020),
of Pb(II) in aqueous solution include the electrostatic thiourea (Zhu et al. 2020) and so on. Low-temperature
attraction, H-bonding, ion exchange, physical sorption, plasma method has become one of the research hot-
and oxidation/reduction. In addition, the three com- spots in recent years due to its low cost, environmentally
posites are stable and reusable, and can be applied for friendly and good performance.
the treatment of Pb(II) polluted wastewater (Liu et al. Fan et al. (2020) prepared a thiol-modified straw bio-
2022b). In terms of increasing magnetism, the combina- char (RS), which increased the thiol groups on the bio-
tion of biochar and magnetic adsorbents (such as mag- char surface, complexed with Pb(II) and Cd(II) effectively
netic nano-ferric oxide, zero-valent iron, Co F
­ e2O4, etc.) (61 and 45 mg·g−1, respectively), and it was shown that
to generate magnetism can increase the convenience of RS selectively adsorbed Cd(II) than Pb(II) in binary-
biochar recovery and improve the sorption capacity for metal systems. The results suggested that the biochar
heavy metals (Karunanayake et al. 2018; Reddy and Lee, modified by ethanol-activated could be a useful strategy
2014; Son et al. 2018). Song et al. (2020) found that the for heavy metal pollution treatment in soils and water
sorption capacity of the synthesized magnetic biochar and therefore was a promising research material for envi-
was significantly increased from 8.0 mg·g−1 to 9.9 mg·g−1 ronmental governance applications. Chen et al. (2022)
as compared to the original biochar. successfully modified o-PEA on porous carbon by low-
temperature plasma method. Cafe/O-PEA has a good
1.3.4 Other methods sorption capacity for U(VI). The maximum sorption
As for the chemical modification methods, in addition capacity of Cafe/O-PEA is 648.54 mg·g−1 at T = 298 K
to the above-mentioned categories, there are some other and pH = 6.0 at 1 h, which is much higher than that of
modification methods. Modified methods with materials most carbon matrix composites. Experimental results
such as oxidants (containing hydrogen peroxide) (Wang show that the sorption of U(VI) is related to the compl-
and Wang 2019; Qin et al. 2019), carbonic acid materi- exation of Cafe/O-PEA with -NH2, phosphate and -OH
als (Wang and Wang 2019), inorganic materials (such groups. Therefore, low temperature plasma method is an
Liu et al. Carbon Research (2022) 1:8 Page 15 of 21

efficient, environmentally friendly and low-cost mate- 1.5 Mechanism of pollutants removal from water and soil
rial surface modification method, which can effectively by modified biochar
enrich U(VI) in aqueous solution, and has positive signif- The anaerobic heating process increases the specific sur-
icance for the treatment of wastewater pollution. face areas and pore volumes of biochar, which is condu-
cive to pore filling, thus improving the sorption capacity
1.4 Biological modification methods of pollutants. There are a large number of O-containing
The use of microorganisms to adsorb heavy metals from groups on the surface of biochar, such as hydroxyl groups
aqueous solutions has proven to be very promising, and carboxyl groups, which can make surface complexa-
low-cost, easy to operate and efficient, especially in the tion, ion exchange, and the electrostatic attraction with
treatment of low concentration heavy metal wastewater. heavy metal ions. The specific mechanism of the binding
Residual biomass of industrial microorganisms, includ- action can be judged by the changes of biochar functional
ing bacteria, algae, fungi, and yeast, is able to efficiently groups before and after the sorption of metal ions, such
accumulate heavy metals. The biological sorption process as the movement, increase or disappearance of the peak.
includes the following mechanisms: cross-cell membrane The specific sorption mechanism of different heavy metal
transport, complexation, ion exchange, precipitation, and ions is also different, which affects the properties of bio-
physical adsorption. The microbial surface contains large char, vice-versa.
amounts of functional sites such as amino, carbonyl, car-
boxyl, and hydroxyl groups etc. This may help to improve 1.5.1 Mechanism of heavy metals removal from water
the sorption effect of biochar by surface grafting and / by modified biochar
or functional group exchange (Zilouei et al. 2014; Wang Heavy metal pollution in environmental water, includ-
et al. 2021). ing heavy pollutant metals (such As(III), Cr(VI), Ni(II),
Under certain conditions, bacteria have a good sorp- Zn(II), Cu(II), Cd(II), Hg(II), U(VI), Pu(IV) etc.) and
tion effect on different toxic heavy metals (Chakravarty metal-like metals (such As(III), Se(IV) and As(V)), has
and Banerjee 2012). Due to the lack of long-term stabil- become a serious challenge (Schwarzenbach et al. 2010;
ity of biochar in heavy metal remediation, phosphate- Yang et al. 2021; Cheng et al. 2021; Li et al. 2021). Heavy
solubilizing bacteria (PSB) can increase the release of metal intake can cause a variety of human diseases, even
phosphorus and react with Pb(II) to form stable molyb- cancer. Biochar is an efficient, and ecological adsor-
denite. Chen et al. prepared an alkaline biochar produced bent for water purification. After surface modification,
from rice husk (RB) and a slightly acidic biochar pro- the porosity, reactivity and sorption capacity of biochar
duced from sludge (SB) as raw materials, and modified are increased significantly. The mechanisms of biochar
them with PSB. The results showed that Pb(II) concentra- elimination of heavy metals from wastewater mainly
tion in water decreased by 18.61 and 53.89% after add- include complex formation, electrostatic behavior and
ing RB and SB, respectively. PSB modification improved ion exchange (Fig. 9). Therefore, using biochar to remove
Pb(II) removal rates of the two biochar to 24.11 and heavy metals is a promising strategy (Liu et al. 2022a;
60.85%, respectively. The results showed that the uniform Liang et al. 2021; Srivastav et al. 2022; Chen et al. 2021;
distribution of PSB enhanced the release of phosphorus Wang et al. 2019b).
on the surface of biochar, regulated the surface pH value Different modification methods lead to differ-
of biochar, and significantly promoted the formation of ent removal mechanisms of heavy metals (Cai et al.
stable pyroxenite on the surface of biochar. Therefore, 2022). Therefore, if the modification method is correctly
the combination of biochar and PSB is a promising can- conducted, the biochar will have sufficient heavy metal
didate for heavy metal remediation (Chen et al. 2019a). removal capacity, and the heavy metals will be more sta-
The dynamic effects of maize biochar and a heavy metal- ble in biochar, thus enhancing the chemisorption and
resistant pseudomonas on the stability of soil contami- removal mechanism. For example, the pyrolyzed sulfate
nated with mixed Cd(II) and Cu(II) and its potential lignin biochar modified with ­CO2 at 800 °C and impreg-
mechanisms were investigated (Tu et al. 2020). The nated with F­ eOx improved the sorption efficiency of arse-
results showed that the biochar of the inoculated strains nic in an aqueous solution (Cha et al. 2021). The sorption
increased the soil pH, reduced the exchange and bio-uti- capacity of the modified reed straw biochar prepared
lization of Cd(II) and Cu(II), improved the soil enzyme by microwave treated nano-magnetite was 9.92 mg·g−1,
activity, and improved the soil microbial community. significantly higher than that of the original biochar
After biological modification, the biochar could adsorb (8.03 mg·g−1) (Song et al. 2020).
metal ions more efficiently and fix the adsorbed metal On the other hand, it is an effective way to recycle bio-
ions more strongly. The soil quality can be improved at char from water by adding magnetism to biochar through
the same time. modification. Liang et al. (2022) prepared magnetic
Liu et al. Carbon Research (2022) 1:8 Page 16 of 21

Fig. 9 A. B. The main mechanisms of biochar adsorption of heavy metals in water (Chen et al. 2021; Wang et al. 2019b) Reproduced with
permission from Elsevier, Copyright ©2021,2019. C. Adsorption mechanism of biological cells for heavy metals removal."Reproduced with
permission from Elsevier, Copyright ©2020." D. Three novel methods for heavy metals’ removal: chemical modified biomaterial; chemical and
biomass material composites; multiple biomass system. (Qin et al. 2020) "Reproduced with permission from Elsevier, Copyright ©2020."

poplar sawdust biochar by co-pyrolysis of F ­ eCl3/CaCl2 1.5.2 Mechanism of soil heavy metal pollution treatment
mixed molten salt. ­Fe2O3 generated in-situ made bio- by modified biochar
char superparamagnetic, which was beneficial to biochar As the most common soil pollution problem, heavy
recycling. The results showed that the low-cost and reus- metal pollution has attracted wide attention all over
able ­Fe2O3/biochar had the potential for efficient and fast the world. A large number of studies showed that bio-
removal of antibiotics in water. The efficient elimination char could effectively fix metals in contaminated soils
of metal ions from wastewater using biochar is gener- due to its large surface areas, rich binding sites and
ally attributed to the high sorption ability. The surface functional groups. Therefore, the use of biochar in
functional groups form strong inner-sphere surface soil remediation has become the consensus of more
complexes with metal ions. Some kinds of modified bio- scientists and environmental remediation enter-
char could reduce the metal ions from high valent to low prises. The characteristics of biochar are restricted
valent, and thereby can form solidification on biochar. by the raw materials in production or source of raw
The magnetic biochar could be separated from a large materials, as well as the pyrolysis conditions, result-
volume of aqueous solutions easily using magnetic sepa- ing in differences in pH values, organic carbon con-
ration method. Overall, the biochar is a promising mate- tents, cation exchange capacities (CEC), microporous
rial in wastewater treatment in real applications. Biochar structures, SSA, mineral contents, active sites and
could not only preconcentrate metal ions, but also solid- functional groups. These differences, combined with
ify the metal ions and thereby immobilize the movement the differences in soil properties, will affect the metal
of metals in environment. mobility and bioavailability of metals by biochar. This
Liu et al. Carbon Research (2022) 1:8 Page 17 of 21

Fig. 10 Biochar-heavy metal interaction mechanism in soil (He et al. 2019) "Reproduced with permission from Elsevier, Copyright ©2019."
Liu et al. Carbon Research (2022) 1:8 Page 18 of 21

makes it difficult to predict and understand the addition of biochar, and the surface complexation of
mechanism of metal-biochar interaction in different rice biochar increased the sorption capacity of soil to
soils. The effects of biochar on the mobility and bio- Pb(II) ions (Jiang et al. 2012). For Cr(VI) ions, the key
availability of metals in soils are as follows: (1) direct factor of Cr(VI) sorption by biochar is that the oxygen-
interactions between metals and biochar, includ- containing functional groups reduce Cr(VI) to Cr(III).
ing electrostatic attraction, ion exchange, complexa- The positively charged Cr(III) ions form a strong elec-
tion and precipitation; (2) affecting soil properties, trostatic bond with the negatively charged active sites
thereby indirectly affecting the availability of metals of biochar, hence achieving the in-situ fixation of
in soil, that is, indirect interactions (Fig. 10) (He et al. Cr(III). In conclusion, the biochar could adsorb Cr(VI)
2019). ions with high sorption ability. The Cr(VI) is reduced
The mechanism and function of biochar sorption to Cr(III) and then Cr(III) could form precipitate eas-
and fixation of heavy metal ions (Cd(II), Pb(II), Cu(II) ily (Qiu et al. 2021). The sorption-reduction-solidifica-
and Ni(II)) in acid soil were studied. It was found that tion strategy is a suitable method to immobilize heavy
the fixation ability of biochar to soil heavy metals was metal ions in pollution treatment (Hu et al. 2020; Hao
related to the surface functional properties and struc- et al. 2022). The mechanisms of heavy metal sorp-
tures of biochar and soil. The content and type of sur- tion by bacteria include intracellular, extracellular
face functional groups of biochar are the key factors and cell surface sorption (Fig. 11). Intracellular sorp-
for the fixation of heavy metals (Uchimiya et al. 2010). tion occurs when heavy metal ions are transferred
When biochar was added to alkaline soil with high onto certain organelles to form precipitates or other
clay content and acidic soil with erosion, it showed bioaccumulation. Extracellular sorption is mediated
that the sorption mechanism of Cu(II) ions in the soil by exopolysaccharides (EPSs) such as glycoproteins,
by biochar was mainly electrostatic sorption, and the lipopolysaccharides, and soluble polypeptides. Cell
mechanism of action was the surface complexation surface sorption is generated through the interaction
and precipitation of functional groups and free π elec- of heavy metal ions with negatively charged groups on
trons on the surface of carbon materials and Cu(II) EPSs or peptide / protein functional groups on the cell
ions (Uchimiya et al. 2012). 3% and 5%(W/W) rice bio- wall. Among the above methods, cell surface sorption
char were mixed with soil, and it was found that the is considered the most promising heavy metal sorption
amount of negative charge in soil increased with the technique (Wang et al. 2021).

Fig. 11 The mechanisms of microbial adsorption of heavy metals. (Wang et al. 2021)
Liu et al. Carbon Research (2022) 1:8 Page 19 of 21

2 Conclusion and perspective Competing interests

Xiangke Wang is an editorial board member for Carbon Research and was
In conclusion, physical, chemical and biological modi- not involved in the editorial review, or the decision to publish, this article. All
fications can increase the specific surface areas, active authors declare that there are no competing interests.
sites, pore volumes and functional groups of biochar,
Author details
thereby enhancing the sorption and fixation, and 1
Faculty of Applied Sciences, University Technology MARA​, 40450 Shah Alam,
catalytic reduction/degradation of heavy metals and Malaysia. 2 School of Life Science, Shaoxing University, Shaoxing 312000, China.
3
organic contaminants in the environment, as tabulated College of Environmental Science and Engineering, North China Electric
Power University, Beijing 102206, China.
in Table 1. It is of great significance to construct new
modified biochar with environmental protection and Received: 1 April 2022 Accepted: 9 May 2022
strong sorption capacity, and to study its fixation abil-
ity of heavy metals in soils, water and its mechanism
for the remediation of heavy metals in the environment
and the application of biochar. Although a large num- References
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Chen Z, He X, Li Q, Yang H, Liu Y, Wu L, Liu Z, Hu B, Wang X (2022) Low-
Ethics approval and consent to participate temperature plasma induced phosphate groups onto coffee residue-
No. derived porous carbon for efficient U(VI) extraction. J Environ Sci
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Agree. Extremely Stable Amidoxime Functionalized Covalent Organic
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