Biochar as the effective adsorbent to combustion gas

eous pollutants:
Preparation, activation, functionalization and the ad
sorption mechanisms

ABSTRACT
The massive combustion utilization of fossil fuel in human indu
strial activities, such as power plants, waste
incineration, and kiln combustion for cement production, would e
mit serious gaseous pollutants (SO2, NOx, VOC,
and mercury), aerosols and CO2. There is a growing interest in u
sing novel solid sorbents, i.e., activated carbon
(AC), zeolites, carbon nanotube, carbon molecular sieve, and MO
Fs (metal-organic frameworks), for their ability
to capture gaseous pollutants from combustion flue gas through a
dsorption processes. However, these emerging
alternatives are generally expensive, limiting large-scale industri
al utilization. Biochar, as a stable carbon-rich
solid by-product from biomass thermal treatment, is not only cap
able of replacing coal as fuel in power plants
but also widely reported to be an effective and cheap sorbent fo
r removing the gaseous pollutants in flue gas,
including SO2, NOX, Hg, CO2 and VOC, due to its high porosity a
nd specific surface area and surface functional
groups. In this review, the physical activation, chemical activati
on, and novel modification methods including
microwave, ultrasonic, plasma, ball-milling, and molten salts were
introduced as their optimization to the porous
properties and active surface functional groups for biochar sorb
ents. The functionalized treatments including
metal, ammonia/amines, and halogen modification on activated
biochar were reviewed to observe the further
improved adsorption performance of biochar, for possible enginee
ring application. The abundant amounts of the
oxygenic functional group increase the number of active sites ont
o which NH3 or Hg can be adsorbed, resulting in
higher NO and Hg removal efficiencies. Oxygenated anchoring
sites are also effective intermediate stage to
introduce the nitrogen functional groups, which are generally mor
e effective than the porous texture for acidic
SO2 and CO2 adsorption, especially at adsorption temperature hig
her than ~100 ◦C. The redox reactions of metal
catalyst in biochar and the improved adsorption ability of NH3
and Hg mainly determine the removal perfor-
mance of biochar for NOx and Hg0. The halogen addition to fo
rm C-halogen groups can transform Hg0 into
mercury halide retained on the biochar. The practical removal
performance of various gaseous pollutants is
affected by the adsorption conditions, such as adsorption tempera
ture, humidity and impurities concentrations in
simulated flue gas, selectivity, synergistic adsorption of typical ga
ses, and regeneration capacity. The adsorption
isotherm models and the adsorption kinetic models are helpful f
or predicting the adsorption amount and con-
trolling mechanism and calculating the energy of adsorption to ind
icate the strength and potential of adsorption
and desorption. Finally, the review presents the research gaps
on biochar adsorption mechanisms, industrial
application and evaluation of economy and energy-saving analysi
s.

1.
 contributed significantly to the 4

Introduc 1% increase in energy demand.

tion The

massive combustion utilization of fossil fuel in

According to the “BP Statistical Review
various human industrial
activities, such as power plants, waste incinera
World Energy 2020”, the
tion, and kiln combustion
global consumption of primary energy reached
for cement production, would emit serious g
583.9 EJ in 2019 with
aseous pollutants (SO2,
the ratio of 84.3% is still the fossil fuel and
NOx, CO, VOC, HCl, mercury and NH3), aeroso
y 5.0% is the renewable
ls (PM10, PM2.5) and CO2
energy including biofuel. However, the renew
[1]. The anthropogenic emitted CO2 is the ch
able energy sector has
ief culprit of greenhouse
gas (GHG) to aggravate the global warming, thus it can also be deemed
as one type of gas pollutant. At present, there are various typical
pollutant control devices installing in power plants and other types of
industrial plants, such as the flue gas desulfurization (FGD) which can
remove the SO2 and soluble Hg2+ simultaneously, the selective catalytic
reduction (SCR) and selective non-catalytic reduction (SNCR) for
reducing NOx, the activated carbon (AC) which is used to adsorb Hg, and
the developing technology of monoethanolamine (MEA) solvent and the
CaO-based and Li4SiO4-based sorbents achieved by a reversible reaction
between a calciner and a carbonation reactor [2,3], which separates CO2
from the other flue gases [1,4]. However, the gaseous pollutants still
emit enormously in global perspective because the complete capture is
impossible. Zhong et al. [5] reported that the global total SO2 emission
from all sources was estimated as 105.4 Mt/year in 2014, with a pre-
dominant contribution of 98% from anthropogenic sources. Approxi-
mately 10,000 t of SO2 is produced by a medium-sized coal-fired plant
per year [6]. The global increasing emissions for NOx is from 68 Mt/year
to 122 Mt/year over the period 1970–2012, estimated by the global
anthropogenic emission time series of EDGAR (Emissions Database for
Global Atmospheric Research) [7]. Streets et al. [8] estimated that the
global environmental Hg emissions have grown from 2.19 Mt/year in
2010 to 2.39 Mt/y in 2015 at the rate of 1.8%/year, with the contri-
bution of coal combustion and municipal waste of 29.2%. The latest
estimates from EDGAR [9] confirmed that the global anthropogenic CO2
emission in 2018 reaches 37.9 Gt CO2, which is 1.9% higher than that in
2017. The VOC emitted by human activities is about 142 Mt/year [10],
and it is reported that 44.07 Mt VOCs is emitted annually by the
coal-fired power plants [11].
Some novel solid sorbents have been attempted as technology op-
tions to remove gaseous pollutant from combustion flue gas through
adsorption processes. The widely used solid sorbents include activated-
carbon (AC), carbon nanotube, carbon molecular sieve, zeolites, and
MOFs (metal-organic frameworks) [12,13]. However, these emerging
alternatives tend to be expensive and have limited the industrial utili-
zation on a large scale. Biomass is an important type in renewable en-
ergy families and it is the only renewable carbon source which can
produce bio-solid, bio-oil and bio-gas synergistically through thermal
pretreatments like torrefaction, pyrolysis, gasification, and hydrother-
mal carbonization (HTC). The biosolid, as the stable carbon-rich solid
by-product, is called as biochar and hydrochar when it is derived from
HTC process. The biochar is not only capable of replacing coal as fuel in
power plants [14–17], but also utilized to be cheap and effective gaseous
adsorbent for adsorption removal of flue gas pollutants such as SO2,
NOX, CO2, Hg and VOC. Its porous texture, high specific surface area,
and ample surface functional groups and aromatic surfaces make it an
excellent candidate for this application.
At present, there have been several review papers that have
described the application of biochar as the gas adsorbent. Qian et al.
[18] and Cha et al. [12] have shortly introduced the CO2 adsorption
performance of biochar and biomass-based activated carbon. Chen et al.
[19] has paid attention to the modification methods on the structure
evolution of pyrolyzed biochar, and described that the porosity of bio-
char improved the adsorption ability of gas pollutant (mainly CO2, SO2,
NOx) and the special functional groups affected the sorption stability.
Bamdad et al. [20] reviewed the adsorption isotherms, mechanisms, and
reaction systems of dynamic and static tests for removal of CO2 and H2S
by biochar. Dissanayake et al. [21] summarized the potential of biochar
as CO2 capturing media, their review work found that the micropore
area showed an apparent positive correlation with adsorption capacity
of CO2 onto biochar. The review work from Xu et al. [22], Yang et al.
[23] and Liu et al. [24] commented the research progress of novel
carbon-based solid sorbents including biochar for gaseous Hg removal.
Zhang et al. [10] discussed recent research developments for the
adsorption of VOC onto engineered carbon-based sorbents including
biochar. Gwenzi et al. [25] shortly reviewed the removal performance of
biochar for application into systems of air pollution control, including
the SO2, NOx, Hg, CO2 and VOC.
These review publications are all highly valuable to understand the
advantages of biochar on adsorption of typical gaseous products that
may cause atmospheric hazard. However, they are still not compre-
hensive enough to find out how the biochar works as the effective
adsorbent to gaseous pollutants from combustion flue gas. In compari-
son to previous reviews, this review work concentrates on the adsorption
by biochar rather than other carbonaceous solid adsorbent and con-
centrates on the adsorption of only gaseous pollutants rather than
adsorption from liquid or solution which often happens in other reviews
to result in confusing description (especially for heavy metals and VOCs)
[25]. Subsequently, both the methods of biochar preparation, activa-
tion, and functionalization and the subsequent adsorption conditions
and mechanisms need to be elaborately considered in the perspective of
individuality and universality of various gas types, the systematical ef-
forts for these are undoubtedly benefit to improve the theory and
technology of gaseous adsorption of biochar. Therefore, this study aims
to achieve a comprehensive understanding on the correlation among
biochar characteristics, adsorption conditions, and adsorption perfor-
mance for a typical gaseous pollutant or the simultaneous adsorption
performance to multiple types of pollutants. Such an understanding will
guide the design of biochar-based adsorbents for practical application.
2. Knowledges for understanding the gas adsorption of biochar
2.1. Gas adsorption principles
Adsorption presents the process that the adsorbate transfers from the
fluid including gas and liquid to the adsorbent surfaces, it is mainly
affected by two types of mechanisms including physisorption (i.e.,
physical adsorption) and chemisorption (i.e., chemical adsorption). The
physisorption is characterized by the diffusion of adsorbate into adsor-
bent surfaces, driven by physical forces resulting from concentration or
pressure gradients. This mechanism is typically described by a weak
interaction between adsorbate and adsorbent, which stems from inter-
molecular forces (e.g., Van der Waals forces). As expected for any
physisorption processes outlined by the Le Chatelier principles, the
adsorption capacity of biochar drops with the rise of adsorption tem-
perature [26]. In contrast, the chemisorption however is governed by
chemical interactions between the adsorbate and adsorbent surfaces,
and the electron transfer between adsorbate and surface function groups
in adsorbent forms chemical bonds. Generally, physisorption mainly
occurs in either monolayer or multilayer and is a reversible process,
while chemisorption indicates that the adsorbate is chemically bonded
with the adsorbent and thus tends to be non-reversible [27,28].
In the gas-solid reaction system occurred in gas adsorption process of
porous biochar, the macropore (>50 μm) in solid sorbent serves as a gate
of gas flow, allowing the gas molecules transporting into the biochar
interior rapidly for the following diffusion into the narrower pores; the
mesopore (2–50 μm) serves as a molecule transmission channel from the
surface to adsorption sites; and the micropore (<2 μm) serves as the
main physisorption sites for gas molecule. The micropore adsorption
generally follows the mechanism of volume filling of the adsorption
space rather than layer-by-layer surface coverage [29]. According to the
adsorption potential of theory of micropores volume filling, the internal
adsorption potential of micropores would be apparently promoted and
the vacant pores are gradually filled with adsorbate [30]. The high
adsorption potential of biochar is thus mainly related with its highly
developed micro-porosity and large surface area [31], and the rich
porous structure and the formed abundant active sites would be bene-
ficial to the diffusion and adsorption of gas molecules [32]. Pore diffu-
sion can be further classified into ordinary diffusion and Knudsen
diffusion. Ordinary diffusion presents when the pore size of the adsor-
bent is larger than the mean molecule free path of the adsorbate, while
molecular transport through the finer pores than the mean free path of
the adsorbate is defined as Knudsen diffusion. For gas-phase adsorption
C. Wen et al.
onto biochar which is dominantly microporous, gas molecular transfer
via Knudsen diffusion primarily, and the Knudsen diffusion coefficient
can be predicted from kinetic theory by correlating the pore size of
biochar with the mean free path of the adsorbate. Gas molecular diffu-
sion in biochar includes two types, namely surface diffusion and pore
diffusion [33].
There are multiple common steps in the typical adsorption processes
of biochar. (1). The gaseous adsorbate diffuses from flue gas streams to
external surface of biochar, which is bulk diffusion and known as
external mass transfer; (2). It further diffuses via macropores and mes-
opores, which is known as surface diffusion; (3). It is adsorbed into the
micropores, which is called intra-particle diffusion to form the adsorbed
species; (4). If the biochar is functionalized to improve the chemisorp-
tion, the adsorbed species would chemically react with the active sites
and functional groups onto the functionalized biochar. The slowest step
determines the rate of the whole adsorption process.
2.2. Biochar preparation, activation and modification
Biomass is the fourth important energy resource in the world,
providing approximately 14% of the global energy requirements. In
developing countries, it is even more important, providing 23.5% of
their energy. Biomass broadly include five different groups depending
upon the source obtained naturally or anthropogenically [34], i.e.,
herbaceous species, wood wastes, industrial residues, aquatic plants
such as algae, and human and animal wastes including the municipal
solid waste. As mentioned above, the thermal pretreatment processes on
biomass such as torrefaction, pyrolysis, gasification, HTC, are available
to form the biochar as gas adsorbent. The International Biochar Initia-
tive (IBI) guidelines defines that “the biochar is a solid material obtained
from the thermochemical conversion of biomass in an oxygen-limited
environment”. Note that the hydrochar is produced by the HTC pro-
cess separated from a two-phase mixture of solid and liquid, it is a
somewhat similar product to biochar and can be classified into biochar
generally. The yield and properties of biochar from biomass depend
upon both the employed technique and the process parameters like
biomass properties (feedstock type, particle size), reaction conditions
(reactor type, reaction temperature, heating rate, reaction time, type
and flow rate of carrier gas). Generally, biomass feedstock with higher
lignin content is preferred for the production of biochar, due to it forms
biochar with high porosity and surface area [35]. The potential feed-
stocks for biochar production such as wood and agricultural wastes, food
waste, and sludge, have attracted much attention recently due to their
inexpensive, eco-friendly, and carbon-rich advantages.
The thermal carbonization in the inert atmosphere works to release
non-carbon elements of biomass, mainly oxygen and hydrogen [28],
generating a char structure of rudimentary pore with the tar blocking
the incipient porosity, the formed biochar with limited surface area and
sparse surface functional groups inhibits its sorbent application seri-
ously. Fortunately, if the carbonization process is advanced by the
physical or chemical activation, the tar can be removed and the porosity
is developed to upgrade the physical and chemical structure of biochar
[19]. The activating agents of physical activation include CO2, steam,
H2O2, O2, air or their mixture. As a relative green way, physical acti-
vation could both increase the porosity of biochar and introduce some
surface functional groups onto biochar, such as oxygenic functional
groups from activation of O2, H2O, H2O2, and CO2 and
nitrogen-containing functional groups from NH3 activation, accordingly
may favoring the polarity and hydrophobicity of biochar. Therein, the
CO2 can be recycled as an activation agent to reduce GHG emission after
CCUS technology was widely implemented in the field of industrial
combustion. Activation with CO2 is an oxidative treatment that elimi-
nates carbon atoms and release volatiles with low molecular weight
from the biochar via a heterogeneous reaction (Equation (1)). The high
treatment temperature would increase the reaction rate between the
carbon structure in biochar and CO2 gas and therefore develop the
porous properties. The steam plays as oxidant agent to improve the
porosity of biochar, as the efficient diffusion of steam could enhance
devolatilization and further promote gasification reactions if the tem-
perature is high enough (Equation (2)) [36]. Similarly, the oxidizing
properties of H2O2 is able to cleanse the inner-pores of biochar and
expand the micropores, and increase the number of oxygenic functional
groups (mainly C––O, –OH), leading to a higher Hg adsorption perfor-
mance of biochar activated with H2O2 (biocharH2O2) than that of biochar
activated with H2O (biocharH2O) [37]. It is noteworthy that the activa-
tion or modification methods, such as H2O, H2O2, and CO2, are
expressed as subscript of biochar in this paper for simplicity.
In comparison to the physical activation, the chemical activation
shows some advantages such as lower thermal-treatment temperature,
higher micro-porosity and surface area, which mainly includes the
activation of acids (H3PO4, H2SO4, HNO3), alkalis (NaOH, KOH) and
salts (K2CO3, MgCl2, ZnCl2). KOH activation is widely used to prepare
activated biochar with very high porosity and large BET specific surface
area up to 2000 m2/g (Equation (3)), but the preparation process trig-
gers higher chemical consumption, increased cost, and raised environ-
mental issues. K2CO3 is chosen to replace the KOH sometimes as it can
avoid the high temperature corrosion and environmental hazard of KOH
effectively and shows comparable activating behavior in preparing
porous biochar (Equation (4)), although to a lesser degree leading to
surface area of about 1000–1300 m2/g [38,39]. The activated biochar
modified by H3PO4 had microporous characteristics [40] and presented
the main typical acidic functional groups including phenols and car-
boxylic acids [41]. HNO3 activation can enhance the C and O containing
surface groups via oxidation, it activates the biochar without damage to
its physical morphology [42]. ZnCl2 acts as a dehydrating agent of
biochar at low temperatures and promotes carbon fixation and aroma-
tization at high temperatures, producing a high carbon yield and
well-developed porosity [19].
Some other novel modification methods have been tried to benefi-
ciate the pore texture of biochar adsorbents and/or enhance the surface
active sites onto the biochar. During microwave radiation treatment, the
microwave energy, as a type of electromagnetic energy, is transferred
into thermal energy through molecular interaction of materials, it can
overcome the drawbacks of temperature gradient from the exterior
surface to interior found in conventional heating treatment methods,
achieving uniform and rapid heating of biochar [43]. It is advantageous
to the development of porous properties and add new active sites of
adsorbents [22], however, part of chemisorption sites may be consumed
by the microwave modification after an enough activation, causing the
Hg0 removal of biocharH2O2 decreased from 90.86% to 65.39% [44].
The suitable ultrasonic treatment can prevent the blocking of pores and
aid in enhancing the BET surface area, and then promotes the active sites
capable of further functionalization optimizing the dispersion of active
components such as amine groups and active metal ingredients. The
plasma modification is able to produce energetic electrons, ions and
active radicals that can improve the porous texture and promote the
active surface functional groups on the biochar [23,45]. The plasma
treatment on the biochar can purposively generate various surface
functional groups by reductive, oxidative, or inactive reactions using
different gas environments [22]. For example, the adsorbed oxygen and
water onto biochar can provide the oxygen source for plasma modifi-
cation to generate oxygenic functional groups. Furthermore, the
ball-milling method has also been introduced to produce biochar
eco-friendly. The kinetic energy formed by the moving balls helps to
break down chemical bonds of the referred molecules and produce new
surfaces by fracturing biochar particles [46,47].
These activation and modification methods work to significantly
improve the porosity and affect the specific organic structures in bio-
char. When the biochar has a higher micro-porosity, the adsorption
capacities of various gas pollutants generally become higher via phys-
isorption [48], and would be intensified when the pore distribution of
biochar matches the molecular dynamic size of gas adsorbates [19].
C. Wen et al.

Generally, the atomic ratio of biochar indicates the hydrophilicity
(O/C), aromaticity (H/C) and polarity ((O + N)/C) that can affect the
adsorption capacity of polar and non-polar gas pollutants [25,49], note
that the polarity of biochar is usually expressed by O/C ratios roughly
[35,50]. For example, a hydrophobic biochar surface was generated as
the decrease of hydrogen and oxygen by raising the pyrolysis tempera-
ture, leading to an effective adsorption of nonpolar gas molecules, e.g.,
CO2 [20]. Zhang et al. [40] reported that the H3PO4 activation produced
much oxygenic functional groups and improved the adsorption capac-
ities of polar acetone onto hydrochar. The surface oxygenic functional
groups, e.g., carboxyl, lactone, and phenolic hydroxyl, are closely
related to the acidic character of biochar, which can be effectively
created when the carbon surface of biochar is oxidized by gases and
aqueous oxidants. They are reported to be benefit to the sorption of Hg
to form Hg-OM and polar organic pollutants to facilitate electrostatic
interactions [25]. However, the majority of oxygen functionalities on
the biochar surface was reported to decompose at pyrolysis temperature
of 800 ◦C [51]. It should be noted that certain surface oxygenic func-
tionalities such as ketone, chromene, and pyrone, and nitrogen con-
taining groups can contribute to the basicity of biochar [51]. The higher
proportion of alkaline C–O groups in biochar could lead to stronger
electrostatic or hydrogen bonding interaction with acidic CO2 and SO2
[52].
As a brief result, the gas adsorption onto porous biochar is initially
driven by physisorption via mass transfer of target gas molecules from
the bulk combustion flue gas to the biochar pores, then the modified
biochar drives chemisorption with the chemical reaction between gases
adsorbed and surface functional groups [53].
C + CO2⟶2CO
(1)
C+ H2O⟶CO+ H2
(2)
6KOH + 2C⟶2K + 3H2 + 2K2CO3
(3)
K2CO3 + 2C⟶2K + 3CO (4)
method [51], the amines are nucleophilic owing to the occurrence of a
lone pair of electrons and can thus interact with CO2 [56], it is generally
attached with biochar either through impregnation or through grafting
[57]. Samanta et al. [1] summarized the name and structure of widely
used amine groups for sorbent functionalization. The suitable time of
ultrasonic irradiation can aid in enhancing the active sites capable of
chemical functionalization by amines. Meanwhile, although the occur-
rence of acidic oxygenic functional groups is generally invalid to the
adsorption of acid gas, the oxygenated anchoring sites play as the good
intermediate to develop nitrogen functionalities to the surface of biochar
[58,59]. The pre-oxidation of biochar can be thus considered to enhance
the nitrogen incorporation during the ammonia treatment [58].
In addition, the halogens (Cl, Br, I) have been demonstrated as the
effective modification reagents to promote the Hg0 removal capacity of
biochar from combustion flue gas. The C–Cl groups, as the example,
were acted as activated sites and could be effectively generated during
HCl impregnation and NH4Cl impregnation (Equation (5)), which may
convert Hg0 into HgCl2 and/or other Hg–Cl complexes in the Hg0-
chemisorption process (Equation (6)) [60,61]. However, if the Cl in
biochar is in form of chloride or chlorate and fails to generate the C–Cl
group, it will not be benefit to the Hg0 removal capacity [62]. When the
plasma treatment in Cl2 atmosphere is introduced, the active electrons
collide with Cl molecules to form Cl active radicals, and then attach onto
the biochar to generate more C–Cl groups. The HCl plasma modification
was reported to perform four times higher Hg removal capacity than HCl
impregnation modification [63]. Further, the presence of polyvinyl
chloride (PVC) also acted a beneficial role in Hg0 adsorption as the
successful formation of C–Cl groups during its co-pyrolysis with biomass
[64,65]. The typical functionalized methods will also be expressed as
subscript of biochar for simplicity in this paper, such as biocharMn/Ce,
biocharamine and biocharHCl.
C+ X →C X (X= Cl, Br, I)
(5)
Hg0(ad) + 2C X →2C + HgX2 (ad) (6)

2.4. Research frame

2.3. Functionalization for engineering biochar This review paper summarizes the research on adsorption of various
Some functionalized treatments are considered to further promotegaseous pollutants including SO2, NOx, Hg, CO2 and VOC from com-
the performance of activated biochar for possible engineering applica-bustion flue gas using biochar-based adsorbents, with the research
tion. Doping the oxides of transition metals and noble metals (Fe, Mn, framework presented in Fig. 1. Both the physical and chemical proper-
Ti, Ce, Cu, Co, Ni et al.) onto biochar could promote the activity ties of biochar and the adsorption conditions affect the final removal
biochar materials for effectively capturing NOx and Hg through catalyticcapacities of various gaseous pollutants. Accordingly, the preparation,
reactions [19], the biochar works mainly as a supporter or carrier that activation and functionalization conditions of biochar would be paid
not only increases the dispersion of fine metal oxides but also partic-attention, that is, the physical activation including CO2, steam, H2O2, air
ipatse in the removal process in some cases [23]. The amorphous and O2, the chemical activation including KOH, H3PO4, H2SO4, HNO3,
ultrafine structure of metal oxides from elaborative preparation ZnCl2 and K2CO3, the modification achieved through microwave, ul-
methods generally provides more active sites for catalytic reactions trasonic, plasma, ball-milling, and molten salts techniques, and the
comparison to the corresponding raw crystalline states [32,54,55]. Forfunctionalization for engineering biochar including addition of the ox-
example, the ultrasound treatment was reported to optimize theides of transition metals, the basic sites capable of interacting with acidic
dispersion of active ingredients such as Mn and Fe [22]. Generally, thegas, and the halogens or sulfur species improving Hg removal. The
biochar adsorbents functionalized by metal oxides are capable relevant treating conditions, such as pyrolysis and activation tempera-
achieving good removal performance in a higher temperature range and ture, flow rate of activated gas, concentrations of chemical activation
longer operation time, as redox reactions are found among doped agents, ratios of biochar to activating agent, and processing time, should
metals, carbon structure of biochar, and gas pollutants. Noteworthy, thealso be attended as their influence on biochar characteristics. It is
development of magnetic biochar adsorbent is beneficial to the betternoteworthy that the systematic introduction about the thermal pre-
utilization efficiency of biochar due to it can feasible be recovered fromtreatment of biomass, the physical and chemical properties of biochar,
engineering fly ash. and the relevant analytical methods such as XPS, FTIR, TPD, and XRD,
The surface basic properties of biochar are generally suitable have been given in other relevant reviews [21,51,53], this review work
adsorption of acidic gas such as SO2, NOx, CO2, while the biochar pre-will thus focus on their influence on the adsorption performance of
senting surface acidity is beneficial to the adsorption of alkaline gas. Thegaseous pollutants.
functionalized modifications by incorporating basic sites capable The typical layout of power plant and waste incineration plant with
interacting strongly with acidic gas are benefit to promote the adsorp- possible injection positions of biochar are presented in Fig. 2. There
the
tion capacities of CO2 and SO2 [1], therefore the ammonia modificationare always multiple gas compositions existing in the industrial fuel gas.
of biochar to introduce basic nitrogen functionalities is a promisingThe adsorption conditions, mainly include the adsorption temperature,
C. Wen et al.

Fig. 1. The research framework on biochar adsorbent to combustion gaseous pollutants.

the humidity and impurities concentrations in simulated flue gas, the to 750 ◦C [28] and gasification up to 950–1100 ◦C [68,69] were tried to
selectivity and synergistic adsorption of typical gases, would be relatedproduce the biochars using for adsorption of SO2. The adsorption uptake
to affect the final removal performance of various gaseous pollutants.of SO2 by unmodified biochar is generally at a low amount of less than
The cycle and regeneration capacity of biochar is also important 20 mg_SO2/g_biochar [70]. Iberahim et al. [71] carried out the response
guarantee a satisfactory practical removal performance. The adsorptionsurface method (RSM) using central composite design (CCD) to optimize
isotherm models and the adsorption kinetic models provide the valuablethe production of biochar from sludge. The heating temperature
insight into the predicted adsorption amount and controlling mecha-(200–600 ◦C), heating rate (5–20 ◦C/min), and holding time (60–120
nism and therefore are vital in optimization the design and performance min) during pyrolysis in N2 condition were investigated, with the SO2
of biochar, from them the adsorption energy can be calculated to indi-adsorption capacity as the responses. They found that the pyrolysis
cate the strength and potential of adsorption and desorption. Subse-temperature had the most obvious effect on adsorption capacity of SO2,
quently, the research gap on improving the adsorption performance which increased to reach optimum and then showed falling trend after
biochar, on synergistic adsorption in industrial application and on the450 ◦C with the increment of pyrolysis heating temperature [71]. Yavuz
evaluation of economy and energy saving analysis are presented. et al. [72] prepared the biocharH3PO4 from olive stone at 200–700 ◦C, the
pore volume enhanced up to 400 ◦C and then a shrinking of the pores
3. Adsorption of various combustion gas pollutants by biochar
mainly affecting the mesoporosity was found due to a further increase of
temperature. The high pyrolysis temperature is benefit to increase the
3.1. Adsorption performance of SO2 porosity of biochar and enhance the adsorption ability, but at higher
SO2 is harmful to skin and respiratory system. In order to combattemperature, the high ash volumes in biochar from high temperature
these threats, the Environmental Protection Agency (EPA) of United pyrolysis blocked the pores of biochar and destructed the surface func-
States has revised their National Ambient Quality Standard (NAAQS) fortional group, both of which ultimately hindered the adsorption process
hourly primary standard of SO2 emissions, reducing from 140 ppb down[73]. Bashkova et al. [68] reported the sewage sludge biochars prepared
to 75 ppb in 2012. The European Union demanded 70% lowered SOat 600–950 ◦C had similar removal capacities of ~12–14 mg/g at 25 ◦C
emission by 2029 through the establishment of 2016/2284/EU Regu-(Table S1), it is likely that the presence of high dispersion of catalytic
metals and chemically active calcium oxides during carbonization at
lation [66]. The ultra-low emission retrofitting of China released in 2015
high temperatures may react with SO2 to form sulfites, which offset the
requires coal-fired power plants to limit SO2 emissions to 35 mg/m
unfavorable effect of high temperature on pore and functional groups.
[67]. The adsorption method for the reduction emission of SO2 has the
The higher pyrolysis heating rate is expected to promote the mass
potential to compete with the widespread FGD technology, because
transfer of volatiles and improve the development of the porous texture
its fast process, simple equipment, and effectiveness. Table S1 of theand surface area of biochar, however, the heating rate higher than 12
Supplementary Materials summarizes the biomass precursors, the◦C/min presented lower BET surface area and reduced SO2 adsorption
preparation conditions of biochar, the typical adsorption conditions and capacity. This can be caused by the high internal temperature resulting
the optimum adsorption performance of SOx by biochars. in partial graphitization in the interior of biochar [73]. After carrying
out the experiments of different holding time between 60 min and 120
3.1.1. Influence of biochar preparation conditions
As shown in Table S1, only the pretreatment methods of pyrolysis upmin, the SO2 adsorption uptake was found to reduce after 98 min owing
to pore destruction caused by the extended heating time [73].
C. Wen et al.

Fig. 2. The typical layout of power plant (a) and waste incineration plant (b) with the possible injection positions of biochar.

Sumathi et al. [69] and Iberahim et al. [6,73] also presented the physical activation with CO2 (biocharCO2) and chemical activation with
optimization analysis with the RSM/CCD design, in which the activation KOH (biocharKOH), respectively. The biocharKOH presented the largest
temperature, retention time and flow rate of CO2 were the main vari- surface area and the narrowest pores, and an acidity behavior after an
ables considered for generating porous biochars, and the activation
acid-base titrations exhibited the lowest affinity for the acidic SO2
temperature was found to play the major role. CO2 activation at high
indicated by the Freundlich model, meanwhile the biocharN2 presented
temperature promotes the reaction intensity between the carbon struc-
the more basic surfaces capable of enhancing the affinity of SO2. Despite
ture of biochar and CO2 gas (Equation (1)) and leads to the development
of micropore structure. As shown in Table S1, the biochar prepared its weak interaction with SO2, the biocharKOH still exhibited the highest
1100 ◦C reported the highest surface area and highest removal capacity SO2 uptake which should be controlled by its best porosity character-
of SO2 (~37 mg/g), implying the contribution of physical adsorption istic. Besides, the similar SO2 adsorption of biocharN2 and biocharCO2
[69]. However, other work found the obviously lower optimum acti- was caused by the balance of the lower micro-pore volume and the
vation temperature of 442 ◦C [73] and 753 ◦C [6], respectively. The too higher surface basicity of biocharN2 than biocharCO2. Braghiroli et al.
extended activation temperature accelerates the reaction between car- [76] also compared three types of activation treatments, i.e., CO2, steam
and KOH. The biocharH2O had the highest adsorbed proportion of SO2
bon and CO2, it may encourage more pore widening and collapse rather
than pore development and meanwhile destroy the basic functional (Table S1), owing to its lowest acid oxygenated groups as it had a
groups which acted an active role in the SO2 adsorption. A suitable moderate surface area compared with the other two biochars. Guo et al.
activation time extended from 1 h to 2 h can increase the pore volume, [41] compared the biochar treated by KOH and H3PO4, the biocharH3PO4
presented the main typical acidic functional groups (phenols, carboxy),
surface area, and acidity of the biocharH2O [74], but the prolonged
activation time can also damage the pore structure, indicating as expected, had lower adsorption capacity per BET surface area than
decreasing trend in SO2 adsorption capacity [6,72]. Guo et al. [75] the biocharKOH which contained much basic functional groups (pyrone).
ported that the adsorptive capacities of SO2 were linearly proportional As a result, the adsorption performance of SO2 is affected by both porous
related with the micropore volumes of biochars. Yavuz et al. [72] alsoand chemical properties of biochar, i.e., pore volume, surface area and
observed an almost linear relationships between the SO2 adsorption and acid-base properties.
the textural properties. SO2 adsorbs on smaller pores preferentially due 3.1.2. Impacts of functionalization
to its kinetic diameter of 0.364 nm, and the dipole-oriented single layer
As a Lewis acid, SO2 tends to interact with basic surfaces, that is, the
structure favors the interaction between micropores and SO2 molecule
[72]. sulfur atom in SO2 as the electron acceptor can effectively form stable
complexes with the bases as the electron donor [77]. The linear rela-
Atanes et al. [28] compared the performance of three types of bio-
tionship between the SO2 adsorption and the content of basic groups was
chars from waste cork powder prepared by thermal with N2 (biocharN2
found by Yavuz et al. [72]. The NH3 modification was reported to have a
C. Wen et al.

lower temperature (~700 ◦C) to improve the micropore texture of bio-

char than the CO2 activation [78]. It is noted that the high activationNiSO3 + H2O→ Ni H2SO4
(8)
temperature in NH3 improved the porous texture and then enhance the
impregnation effectiveness of nitrogen [79], however, if the treatmentNiSO3 + C O→C NiSO4 (9)
temperature is too high (≥900 ◦C), the NH3 modification resulted in the
decomposition of nitrogen-containing groups [78]. Shao et al. [70SO2 4 + M2+ + 2H2O→MSO4⋅2H2O (M = Ca, Ce…) (10)
performed an effective work to identify the joint effects of physisorption
and chemisorption on the adsorption of SO2, the CO2 activation and3.1.3. Adsorption conditions
tertiary amine (MEDA) impregnation were employed to prepare the Some studies reported that as increasing the adsorption temperature
biochar from corncobs. CO2 activation can aid in improving BET surface from ~25 ◦C to ~100 ◦C, the amounts of SO2 adsorbed by biochar
area and enhancing the amount of activated sites, leading to decreased continuously [72,75,83]. They described that the high tem-
adsorption amount of 57.78 mg/g of SO2 at 100 ◦C (Table S1). The peratures resulted in SO2 molecules losing their kinetic energies and no
impregnated nitrogen sites from MEDA were mainly observed on the adsorption due to Brownian movement of the SO2 molecules, so that the
micropores of biocharCO2 [79], the nitrogen content thus showed a good adsorption became an exothermic process [83]. The overheating at
linear relationship with the BET surface area and the total pore volume higher temperatures of 150 ◦C and 200 ◦C may cause higher adsorption
of the biochars prepared from different biomasses [79]. When the MDEA potential energy and then suppress the adsorption capacity of SO2 [33,
mass concentration was added to 1% and 4%, the deteriorated pore 78,84]. Furthermore, the adsorption temperature can also affect the
structure significantly destroyed the adsorption of SO2 compared with chemisorption behavior of SO2. Iberahim et al. [73] reported that as the
biocharCO2. However, as the MDEA concentration was higher than 8%, adsorption reaction temperature increased from room temperature to
the micropore structure nearly collapsed completely meanwhile much 50–100 ◦C, an increasing tendency of SO2 adsorption amount could be
nitrogen-containing functional groups (mainly C–N) were generated, the observed because of the enhanced chemical reaction rate between SO2
chemical adsorption was dominant to receive a very high adsorption and active surface sites. Zhang et al. [78] reported that the SO2
capacity of SO2, i.e., 156.22 mg/g at 100 ◦C (Table S1) [70], indicating adsorption capacity of 175.9 mg/g fairly depended upon the porous
the nitrogen functionalities onto the biochar are more influential than texture of biocharNH3 especially micropores at a low adsorption tem-
the pore texture for the adsorption of SO2, with the conversion to N– perature of 30 ◦C (Table S1), the physisorption is the major adsorption
groups (Equation (7)). The ammonia and amine functionalization on power. At the higher adsorption temperature of 120 ◦C, the SO2
biochar for adsorption and reaction of SO2 is manifested in Fig. 3. adsorption capacity of biochar presented a strong linear relationship
with its N/C mass ratio, indicating the chemisorption come from
The pyrolyzed biochar from sewage sludge was impregnated with
nitrogen-containing functional groups were primary factor leading to a
(NO3)2 [80], the Ni and NiO phases were found to coexist in biochar and
higher sorption capacity of 115.4 mg/g at 120 ◦C than biocharCO2
the oxygenic functional groups increased. SO2 could be absorbed on the
(Table S1).
surface of biochar to react with oxygen species to generate NiSO3, fol
The adsorption capacity increased from 16.65 mg/g in dry adsorp-
lowed by the reaction with H2O to generate Ni–H2SO4 (Equation (8) tion atmosphere to 37.72 mg/g in atmosphere with 15% moisture [73],
furthermore, SO2 was adsorbed on the NiO surface to form sulfate, the nearly half SO2 removal capacity at dry atmosphere compared with
possibly as C–NiSO4 (Equation (9)). However, Sumathi et al. [81] re- that at wet atmosphere was also indicated by Bashkova et al. [68] and
ported that if the biochar impregnated with Ni and Ce catalyst, the Iberahim et al. [6]. As the humidity increased from 0 to 50–60%, the
adsorbed amount of SO2 decreased regularly, due to the pore blockage sorption capacity of SO2 increased continually [6,79,81,82]. The H2O
by the Ni and Ce metals. When the SO2 was dissolved in the alkaline accumulated on the surface and interior pores of biochar favors the
water membrane formed on the biochar surface, the minerals in biochar formation of a liquid membrane which would lead to the SO2 adsorbed
could react with them to form stable sulfates via catalysis oxidation by biochar easier than the adsorption in gas-solid reaction. If the SO2,
(Equation (10)), the contribution to SO2 sorption from minerals in bio- O2, and H2O were all adsorbed on the surface of biochar, the SO2 was
char was reported to be 44.6%–85.5% [82]. first physically adsorbed onto the biochar, then oxidized to SO3 and
1 transformed to H2SO4 (Equations (11) and (12)) [81]. Three forms of
R2CH3N+ SO2 + O2 + H2O→(R2CH3NH)2⋅SO4 (7)
2 adsorbed sulfur-containing substances could exist, i.e., weakly adsorbed
SO2, physically adsorbed SO3, and strongly adsorbed H2SO4 [68].

Fig. 3. The ammonia and amine functionalization on

biochar for adsorption and reaction of SO2 and CO2.
Route 1: The nitrogen-containing functional groups
(C–N, –NH2, etc.) onto biochar are generated from
ammonia and amine modification, they interact with
SO2 to form N–H groups (Equation (7)). Route 2: The
similar nitrogenous functionalities react with CO2 to
form N–COO groups (Equation (64)). Therein, the
pre-oxidation and ball-milling treatment of biochar
help to form acidic oxygenic functional groups, which
can act as an effective intermediate stage to introduce
nitrogen functionalities onto the biochar.
C. Wen et al.
Nevertheless, the adsorption capacity was also reported to be decreased
at the high humidity of 30% and 60% [73], this could be attributed to
the decrease in SO2 partial pressure leading to SO2 molecules more
difficult to compete with water vapor to occupy the biochar surface.
Besides, Xu et al. [82] found that the SO2 adsorption by biochar from
sewage sludge increased with the humidity raising from 0% to 20% and
then decreased until 50%, too much H2O tended to induce aggregation
of the clay minerals rich in sludge biochar, which blocked or occupied
the active sites for the adsorption of SO2. Bashkova et al. [68] described
that at wet air adsorption conditions, the SO2 adsorption capacity of
biochar from sludge increased with increasing temperature of carbon-
ization, as the chemically active calcium oxides and high dispersion of
catalytic metals was formed during high temperatures carbonization.
The sulfuric acid derived from SO2 reacted with inorganic oxides and/or
salts in biochar to form more soluble sulfates in biochar, improving the
chemisorption of SO2.
Zhang et al. [79] paid attention to the influence of flue gas compo-
nents in the SO2 adsorption of biochar. With the raise of O2 concentra-
tion from 0 to 14%, the nitrogen-containing groups in biochar might be
oxidized, leading to the SO2 adsorption capacity reduced generally. The
presence of O2 may promote the adsorption process although the su-
periority was not as good as the humidity [82]. The strong adsorption
was related to the oxygenated groups onto the biochar, which were
believed to be catalytic centers for SO2 oxidation to SO3 [68]. In the
presence of NO, the SO2 adsorption capacity of biochar was clearly
better than that without NO, and the SO2 adsorption uptake first
enhanced and then dropped as the increase of NO concentration, with
the maximum adsorption uptake of 216.19 mg/g at 500 ppm NO [79].
The synergistic adsorption effect of NO and SO2 may be helpful to
generate the (NO2)(SO3) intermediates, which was reported to adsorb
effectively at the nitrogen-containing adsorption sites (Equation (13)).
SO2 (ad) + O(ad)→SO3 (ad) (11)
SO3 (ad) + H2O(ad)→H2SO4 (ad)
R2N CH3 + NO+ SO2 + O2→R2CH3N⋅(NO2)(SO3)
3.2. Adsorption performance of NOX
The concentration of NO in combustion flue gas mainly depends on
the nitrogen content in fuel and typically ranges from 100 to 1000 ppm
[85]. It causes environmental problems such as photochemical smog,
acid rain, ozone layer depletion, and global warming. SCR is the most
widely used technology worldwide to reduce NOx emissions among the
various measures. NH3, as the reducing agent in SCR processes, is used to
convert NOx into harmless N2 and H2O (Equation (14)). The catalysts
most frequently used are V2O5/TiO2 catalysts mixed with WO3 or MoO3.
Recently, the low-temperature SCR catalysts capable of working under
300 ◦C or even 100–200 ◦C have attracted more attention, resulting in
the removal systems with low energy consumption and ease of retro-
fitting [86]. Biochar based catalysts were reported to present a high NOx
removal capacity at relatively low temperatures of 100–250 ◦C through
suitable treatments, such as impregnation with metals such as Fe, Mn, V,
Cu, and Ni, that create ample oxygenic functional groups onto the bio-
char, assisting the adsorption and chemical reaction of NOx. Table S2 of
the Supplementary Materials summarizes the preparation conditions of
biochar, and the typical adsorption conditions and optimum adsorption
performance of NOx by biochars.
4NH3 + 4NO + O2 →4 N2 + 6H2O [SCR reaction]
(14)
3.2.1. Influence of biochar preparation conditions
Qin et al. [87] reported that with the carbonization temperature
increased from 500 ◦C to 900 ◦C, the specific surface area of biochar and
the NOx removal first increased until 700 ◦C and then decreased. It is
noteworthy that the NOx adsorption capacity on biochar without any
functionalization at temperature range of 100–300 ◦C is very poor [81,
88]. Al-Rahbi et al. [88] reported that the KOH activation provided the
best NO removal efficiency of ~75% after 120 min which was related to
the increase in micropore volume and BET surface area (Table S2),
followed by K2CO3, NaOH and Na2CO3 activation with 37%, 30% and
19% removal respectively. Ko et al. [89] observed that the pore volume
and specific surface area of biochar from municipal waste only increased
slightly after the HCl treatment, thus without the improved effect on the
NOx removal. The kinetic diameter of NO is 0.3 nm, biochar with similar
pore diameter should have an observable adsorption efficiency [88],
both increasing micro-porosity and surface area of the biochars were
observed to correlate directly with the increased NO removal efficiency
[88].
Cha et al. [86] presented that the biochars prepared from rice straw
and sewage sludge served as SCR catalysts between 50 and 250 ◦C. In
comparison with the biocharH2O, the biocharKOH created more micro-
pores and mesopores, specific surface areas, active nitrites, and oxygen
functional group amounts (mainly C––O and C–O), which increased the
amount of active sites onto which NH3 can be adsorbed, the higher NO
removal efficiency was thus observed due to reaction between adsorbed
NH3 and NO (Equation (14)). Yang et al. [90,91] attempted the HNO3
modification and found an apparent porous structure and the increased
surface acidic functional groups of biochar, showing an impressive
de-NOx efficiency. When the activation temperature increased for acti-
vation process at steam and KOH, more micropores and mesopores were
generated, resulting in the generally increased total pore volume and
specific surface area for both biocharH2O [74,92] and biocharKOH [88,
92], while the oxygen functional groups increased for biocharH2O but
decreased for biocharKOH with increasing temperature [92]. The former
is because the aromatization reaction that takes place at high tempera-
tures, indicating the transformation of aliphatic or alicyclic compounds
into aromatics, while the latter attributes to breakage of chemical bonds
such as carboxylic group bonds since 700 ◦C. As a result, the functional
groups that developed onto the biocharH2O prepared at 700 and 800 ◦C
(12)
acted
NO as active
x removal sites on which
compared NHprepared
with that 3 can be adsorbed,
at 600 ◦C,resulting in abiochar
even if the higher
prepared at 600 ◦C had the best specific(13) surface area. By contrast, the
NOx removal efficiencies of biocharKOH prepared at 700 and 800 ◦C were
lower than that prepared at 600 ◦C owing to the damage of oxygenic
functional groups.
During steam activation, the specific surface area increased firstly as
the water content raised from 10 to 60% and then decreased when it
raised further to 80% [92]. Under the high water vaper concentration
from 40 to 80%, the oxygenic functional groups developed more easily
onto the biochar to create more active sites which played the dominant
role in the increased NOx removal efficiency [92]. The de-NOx perfor-
mance of biochar appeared to be affected more by chemical properties
(mainly oxygenic functional groups on active sites) instead of physical
properties under this circumstance [92]. With the weight ratio of KOH to
biochar increased from 0.5 to 2, the micropores were developed and the
amount of oxygenic functional groups increased, both of which were
benefit to the adsorption of NH3 and increase of NOx removal.
Furthermore, the proportion of N-6 groups (pyridine nitrogen) formed
by the increased nitrogen ratio from urea increased de-NOx activity of
the cotton stalk biocharH3PO4 significantly [93].
3.2.2. Impacts of functionalization
The biochar materials with transition metal oxide catalysts are
widely recognized
catalysts to fit
have been in theextensively
studied low-temperature
due tofluetheir
gas.superior
Mn based
low SCR
tem-
perature performance and CeO2 has also been used as a promoter to the
SCR catalyst owing to its unique acid-base and redox properties. Singh
et al. [94] suggested that the NO conversion capacities of Mn/Ce func-
tionalized biochars were much more dependent on the metal loading
content than the pore structure, the NO removal capacities increased as
the addition of Mn and Ce. Yang et al. [90] reported that the conversion
C. Wen et al.

capacities of NO within 125–225 ◦C followed Mn > Ce > V > Fe, and the L-H mechanism and significantly enhanced the de-NOx efficiency due to
biocharMn presented the highest NO removal efficiency of 87.6% at 200 the “fast SCR” reaction shows a markedly higher reaction rate than the
◦C (Table S2). Another study presented the Fe and Mn presented rela-
“standard SCR” reaction [90,98]. Oxides of Zr, Ni and Co were doped
tively higher NOx removal abilities than Cu and Al in higher temperature into Mn oxide biochar catalysts, thereinto the biocharZr/Mn catalyst
section of 250–400 ◦C due to the strong adsorption energy indicated
presented the highest NO removal of 86% at 200 ◦C (Table S2) [100],
the density functional theory (DFT) theoretical calculations [87]. The
similarly, the biocharSm/Mn catalyst showed the high NO conversion of
micropores would be reduced after the impregnation of metals, e.g., Mn,
85% at 200 ◦C (Table S2) [95]. The high activities of biocharZr/Mn and
Ce, Sm, due to blocking of the pores [86,89,90,95,96]. The bimetallic
oxides were found to enter the interlayers or pore holes and caused the biocharSm/Mn were related to the high Mn4+ concentration, chemisorbed
collapse or block of pore holes to result in the larger pore size, thus the oxygen, excellent reducibility and more Brønsted acid sites and weak
catalysts were typical mesoporous materials with most of the pores Lewis acid sites, which increased more active sites and facilitated the
3–4 nm [95]. oxidation of NO and followed the L-H reaction mechanism: on one hand,
The redox reactions of metal catalyst in biochar and the adsorption the coordinated NH3 onto the Lewis acid sites would be oxidized to form
–NH2 intermediates which can be promoted by the more Mn4+ ratio, the
ability of NH3 mainly determine the de-NOx performance of the biochar
–
with metal catalyst [81,94]. Yang et al. [91] revealed that Mn/Ce oxidesand H2O NH 2(ad) reacted with NO(ad) to generate NH2NO and then formed N2
(Equation (25)). On the other hand, the adsorbed NO2 was
had a low degree of crystallinity and dispersed well on the biochar oxidized to NO2 and/or NO3 species, and then reacted with NH4+ onto
surface, and the higher fractions of Mn to Ce, i.e., 5:5 and 7:3, on bio-
charMn/Ce catalysts were beneficial for the conversion of NO. The highly the Brønsted acid sites to generate NH4NO2 or NH4NO3, also formed N2
dispersed Mn increased both the number of oxygen vacancies and theand H2O finally (Equations (26) and (27)).
surface oxygen functional groups, as its low binding energy indicates the The biocharMn/Ce from co-activation of H3PO4 and steam exhibited a
actived Mn state and strong redox properties of Mn4+ (Equation (15) high NO conversion of 95% at 280 ◦C (Table S2) [96], as the H3PO4
[91,96]. The oxygen vacancies would adsorb oxygen to form theactivation apparently increased the BET surface area of biochar while
chemisorbed oxygen, which is more active and has higher mobility than the steam activation mainly led to an increase in the acidity and
the lattice oxygen and plays the important role in the catalytic reaction oxygenic functional groups of the biochar catalysts [94]. However, the
[90,96]. As the number of oxygen vacancies from Mn increased, thealkali metals presented in the flue gas or cotton biochar itself may
oxygen storage and release cycle between Ce3+ and Ce4+ was enhanced, neutralize the Lewis and Brønsted acid sites, thus inhibiting the initial
which is positively related to the electron interaction between Mn and protonation of NH3 to NH4+ and causing a relatively low NO removal of
Ce species with oxygen converted from CeO2 to Mn2O3 (Equation (16) 65% at 280 ◦C (Table S2) [94]. Liu et al. [97] carried out the air
and is able to accelerate the conversion of O2 into chemisorbed oxygen oxidation treatment before and/or after loading biochar with Mn. The
(Equations (17) and (18)) [91,96,97]. The surface oxygenic functional oxidation treatment introduced more oxygenic functional groups on the
groups (e.g., carboxylic group) can not only help to adsorb NO but also catalyst that could produce the high-valence state Mn (Mn4+) through
improve the dispersion of active phase to generate more adsorption sites electron transfer. After pre-oxidation of biochar, the pore volume and
for NH3 [90]. The amount of NH3 desorption tested by NH3-TPD is usedspecific surface area enhanced, and the C–O groups were oxidized to
to express the surface acidity of biochar catalysts governed by both the acidic carboxyl groups, and after further post-oxidation, the contents of
Lewis acid sites and Brønsted acid sites [95,98]. The Lewis acid sites areMn4+, chemisorbed oxygen and the surface acidity increased, which
derived from highly dispersed and unsaturated Mn or Ce sites [90 improved the adsorption of NH3, the conversion of NO to NO2, and the
while the Brønsted acid sites are related to surface hydroxyl groups [98 redox capabilities of the biochar catalysts. The biochar after two
NH3 is able to adsorb on both the Lewis and Brønsted acid sites (Equaoxidation treatments thus reached the NO conversion of 97.0% at 150 ◦C
tion (19)). The coordinated NH3 onto the Lewis acid sites is capable (Table S2). The metal functionalization on biochar for adsorption,
forming –NH2 species and NH4+ can be generated from the protonation catalysis, and reaction of NOx is presented in Fig. 4.
(15)
2MnO2 →Mn2O3 + O
adsorbed NH3 on the Brønsted acid sites, respectively (Equations (20)
and (21)). The biochar catalyst exhibiting the high surface acidityMn2O3+2CeO2→2MnO2 + Ce2O3 (16)
generally indicated that more NH3 can absorb on its surface [96]. Based
on the above reasons, the higher catalytic activities of NO compared M(n 1)++O(ad)→Mn+ 1(M= Mn, Ce…)
O2→Mn+ (M = Mn, Ce…) (17)
with the biochar without metal impregnation were widely achieved [86 2
89,98], a high NO removal capacity of 99.2% at 175 ◦C was thus achM(n 1)+ +
(18)
ieved by Yang et al. (Table S2) [91].

Some catalytic processes of biochar catalyst were recognized as NH3 (g) Lewis⟶acid sites NH3 (ad) (19)
Eley-Rideal (E-R) mechanism indicating the reaction between the
adsorbed NH3 and gaseous NO. The NH3 was adsorbed quickly onto theNH3 (ad) + Mn+ →M(n 1)+Bronsted
± NHacid + H+(M = Mn, Ce…)
sites
2 (ad)
Lewis acid sites as coordinated NH3 on the surface of MnOx, and the (20)
interaction of coordination and adsorbed oxygen on the surface
Eley-Rideal
⟶ mechanism:
catalyst could generate –NH2, which reacted with the gaseous NO NH3 (g) + H+ NH+4 (ad)
(21)
generate NH2NO, and finally decomposed to form N2 and H2O (Equation
(22)) [94,96]. Similarly, the coordinated NH3 can also be activated
Ce4+ to generate –NH2, and Ce3+ was oxidized by O2 to replenish the NH2 (ad) + NO (g) →NH2NO (ad) →N2 (g) + H2O (g)
Ce4+ for the single CeO2 catalysts [91]. M (22)
The other mechanism named as Langmuir-Hinshelwood (L-H) Langmuir-Hinshelwood mechanism:
mechanism presenting the reaction between the adsorbed NH3 andNO(g) → NO(ad) + O2(ad)π ⟶bondsNO2 (ad)
adsorbed NO2. The π-bonds in the graphite crystallite and the oxygenic (23)
functional groups as well as chemisorbed oxygen strengthened by the2NH3 (ad) + NO (ad) + NO2 (ad)→2 N2+3H2O
impregnation of Mn were beneficial to the oxidation of NO to NO NH2 (ad) + NO (ad) →NH2NO→N2 + H2O (24)
(Equation (23)) [90,96,97]. The adsorbed NO2 was much more stable
(25)
than NO owing to the strong binding between NO2 and carbonaceous
surface [99]. The coexistence of NO2 and NO would arouse the “fast
SCR” reaction of NO2, NO and NH3 (Equation (24)), which follows the
C. Wen et al.

Fig. 4. The metal functionalization on biochar for adsorption, catalysis, and reaction of NOx, Hg, SO2 and CO2. Note that the dash line simply expresses
the
adsorption of NOx, NH3, Hg, O2, SO2, CO2 from atmosphere to surface pore of biochar. Route 1: The sulfuric acid derived from SO2 reacts with inorganic oxides
and/
or salts in biochar to form sulfates in biochar (Equations (8)–(10)). Route 2: Basic metal oxyhydroxides interact with CO2 to form carbonate (Equation (67)). Rout
e 3:
The sophisticated details to transfer NOx are described in Section 3.2.2. Route 4: The loss of oxygen from a metal oxide could be replenished by the lattice oxygen
M(n
in 1)+ + NO2 (ad) →Mn+ + NO 2 (M= Mn, Ce…) ranges. Liu et al. [93] reported that at low temperatures of 50–150 ◦C,
another metal oxide with higher oxidizability during the bimetal redox reactions (Equations
some(15)
NO and
was(16)), and the Hg
transformed adsorbed
to 0NO 2 on theonto biochar
surface can be oxidized
of biochar H3PO4, which
NH+4 (ad) + NO 2 (ad) →NH4NO2→N2+2H2O
by
both lattice oxygen and chemisorbed oxygen replenished by gaseous O2 to produce HgO (Equation (31)).
3.2.3. Adsorption conditions

induced the “fast-SCR” reaction (Equation (24)). However, NO2 was no

longer generated at the high-temperature region of 225–300 ◦C, there-
fore, NO was mainly reduced by the “standard-SCR” reaction.
For biocharMn prepared from straw, as the reaction temperature The addition of O2 was essential to boost the adsorption of NOx via
raised from 50 ◦C to 200 ◦C, the removal capacity of NOx was reported the addition of the oxygenic functional groups and the catalytic oxida-
decrease from 86% to 41%, but the removal efficiency promoted againtion of NO to NO2 [88]. Sumathi et al. [84] reported that the removal of
to 85% at a higher temperature of 200–250 ◦C [86]. For the biochar NO at 15% H2O was nearly identical to that at dry condition, as the
prepared from co-activation of H3PO4 and steam [96], the NO conver-process of adsorption, reduction and catalytic oxidation of NO would
sion increased as the temperature increased from 160 to 280 ◦C. Sumathi happen simultaneously on the system of H2O–O2–NO-biochar, but the
et al. [81] found that the optimum reaction temperature for removal removal of NO was deterred at higher percentage of H2O, possibly owing
NOx on biocharNi and biocharCe was around 200 ◦C between 100 and to the low solubility of NO in H2O and the pore blockage derived from
300 ◦C. Cerium oxide has high oxidation activity to decompose NO, but the salt by-products. The biocharMn from peanut shell was subjected to
at the higher 300 ◦C, the oxygen-containing groups formed on biochar water vapor or SO2 to check the resistance of biochar catalysts [90].
were attached to the carbonaceous group to generate CO and CO2, thusWhen 10% H2O was added, the NO conversion of biocharMn dropped
lowered the conversion of NO [84]. Two temperature windows for thefrom 87% to 81% and exhibited a rapid recovery after stopping the H2O
biochar SCR test were found by Wu et al. [74], one was between 180 andflow, implying that H2O did not lead to permanent deactivation of
240 ◦C and the other was between 260 and 280 ◦C. The biochars with biocharMn catalyst. When the SO2 was added, the NO conversion drop-
most micropores promoted the conversion of NO at the temperatureped from 87% to 71% and recovered to about 79% after the SO2 flow
range of 180–240 ◦C while the presence of mesopores as well as the was stopped, suggesting a certain of irreversible deactivation for bio-
higher dispersion of metals and acidity in the biochars catalyst benefited charMn. Furthermore, it implied that the addition of Ce could promote
NO conversion at the reaction temperature above 260 ◦C. Chen et al. the H2O and SO2 resistance of catalysts [91]. Chen et al. [100] detected
[100] presented that when temperature raised from 75 ◦C to 175 ◦C, the the biocharZr/Mn catalysts in the presence of SO2 + H2O at 200 ◦C, they
NO conversion of biocharZr/Mn promoted rapidly, and then stayed stable found that the NO conversion of biocharZr/Mn declined from 86% to 60%
after 200 ◦C until 250 ◦C. The phenomena can be explained with the helpand recovered to 87% with the addition and stopping of H2O and SO2,
of an in-situ DRIFTS analysis. Both the Lewis and Brønsted acid sitesindicating the good renewable activity of biocharZr/Mn.
were found on the biocharZr/Mn catalysts. The amount of Brønsted acid
sites were more than that of Lewis acid sites but the Lewis acid sites had
3.3. Adsorption performance of Hg
better thermostability than the Brønsted acid sites which totally dis-
appeared at 250 ◦C. It appears that the Brønsted acid sites mainly Mercury has received increasing attention worldwide due to its
worked at the low and medium temperature (≤200 ◦C), while the Lewis toxicity, migration and accumulation in organisms. The United States
acid sites served as catalytic role in the entire studied temperature
issued the Clean Air Mercury Rule (CAMR) in 2005, which planned
reduce mercury emissions from 48 tons to 34 tons from 2010 to 2017
C. Wen et al.
and the mercury emission control rate of 70% was achieved in 2018.
Meanwhile, the emission standards of pollutants for stannum, antimony
and mercury Industries (GB/30770-2014) in China stipulated that the
emission limit of mercury in new enterprises should be 0.01 mg/m3. The
adsorption of Hg0 on biochar mainly follows: the Hg0 in combustion flue
gas firstly diffuses to exterior surface of biochar, which is called as
external mass transfer, the Hg0 then diffuses into micropores of biochar,
which is known as intraparticle diffusion, and the Hg0 is further oxidized
or reacted by the active sites onto the biochar. Both homogeneous and
heterogeneous oxidation may promote the retention of Hg in the bio-
char. Fuente-Cuesta et al. [101] reported that about 35–60% of gaseous
Hg was found to be the oxidized form in biochars, reflecting the
occurrence of heterogeneous oxidation. Table S3 of the Supplementary
Materials summarizes the preparation conditions of biochar, and the
typical adsorption conditions and optimum adsorption performance of
Hg by biochars.
3.3.1. Treatment conditions of biochar
The high carbonization temperature generally increased the micro-
pore volume and surface area of biochar, and the developed micro-
porosity could provide more physisorption sites for Hg0 capture [27,
61,102,103]. The atom radius of gaseous mercury is approximately 0.15
nm, the effective collisions between mercury and micropores less than 2
nm were expected to be conductive to the adsorption of Hg0 [30]. Shi
et al. [104] reported that the carbonization temperature between 400
and 600 ◦C mainly controlled the mesopore fabrication. At higher py-
rolysis temperatures of 500–700 ◦C, chemisorption began to dominate
the Hg0 removal instead of physisorption affected by BET surface area,
then the decrease of the organic functional groups (mainly C––O) [105,
106], the decomposition of C-halogen functional groups [105] and
sulfur species [107] at excessive high temperature would weaken the
chemisorption and removal performance for Hg0. Pyrolysis temperature
had impacts on the removal performance of Hg0 due to the influence in
the physicochemical properties of biocharFe/Cl [64], both C–Cl group
and iron oxides could supply the active sites useful for the removal of
Hg0 but decreased at high pyrolysis temperature of 800 ◦C. The related
reactions would be introduced in Section 3.3.3.
Shan et al. [108] reported that after microwave activation of biochar,
the Hg0 removal capacity was enhanced from 21.4% to 53.7%, as its
obvious advantageous for the development of the porosity and specific
surface area and the oxygenic functional groups. The Hg removal effi-
ciency of biochar by ultrasound treatment after NH4Cl loading was re-
ported to be 15–25% higher than that without ultrasound treatment
[109]. The ultrasound process is thought to increase the BET surface
area and improve Hg removal efficiency by enhancing the further
functionalization effect including the dispersion and penetration of the
NH4Cl [109] and dispersion active ingredients such as Mn and Fe [108],
Fe and Cu [43], and Mn and Ce [54].
Biochar was subjected to the modification of N2-plasma [110], the
adsorbed oxygen and water onto biochar can supply the oxygen source
for plasma modification to produce oxygenic functional groups, i.e. C–O,
C––O and O–C––O from water and C–O, C––O from oxygen (Equations
(28)
and Hand
2O (29)), thereby
treatments byassisting
dielectricwith the oxidation
barrier dischargeof Hg 0. Withhigher
plasma, the O2
contents of oxygenic functional groups (carbonyl and ester groups) were
obtained by increasing O2 and H2O concentrations to 50% and 9%
respectively, and increasing plasma treatment time up to 30 min, which
also resulted in an enhancement of Hg0 adsorption capacity [111],
although the pore volume and surface area of biochar decreased slightly.
The non-thermal plasma has characterized a promising application
prospect in modifying biochar to bring specific functional groups onto
the biochar, due to its high efficiency, simple operation and environ-
ment friendly.
Shi et al. [104] carried out the co-pyrolysis of rice straw together
with nanoscale CaCO3 template, the treatment clearly promoted the
specific surface area from 107.7 to 742.5 m2/g and successfully
fabricated a hierarchical porous structure of biochar with a balanced
distribution of micropores, mesopores, and macropores. The pores with
20 nm width derived from the 20 nm-CaCO3 nanoparticles serve as a
sacrificed template, and pores with 5 nm width were probably formed
via the activation of CO2 released with CaCO3 decomposition at high
pyrolysis temperature. The ratio of mesopores controlled by carbon-
ization temperature could be an important reason in the Hg0 removal
capacity of hierarchical biochar, as a stronger correlation of Hg0
removal capacity with the proportion of mesopores than that of micro-
pores. Large numbers of oxygenic functional groups (C––O and COO)
were also generated, and served as active sites and oxidized Hg0 into
HgO (Equations (30) and (31)). The Hg0 removal capacity by the hier-
archical biochar was 65% higher than that of raw biochar at 180 ◦C,
owing to their hierarchical porous properties and large numbers of
functional groups.
Xu et al. [112] prepared the biochar sorbents from biomass and PVC
under isothermal smoldering, this process presented the highest Cl
content and the highest Hg0 adsorption efficiency compared with the
isothermal heating and non-isothermal heating in N2 atmosphere, as
smoldering allowed the sufficient time of HCl released from PVC to
interact with cellulose in biomass to produce more C–Cl functional
groups which impacted significantly on Hg adsorption process.
Plasma
H* + O*̅̅̅̅→ OH* (28)
Plasma
C+ O*+ OH*̅̅̅̅→ COOH (29)
C= O+ e → C O
(30)
Hg0(ad) + O*(ad) →HgO(ad) (31)
3.3.2. Activization conditions of biochar
The biochar have a developed pore structure in the higher temper-
ature of 700–900 ◦C during activation in CO2 condition [30,104,113].
However, when the increased temperature surpasses a certain limit
(~800 ◦C), thermal annealing at high temperature leads to the walls of
the pores become thin and pore collapse, micropores tend to form large
pores as a result of CO2 over-etching [104], as well as the high ash
content of biochar offers a diffusion resistance and may sinter and block
pores, all of those result in the destructive pore structure and decreased
surface area [113]. Walnut shell biochars were prepared in pyrolysis
atmosphere of N2, O2/N2, and CO2/N2, respectively [114]. The results
indicated that the Hg0 adsorption capacity of biocharO2/N2 were worse
than that of biocharN2 whereas CO2 atmosphere greatly improved the
adsorption capacity. The activation reaction occurred between CO2 and
biochar resulted in the pore structure of biocharCO2/N2 better than that
of biocharN2, which was conductive to the diffusion and mass transfer of
Hg. As the increase in CO2 concentration, the pore volume and BET
specific surface area increased gradually, and more oxygenic functional
groups and organic Hg-OM species were generated (Equation (32)),
therefore the Hg adsorption capacity of biocharCO2/N2 presented an
overall increasing trend [114].
Steam activation was widely conducted to help the Hg0 adsorption of
biochar [109,115–120]. Shu et al. [37] suggested that the steam acti-
vation enhanced the surface area (414.9 m2/g) and micropore volume of
biochar apparently, resulting in better Hg adsorption characteristics.
H2O2 activation was also widely conducted [30,37,44,85]. The
oxidizing properties of H2O2 could cleanse the inner-pores of biochar,
thus helping expand the micropores. Meanwhile, the number of
oxygenic functional groups (mainly C–O, –OH) increased, which act as
possible chemisorption centers for Hg0 and facilitate the process of
electron transfer and the oxidization of Hg0 onto the biochar (Equations
(31) and (33)) [37,44]. These two reasons played important roles in the
higher Hg adsorption capacities of biocharH2O2 than biocharH2O [37].
Shen et al. [30] reported that the specific surface areas, micropore
C. Wen et al.
volumes and total pore volumes of biochar increased as the concentra-
tion of H2O2 increased from 10% to 30%. Yang et al. [44] reported that
biochar modified with 30% H2O2 exhibited good initial adsorption rate
and Hg0 capture ability of 90.86% at 120 ◦C (Table S3). Nevertheless,
Shu et al. [37] found a slightly ruined pore structure after 30% H2O2
modification, too higher concentration may arouse much powerful
oxidizing effect and make the collapsed inner pores and decreased
specific surface area [85], as well as may accelerate the esterification
reaction between –COOH and –OH, which eliminated the chemical
adsorption sites of Hg and resulted in a worse removal of Hg [37].
Recently, Liu et al. [121,122] developed an ultraviolet/H2O2 oxidation
modification technology on biochar from straw, corn stalk and seeweed.
They indicated that through producing abundant OH free radicals with
high activity, the UV/H2O2 modification could not only improve pore
structure of biochar, but also produce more oxygenic functional group
on the surface of biochar. The chemisorbed oxygen, C–O group [121],
C––O and COOH/COOC [122] showed crucial roles in promoting the
adsorption of Hg0. As a result, the Hg0 removal efficiency of bio-
charUV/H2O2 was improved from 48.41% to 91.34%, compared to the
biochar after microwave steam activation [122].
Hg0(ad) + C = O→Hg OM + C O (32)
COOH+ Hg0(ad) → COOHg + H*
3.3.3. Impacts of functionalization
3.3.3.1. Halogen and sulfur. It is well known that mercury species may
react with halogen (Cl, Br, I) and sulfur, the presence of these relevant
elements in biochars make them good potential sorbents for mercury
species (Fig. 5). HCl impregnation with biochar was conducted by au-
thors [102,120,123,124]. HCl modification reduced the ash in biochars
significantly [120] and created the increased surface area from 29.9 to
110.1 m2/g, these formed micropores effectively capable of adsorbing
the Cl atoms onto the internal surface of biochar [124], besides, new
formed sites (C–O, C––O, O–H, C–Cl) during HCl impregnation acted as
chemisorption sites, both of which caused a marked improvement in Hg0
adsorption performance [123,124]. The other halogen acid, HBr was
impregnated on rice husk biochar, the enrichment of the brominated
functionalities played the dominant role in its improved Hg adsorption
capacity [125].
Fig. 5. The halogen and sulfur functionalization on
biochar for adsorption and reaction of Hg0. Route 1:
The C-X groups in biochar convert Hg0 into HgX2 or
other Hg-X complexes (Equation (6)). Route 2: The
oxygenic functional groups (mainly C–O, –OH) act as
chemisorption centers for Hg0 and facilitate the oxi-
dization of Hg0 onto the biochar to form HgO, Hg-
OM, and -COOHg (Equations (31)–(33)). Route 3:
The sulfur-containing groups (C–S) on biochar react
with Hg0 to form HgS (Equation (39)).
The ammonia halides (NH4Cl, NH4Br, NH4I) were also widely used to
modify the biochar. The halides majorly absorbed on the micropore
religion, leading to the partly blockage of inner pore structure and the
reduced micropore volume and surface area [126]. The Hg0 removal
capacity enhanced as the increase of NH4Cl loading, owing to more
chemisorption sites were introduced by the higher impregnation amount
on the surface of biochar [127]. The chemisorption process of Hg0 was
that the C–Cl groups formed in biochar during NH4Cl impregnation
acted as activated sites, which can convert Hg0 into HgCl2 or other
Hg–Cl complexes (Equations (6) and (34)) [60,61]. The optimum NH4Cl
loading was reported to be about 5% [109], and the Hg removal effi-
ciency no longer increased [127,128] or even decreased for NH4Cl
loadings >7% [109], might be ascribed to the biochar surface saturation
causing pore destruction and diminution of surface area. Similarly, an
increase in loading value of NH4Br reported by Yang et al. [103] would
generate more chemisorption sites, the removal efficiency of Hg
increased from 78.13% to 98.07% at 120 ◦C (Table S3). C–Br and C––O
groups served as the chemisorption sites, they can participate in the
reactions to result in the removal of Hg (Equations (6), (30) and (31)).
Besides, Zhu et al. [99] observed the Hg removal efficiencies of modified
biochars increased in the following sequence: HBr (pH: ~0.7) > NH4Br
(pH: ~5.0) >solutions
impregnation CaBr2 (pH: 6–8). On
increased, the one hand, functional
oxygenic as the pHgroups
valueslike
of
lactone and carbonyl as the active(33)
sites might be destroyed, on the other
hand, the protonation effect was enhanced with the pH value decreased,
leading to the accumulation of positive charge on biochar surface and
subsequently promoting the electrostatic attraction between Hg0 and
bromide ions. Zeng et al. [118] reported that the impregnation of iodine
could be beneficial to the formation of chemisorption sites and favored
the Hg adsorption, while 3% NH4I addition can generate almost the
same amount of adsorption sites and similar Hg0 removal ability as 5%
NH4I, as the above-mentioned effects caused by too much halogen
impregnation contents [126]. The main mechanisms of ammonia ha-
lides modification on Hg removal refer to that the impregnated halogen
ion reacts with carbon atom onto the biochar to produce the C-halogen
groups, while the O2 in flue gas is adsorbed onto biochar to generate the
chemisorbed oxygen and/or weakly bonded oxygen species (O*). Both
of which are the dominant chemisorption sites and positively influence
in the removal process of Hg0. The former oxidizes mercury to form
mercury halides (Equation (6)) [126], while the latter reacts to form
C–O groups and HgO (Equations (30) and (31)). C––O groups generally
C. Wen et al.
serve as electron acceptors and facilitate the electron transfer for the
oxidation of Hg0 during this process [61,123].
Both the two types of modifying agents, i.e., ammonia halides and
potassium halides, followed the same sequence of Hg removal effi-
ciencies: biochar < biocharNH4Cl < biocharNH4Br < biocharNH4I [117,
118] and biochar < biocharKCl < biocharKBr < biocharKI [117,126,129].
The amounts of C-halogen groups dominantly decide the effects of
halide modification on Hg removal capacity as they mainly react with
the Hg0 to produce mercury halides. It is noteworthy that the production
of C-halogen groups depends upon both the reducibility and the size of
halide ions [129]. The reducibility of halide ion presents the sequence of
I > Br > Cl , the iodine ion is thus readily to donate electron and in-
teracts with carbon atom to generate covalent bonds that serve as major
chemisorption sites [118]. Meanwhile, the higher size of halide ion
possibly has higher surface exposure and provides more probability to
interact with carbon atom and produce covalent bonds as the higher
London dispersion forces [118,129], resulting in stronger ability to form
chemisorption sites [126], thereby the Hg removal efficiency of biocharI
is usually the highest as its highest ionic radius of 2.20 Å, compared with
Br with 1.96 Å and Cl with 1.81 Å, respectively [117]. Besides, the
halogenated activated carbon models were adopted using DFT method
to find that the halide type has no significant impact on the adsorption
energy of Hg, but has a greater effect on the activation energy barrier of
HgX (X = Cl, Br, I) formation in the order of HgI < HgBr < HgCl [130].
The modification effects of ammonium halides were generally better
than that of potassium halides in the Hg removal efficiency [129]. On
one hand, with the example of iodine, the finer size of NH4I (4.8 Å)
compared to KI (6.7 Å) possibly resulted in less blockage of porous
structure and easier access of Hg to active sites [117]. On the other hand,
the amino groups adsorbed onto the biochar would further react with
halide ion to form the C–NH2-halogen groups (Equation (35)) [123,
129], which was also beneficial to form more chemisorption sites than
potassium halide. Shen et al. [123] compared three types of Cl
impregnation and found that Hg adsorption efficiency by biocharNH4Cl
was much better than those by biocharHCl and biocharZnCl2. The superior
performance of NH4Cl to ZnCl2 was also attributed to the
above-mentioned finer size of NH4Cl and the presence of amino groups.
Meanwhile, the hydrogen bonding and hydroxyl caused by HCl
impregnation had positive impacts on the adsorption of Hg0, causing a
better capacity than biocharZnCl2 which had a poor pore structure. Yet,
the biocharZnCl2 still presented higher Hg adsorption capacity than
biocharH2O2 [37], which was attributed to the chloride surface com-
plexes as possible Hg0 active sites although blockage of some inner pores
happened. Cl would interact with carbon in biochar to generate lots of
[Cl–C–Cl]2- groups onto the biochar (Equation (36)), these groups can
provide more active sites to promote chemisorption of Hg0.
The non-thermal plasma is able to promote the porosity and boost
the active functional groups onto the biochar, therefore was considered
to activate biochar for Hg0 removal [45]. The energetic electrons and
active free radicals formed in the 1% Cl2 plasma system led to a porous
surface properties of biochar [45,131]. The chlorine molecules collided
with active electrons to generate Cl active radicals (Cl*), and then
contacted on the biochar surface to produce more C–Cl groups (Equa-
tions (5) and (37)), which promoted chemisorption and enhance the Hg0
capture efficiency from 8.2% to 84.2%, up to 583.0 μg/g for tobacco
biochar (Table S3) [45]. HCl non-thermal plasma was also utilized to
bring in Cl active sites [63], the active free radicals produced by the
discharge cycle bombarded and reacted with the surface of biochar,
leading to the collapsed pore walls and blocked pore entrance, mean-
while, HCl plasma modification promoted Cl-containing active sites
successfully onto the biochar and significantly performed four times
higher Hg removal capacity than HCl modification [63]. The Cl active
sites could react with Hg0 heterogeneously via electron-transfer process
and generated Hg2Cl2 compounds (Equation (38)). Cl appears to react
preferentially with Hg than O and S, as the introduction of HCl plasma
inhibited the production of HgO and HgS.
The biochar price for Hg adsorption can be further reduced if the
sources of carbon and halogen are obtained cheaply and with an
affordable synthesis routine. The polyvinyl chloride (PVC) with over 50
wt% Cl was able to co-pyrolyze with biomass wastes to generate the Cl-
rich biochars [64,112], the C–Cl groups were successfully introduced
and performed the beneficial adsorption of Hg0, although the
co-synthesis dropped the specific surface area of biochar [64,65]. The
chemisorption was enhanced greatly and the Hg0 adsorption efficiency
reached about 82% at 140 ◦C (Table S3) [64]. PVC was also used to
prepare the hierarchically biochar with CaCO3 as template [65], the
H–Cl group released from PVC reacted with C––C groups to generate
C–Cl groups, the high removal efficiency of 90% at 120 ◦C shown in
Table S3 was thus ascribed to the synergistic effects of the
well-developed hierarchically pores (554.9 m2/g) especially mesopores
and high Cl active sites which were beneficial to rapid Hg0 trans-
portation. In this study, the DFT surface model was established to
simulate the reaction process of Hg0 on biochar (Fig. 6), in which the
biocharCl doped with di-chlorine was obtained to build the active sites of
C–Cl bond and the adsorption energy was calculated. The results pre-
sented that the loading of dichloride atoms and carbonyl groups on
biochar model enlarged adsorption energy, and would directly facilitate
the adsorption process of Hg0 [65]. Similarly, the waste brominated
flame retarded plastic (BFR) was utilized to produce the Br-rich biochar
[105]. Br was doped into the biochars as Br and C–Br groups, therefore
the biocharBr presented much better Hg0 removal efficiency than raw
biochar. It can be found that the C––O groups participated in Hg0 cap-
ture reaction only until C–Br bonds were exhausted as the higher reac-
tivity of C–Br bonds. It was also noteworthy that the excessive ratio of
biochar/BFR plastic to 1:2 was adverse to Hg0 removal, as the pore
structure of biochar was deteriorated caused by the aggregation of
melted plastic residues.
The introduction of sulfur-containing functional groups can also
effectively promote the Hg removal performance of biochar. The rice
husk was physically mixed with elemental sulfur and carbonized to
generate biochar [116]. The sulfur can dope into the biochar via
monolayer surface deposition or volume pore filling, and reduced both
the pore volume and surface area, especially for the low carbonization
temperature of 300 ◦C, at which the lacking microporous structure was
entirely blocked by the overloaded sulfur molecules, thus dramatically
reducing the adsorption capacity of Hg. At the higher carbonization
temperature, there are abundant micropores to adsorb the sulfur mole-
cules, forming the organic sulfur such as sulfone and sulfoxide. The
doped sulfur, including the retained elemental sulfur and formed
organic sulfur, can play as new adsorption sites for the removal of Hg0
mainly via chemisorption to generate S–Hg–S and S–Hg–O bonds,
resulting in a removal performance of 344.3 μg/g at 150 ◦C (Table S3).
Zhang et al. [132] carried out a H2S plasma modification, the amount of
sulfur-containing groups (C–S) and carboxyl groups on biochar
increased, which mainly formed HgS and HgO to retain the Hg removal
efficiency of 95.5% at 30 ◦C shown in Table S3 (Equation (39)). Li et al.
rolysis which could
[60] presented that work as chemisorption
the waste tire generatedsites and (ZnS)
sulfide oxidizeduring
Hg0 into
py-
stable HgS on biochartire, however, the further process of microwave
activation or chemical modification of NH4Cl to the biochar possibly
removed or covered inherent sulfide active sites, unfavorably inhabited
the Hg capture of biochartire. Furthermore, the pyrolysis of medical
residue generated sulfate, which is not useful to the adsorption of Hg.
Sulfurized biochar from co-pyrolysis of scrap tire and wood was pre-
pared as economical sorbents [107]. The occurrence forms of sulfur in
the biochar were organic sulfur (aliphatic sulfur, sulfoxide), sulfide,
elemental sulfur and sulfate. The biochar with the largest amounts of
elemental sulfur and organic sulfur showed the optimal Hg0 capture
capacity, strengthened by the higher ratio of tire and higher pyrolysis
temperature. Both of the organic sulfur and elemental sulfur act as active
sites for the removal of Hg0 and then are transformed into HgS (Equa-
tions (39)–(41)) [133], as shown in Fig. 5. From DFT calculations, Liu
C. Wen et al.

Fig. 6. The typical configuration of Hg0 adsorption on biochar using DFT model, including (a) model of biochar, (b) chlorinated Cl-biochar model, (c) C––O/

biochar

model
et al. and (d) found
[134] C––O/Cl-biochar model. Reprinted
that the adsorption energyfrom
of Ref. [65] with
S-doped permission
carbon for of Elsevier.
performance of tobacco biochar with high ash content. Some metal el-
mercury was 51.76 kJ/mol, the value belongs to chemisorption and ements, such as Fe, Cu, Mn, Ce, and Zr, were purposely loaded into
implies that the doping of sulfur enhanced the electron transfer from Hg0 biochar for improving the Hg removal capacity of biochar.
to the sulfur atom that bonded in carbon (Equation (39)). Biochar was prepared as Fe-based or Fe–Ce based composite with
doped metals of Co, Mn or Cu by the sol-gel and the coprecipitation
methods [55]. The pore structure of biochar was apparently promoted
Hg0(ad) + C X (ad) →C Hg X (ad) (X= Cl, Br, I) by the low contents of metal oxides while
(34)higher contents (~2–3 wt%)
would
the agglomerate
case and block
for NOx removal part ofinpores
mentioned [43,55],
Section which2 was
3.2.2. CeO is similar as
observed
NH4X+ R C→R C NH2 X
(35) and could achieve a synergistic
to have strong oxygen storage capacity
effect with other doped oxides, making the distribution of CeO2 on
2X + C→[X 2ClC* X]2
Cl2 (g)̅̅̅̅→ (36) especially with Cu or Mn and reducing
biochar surface more dispersedly
Plasma the crystallinity of the active component CeO2, which reflected high
oxidizability generating more oxygen vacancies on the biochar support.
(g)
(37)
However, too higher loading amount of Ce would agglomerate and
crystallize the active metals, also limiting the improvement in the Hg
2Hg0(ad) + 2C X→Hg2X2 (ad)
metal ion follows the sequence: Cu2+＜
removal. As the oxidizability of(38)
Co3+＜Fe3+＜Mn4+＜Ce4+, the loss of oxygen from the Cu or Co oxides
Hg0(ad) + C S→HgS(ad) + C could be replenished by the lattice oxygen in Fe2O3, while the lattice
(39)

SO2 + S2 →S0 + O2
(40)

Hg0(ad) + S0→HgS(ad)
(41) oxygen in CeO2 is able to supplement the lost oxygen in Fe2O3 and MnO2

3.3.3.2. Metal modification. The mineral components as a medium during the bimetal redox reactions (Equations (15) and (16)). The
consumption of lattice oxygen promoted the introduction and con-
Hg capture or as a catalyst in the adsorption process also need to be
struction of oxygen vacancies, the Hg0 adsorbed onto the biochar can be
considered. Fuente-Cuesta et al. [101] mixed the fly ash and biochar
oxidized by both the lattice oxygen and chemisorbed oxygen replen-
find that the Hg retention capacity of biochar was not apparently
ished by the gaseous O2 to produce HgO (Equation (31)), and then the
influenced by the fly ash particles presented in simulated flue gas, but
reduced metals were re-oxidized by other metal oxides. The existence of
the heterogeneous oxidation was promoted obviously. Wang et al. [45
chemisorbed oxygen and its mobility and reactivity are related to the
reported that the minerals in the ash, such as Ca and Fe, can act
vacancies, charge imbalance and chemical bonds formed by the metal
catalysts to improve the oxidation of Hg0 to form HgO, helping the good
oxides [96]. This Hg0 removal mechanisms indicating that the adsorbed
Hg combines with the chemisorb oxygen or the lattice oxygen were
C. Wen et al.
described as the Langmuir-Hinshelwood (L-H) mechanism and the
Mars-Maessen mechanism, respectively [23,135].
The calcination temperature significantly affected the formation of
metal oxide components and crystalline phases onto the biochar. During
the preparation of biocharFe/Cu, Cu2O with low catalytic oxidation ac-
tivity or Fe3C with reduced active components was formed at 300 ◦C and
700 ◦C, respectively, 500 ◦C was thus the optimal calcination tempera-
ture to exhibit a high Hg0 removal efficiency of biocharFe/Cu [43]. The
Cu/Fe oxides with Cu molar ratio of 0.3 showed a good dispersion and a
strong interaction, producing more active sites and thus receiving the
Hg0 removal of 90.58% at 130 ◦C (Table S3). The excessive loading
value of Cu/Fe oxides, e.g., 15 wt%, would lead to the blockage of the
partial pore structure and reduce the physisorption performance of Hg,
further inhibited the oxidation or chemisorption process and was not
conducive to Hg0 removal any more. Shan et al. [108] showed that as the
loading amount of Mn/Fe bimetal oxides increased from 1% to 7%, the
surface area and pore volume of biocharMn/Fe increased first and then
decreased, with the maximum value at 4% loading. The well dispersed
active ingredients of Mn and Fe were largely consumed to receive a Hg0
removal capacity of 531.9 μg/g at 120 ◦C (Table S3), accompanied by
the considerable proportion of Mn4+ converted into Mn3+ and Mn2+ and
some Fe3+ reduced to Fe2+. Therefore, the adsorbed Hg0 was oxidized
into HgO or Hg2+ by chemisorbed oxygen, Fe3+ and Mn4+ (Equations
(31), (42)–(44)). The mechanochemical process of ball-milling was
applied to synthesize the composites of metal oxides and biochar, the
metal composites of Fe and Mn was reported to effectively increase the
oxygenic functional groups on biochar as it alleviated undesired func-
tional groups blockage by free metal ions which often found during
conventional wet impregnation, therefore, it is a more favorable method
than wet impregnation to receive the Hg0 removal of ~92% at 150 ◦C
[11]. The FeCl3 modified biochar was doped with Cu or Mn by Zhao
et al. [136]. The biocharFe/Cu had the stronger Hg adsorption capacity
than biocharFe/Mn due to Fe2O3 and CuO presented a synergistic effect.
C––O and –COOH, chemisorbed oxygen, lattice oxygen, metal oxides
and ions, and Cl ions were all effective active sites for the adsorption of
Hg0 assisted by heterogeneous oxidation. A part of Hg0 complexed with
C––O and –COOH to generate Hg-OM and -COOHg (Equations (32) and
(33)), the other part adsorbed on the vacancies of metal cations would
combine with the lattice oxygen in metal oxides to generate HgO. The
high-valent Mn ions from KMnO4 were observed to compete with Fe2O3
to adsorb and oxidize Hg0, failing to present a synergy between Mn and
Fe in this case, due to little cation vacancies and unsaturated chemical
bonds capable of the redox reaction were formed [136].
CeO2 promoted the regeneration of the active ingredient MnO2 due
to the redox cycle occurred to produce new oxygen vacancies, the bio-
char with the Mn/Ce molar ratio of 2:1 presented the Hg capture ca-
pacity of 83.6% at 150 ◦C (Table S3) [54]. However, excessive Mn would
result in the decrease in redox activity and a noticeable decline of sur-
face area, would further leading to the reduction of active adsorption
and oxidation sites, and thereby inhibited the removal of Hg. Zeng et al.
[118] studied the biocharMn/Zr and found that the doping of ZrO2 did not
participate in the capture process of Hg0 directly, but could help to
improve the dispersity of MnOx and inhibit the pores blockage raised by
NH4I modification, thereby could benefit the formation of high
oxidation-state Mn. The Hg0 adsorption capacity of biocharMn/Zr after
1440 min was up to 5587.0 μg/g at 150 ◦C and the Hg0 oxidation ratio
was higher than 30% after reaching adsorption equilibrium. The
chemisorption sites of C–I groups dominated the removal of Hg0 at the
initial reaction stage. As reaction progressed, chemisorption was
weakened owing to the gradual depletion of adsorption sites, never-
theless catalytic oxidation affected by hydroxyl oxygen and lattice ox-
ygen substituted chemisorption and dominated the capture of Hg0 at the
latter reaction step. O2 in the combustion flue gas replenished the hy-
droxyl oxygen and lattice oxygen to maintain the continuous oxidation
process. Tang et al. [128] also found that ZrO2 did not take part in Hg0
oxidation directly and rendered the well dispersed active components of
Cu. The superior performance of biocharCu/Zr of 98.87% at 120 ◦C shown
in Table S3 might be attributed to the low crystallinity, strong redox
ability of Cu and good porous properties. Li et al. [137] studied a
Co-enriched biochar for sufficiently and properly utilizing the Siberian
Iris. The cobalt species in the biochar existing mainly as cobalt oxides
were non-crystal and highly dispersed, which was benefit to the
Co3+/Co2+ redox cycle and could produce active oxygen species with
the assistance of gaseous O2 to receive the Hg removal efficiency of
70.5% at 150 ◦C. Liu et al. [138] tried the eutectic salt (K2CO3+Li2CO3)
synthesis and CuS-doping to produce biochar from rice straw, its
maximum accumulative mercury adsorption capacity were 838 μg/g
over 600 min at 100 ◦C. Cu2+ and S2 both acted as the adsorption sites
and the Mars-Maessen mechanism was identified: Cu2+ ions oxidize the
Hgad0 into Hgad2+ species and then react with S2 to form HgS, accompa-
nied by the formation of Cu + species from Cu2+.
For better separating the spent halogen-modified biochars from fly
ash, one-step pyrolysis of sawdust and FeCl3 was carried out by Yang
et al. [106] and one-step pyrolysis of PVC and Fe(NO3)3-laden wood was
carried out by Xu et al. [64] and Fe(NO3)3 with waste tea by Altaf et al.
[119] to synthesize the biocharFe/Cl. The catalysis of Fe promoted the
release of volatile matters during co-pyrolysis, and then developed the
porous texture and enhance the specific surface area [64,119]. The
biocharFe/Cl presented much higher Hg0 removal capacity compared
with the biocharCl over a wide range of adsorption temperature up to
250 ◦C, as the chemisorption/oxidation of Hg0 played the more impor-
tant roles to attain a removal capacity of 953 μg/g at 120 ◦C (Table S3)
[106]. On one hand, the C–Cl group was generated after Fe activation
with PVC [64] and more oxygenic functional groups especially the C––O
group were produced with the activation of FeCl3. On the other hand,
Fe3O4 should also be helpful to the removal of Hg0, Fe3+(t) coordination
in Fe3O4 could work as the active sites for the adsorption and oxidation
of Hg0, leading to the production of iron amalgamation, Fe3+ converted
into Fe2+ (Equation (45)) and lattice oxygen which assisted the
adsorption of Hg0 to form HgO [64,106]. Yang et al. [106] found that
the role of Cl in the removal of Hg0 was not apparent due to the Cl in
biocharFe/Cl existed as FeCl2 rather than the effective FeCl3. The Hg0
removal efficiencies were apparently promoted with the increase of Fe
loading ratio, however, the excessive Fe loading may inhibit the
dispersion of Fe3O4 and result in the reduction of pore volume and
physisorption of Hg0, therefore, was not beneficial to the Hg0 removal
[64,106,119].
The DFT method can reveal the molecular structure and the mech-
anism of Hg adsorption on the metal-modified carbon materials more
clearly. Li et al. [139] revealed that the presence of oxygen in the carbon
skeleton can tune the electrons of small-sized Mn clusters, enhancing the
affinity of mercury atoms and lowering the free energy of mercury
adsorption. Zhang et al. [140] found that the mercury adsorption
strength of metal-modified carbon materials was in the order of Ni > Cu
> Zn, by comparing the adsorption energy, adsorption distance, and
various electronic properties. Qin et al. [141] studied the adsorption
reaction of Hg0 on iron-based modified biochar at different chemisorp-
tion sites (oxygen vacancy with electrons) and oxidation sites (mainly
Fe3+, lattice oxygen and chemisorbed oxygen), and found the coupling
between them formed Hg–O–Fe-Ox-1 and the complex Hg-OM. In gen-
eral, the metal functionalization on biochar for adsorption, catalysis,
and reaction of Hg can be observed in Fig. 4.
Mars-Maessen mechanism:
2Mn4+ + Hg0(ad) →2Mn3+ + Hg2+( ad) (42)
Mn4+ + Hg0(ad) →Mn2+ + Hg2(ad+) (43)
2Fe3+ + Hg0(ad) → 2Fe2+ + Hg2(ad+) (44)
Fe3O4 → 3FeO + [O] (45)
C. Wen et al.
3.3.4. Adsorption conditions
3.3.4.1. Temperature. A lot of research studied the Hg0 removal ca-
pacity of biochar under the similar temperature range as upstream of the
dust removal device between 80 ◦C and 200 ◦C and observed the in-
fluence of adsorption reaction temperature in the Hg0 removal [44,65,
85,87]. The biocharH2O2 had poor ability of 83.42% at 80 ◦C and the
better performance of 90.86% at 120 ◦C [44], while the Hg0 uptakes
decreased at higher temperature than 140 ◦C. The similar work on
biocharH2O2 showed the best removal of 78.99% at 130 ◦C between 70
◦C and 160 ◦C (Table S3) [85]. The Hg0 removal performance from hi-
erarchically biochar by CaCO3 template also had the optimum temper-
ature of 120 ◦C between 80 ◦C and 160 ◦C [65]. The physisorption is an
exothermal process, along with the rising temperature, the molecular
kinetic energy and the vibration increase, enhancing the amount of
activated molecules and the collision probability of each other, and
leading to more valid active sites capable of enhancing chemical reac-
tion for Hg0 removal. However, excessive temperature could result in
the weaken of adsorption power, the suppression of physisorption pro-
cess and even re-release of Hg0 on the surface of biochar [13], which
might inhibit the efficiency of Hg removal.
When the reaction temperature enhanced form 80 ◦C–160 ◦C, the Hg
capture efficiencies increased from 81.16% to 93.96% for biocharNH4Br
[103] and from 73.4% to 95.7% for biocharKI (Table S3) [126]. Mass
transfer was the main controlling factor on Hg0 adsorption at 80 ◦C,
while the reaction at higher temperature was mainly controlled by the
chemisorption based on the kinetic simulation. The biocharMn/Zr loaded
with NH4I also presented an increased capacity from 50 ◦C to 250 ◦C
[118]. They reported that the enhancement of Hg0 removal for halogen
activated biochar may be relevant to the elevation of the chemical re-
action between the increased chemically active sites and Hg0 [103,117,
126]. Li et al. [61] observed that the highest Hg0 removal efficiency of
biocharNH4Cl from municipal waste reached 97.3% at 80 ◦C and
decreased to 50.7% at 180 ◦C. They also found the biocharNH4Cl from
medicinal residues had a best Hg0 removal efficiency of 95% at 50 ◦C but
only 62% at 180 ◦C [127]. They explained the chemisorption caused by
Hg reaction with chloride functional groups displayed exothermic
behavior indicated by the negative enthalpy change, higher temperature
thus inhibited chemisorption and Hg would be desorbed. The bromi-
nated biochar, the biochar from co-pyrolysis of wood and PVC and the
biochar from one-step co-pyrolysis of S-containing scrap tire and wood
all showed the optimum temperature of 140 ◦C between 25 ◦C and 220
◦C [105,107,112]. The phenomena were attributed to the
above-mentioned reasons [105]: reactants could acquire more kinetic
energy at high temperature, but too high temperature would restrict the
Hg0 physisorption and cause Hg0 desorption which was confirmed by
Hg-TPD analysis. Zhang et al. [132] found that the amount of
sulfur-containing groups (C–S) and carboxyl groups formed by the H2S
plasma modification helped to retain Hg at 30 ◦C, however, the C–S
bonds were easily broken to release the active S and form the sulfate at
high adsorption temperature of 150 ◦C, which was likely to block the
pore structures of biochar and further inhibited the adsorption of Hg. As
a result, the Hg removal efficiency of wheat straw biochar decreased
apparently from 95.5% at 30 ◦C to 60.8% at 150 ◦C (Table S3).
Biochar loaded with FeCl3 presented excellent Hg0 removal perfor-
mance of ~95% at 120–180 ◦C, and biochar loaded with Fe(NO3)3
presented a significant Hg0 removal of 94.81% at 180 ◦C between 30 ◦C
and 300 ◦C [119], while biochar loaded with Fe(NO3)3 and PVC pre-
sented the optimum Hg0 removal performance of ~80% at 140 ◦C be-
tween 25 ◦C and 220 ◦C [64]. The biocharMn/Fe presented the optimum
Hg0 removal performance at 120 ◦C between 80 ◦C and 140 ◦C [108],
the biocharMn/Ce presented the optimum Hg0 removal performance at
150 ◦C between 130 ◦C and 170 ◦C [54], the biocharCu/Zr loaded with
NH4Cl presented the optimum Hg0 removal performance of 98.87% at
120 ◦C between 30 ◦C and 270 ◦C [128], and the biocharFe/Cu had
optimum temperature of 200 ◦C in the range of 50–350 ◦C [136]. Zhao
et al. [136] observed that at 50 ◦C, the pore texture of biochar was not
destroyed obviously and only the adsorbed mercury species blocked
some narrow pores. At the higher temperature of 200 ◦C, abundant
mercury species were adsorbed meanwhile the thinner pore wall of
biochar was destroyed to cause blockage of the micropores and deple-
tion of the physisorption region. At the highest 350 ◦C, the loaded active
metals onto the biochar were melted and fell, resulting in the depletion
of active centers and worse adsorption capacity of Hg. Furthermore, it
appears that as the reaction temperature raised till to 350 ◦C, the
oxidation capacity was improved due to the reactants could gain more
kinetic energy, accelerating the oxidation reaction of Hg0 [106,118,
119]. However, the reaction temperature higher than 200 ◦C might
reduce the physisorption, as well as HgO and HgCl2 may undergo
decomposition and desorption caused by the catalysis of metal species
[136], which would suppress the Hg0 adsorption capacity at high
temperature.
3.3.4.2. Flue gas. As the combustion flue gas is cooled gradually, ho-
mogenous reactions between Hg and other gas components and het-
erogeneous interactions of Hg with fly ash particles and biochar
adsorbents may happen, the interactions of biochar with the gases via
adsorption and homogenous/heterogeneous oxidation affect the mer-
cury speciation and retention. Therefore, the impacts of combustion
atmospheres such as flue gas components (SO2, NOx, HCl) and fly ash
particles on homogeneous and heterogeneous reactions and on Hg
removal efficiency of biochar should be assessed. The Hg0 removal ef-
ficiency of biochar was generally higher in simulated coal-fired flue gas
than in N2 atmosphere [101]. This might be relevant to acidic gases, e.g.,
low concentration of SO2, NO, and HCl, promoting the oxidation of Hg0
[105,109].
An unusual result of SO2 on Hg0 removal was observed, i.e., low
concentration of SO2 facilitated the removal of Hg0 apparently whereas
high concentration of SO2 (＞~700 ppm) inhibited Hg0 capture [127].
As discussed in Section 3.1, part of SO2 adsorbed on biochar is oxidized
into SO3 and then reacted with H2O to form H2SO4, both the SO3 and
H2SO4 can react with Hg0 to generate HgSO4 in the oxygen containing
atmosphere (Equations (46) and (47)), thus enhancing the Hg0 retention
and removal efficiency [54,109]. However, when the SO2 concentration
increased, the competition adsorption of the SO2 and Hg0 happened [85,
103,128] and the excessive SO2 was more competitive than Hg0 in the
adsorption onto the biochar as its much higher concentration in flue gas
[126]. The existence of SO2 led to the conversion of active Co3+ to Co2+,
which bonded with SO42 and thus decomposed difficultly at adsorption
temperatures (Equation (48)). As a result, SO2 would not only compete
with Hg0 for the lattice oxygen to form sulfate species but also react with
some metal oxides (such as Mn, Ce) onto the biochar to generate ther-
mally stable metal sulfates (Equations (49) and (50)) [54,112], both
covering the active sites, causing the deactivation and poisoning of
biochar, and destructing the Hg0 removal [43,108]. The experiment
from Li et al. [137] emphasized that the metal sulfates poisoning was the
predominant reason compared with the competitive adsorption between
Hg0 and SO2. The occurrence of Fe could promote the sulfur poisoning
resistance of biochar in 1200 ppm SO2, likely owing to the chemical
reaction of iron oxides and SO2 [64], the biochar generated from
co-pyrolysis of S-containing scrap tire and wood also presented an
excellent poisoning resistance in 1200 ppm SO2 [107], as SO2 adsorbed
onto the biochar should react with sulfide to produce elemental sulfur
which still provides active sites for Hg0 capture.
The existence of O2 and NO generally improved Hg0 removal. The
promoted Hg adsorption by O2 should be attributed to the oxidized
mercury which can be readily adsorbed compared to the gaseous mer-
cury. However, the further increase of O2 concentration to about 10%
had little impact on Hg0 removal performance [107]. More importantly,
the gas phase O2 could replenish the chemisorbed oxygen and
C. Wen et al.

reestablish the lattice oxygen of metal oxides effectively on metalwhich easily caused the deactivation of biochar, thereby further
functionalized biochar [126], increased the Hg0 removal efficiency inhibited the removal of Hg0 [43]. Besides, the promoted Hg removal
facilitating electron transfer and Hg0 oxidation [43,54,85,103,104,108efficiency by SO2 or NO was reported to be restrained by the addition of
112]. For biocharNH4Cl loaded with Cu and Zr, the removal efficiency 3% H2O [127].
advanced little when the O2 content enhanced from 3% to 12% at 120 ◦ A very small number of 15 ppm SO3 was reported to lead to a
and enhanced slightly at 240 ◦C [128]. The removal of Hg0 was mainlyrestricted Hg0 removal effect over biochar [142]. SO3 presented stronger
determined by adsorption at low temperature of 120 ◦C, and 3% O2 was affinity with biochar than Hg0, strengthening the competitive adsorp-
sufficient to the slight catalytic oxidation. Whereas, catalytic oxidation tion between Hg0 and SO3. Furthermore, the metal sulfates were
turned to important at high temperature of 240 ◦C [128] and high generated to seal up the active sites especially in the presence of H2O.
content introduction of metal oxides [118], much contents of latticeThe deposition of H2SO4 and HgSO4 on the biochar further suppressed
oxygen formed in the metal redox reactions can be replenished by the the Hg0 removal. Whereas, as the concentration of SO3 enhanced to 200
high concentration of O2, thus facilitating the oxidation and removal ppm, the oxidation performance of Hg0 enhanced, owing to SO3 assisted
Hg0. the formation of C––O groups and had no obvious damage on the C–Cl
As discussed in Section 3.2, the biochar could be a catalyst for thegroups, both of which played as effective active sites for the removal of
oxidation of NO with chemically adsorbed oxygen to produce new activeHg0 [142].
components such as NO+ and NO2 in the presence of O2. Although NH3 was reported to negatively affect Hg0 removal [98], it presented
gaseous NO is difficult to react with Hg0 homogeneously, the NO2 hasprohibitive influence in adsorption and oxidation of Hg0 for bio-
higher reactivity for the adsorbed Hg0 [43,103,127,137]. The producedcharCu/Zr, which was mainly ascribed to, on one hand, the competitive
NO2 reacted with Hg0 to form Hg(NO3)2 on the biochar (Equations (51) adsorption between NH3 and Hg0, on the other hand, NH3 generated
and (52)) [64,107,109], meanwhile the produced NO2 could also reactadsorbed species such as NH4+ and NH3 that occupied the active sites and
with Hg0 to generate HgO (Equations (53) and (54)) [54,108,127,137 consumed surface active oxygen, which limited to the oxidation of Hg0
helping with the oxidation removal of Hg0. The presence of O2 [128]. However, the adsorbed NH3 promoted the Hg removal process of
necessary as the active N-containing species derived from the reaction Cl plasma modified biochar [131]. NH3 turned Cl to active Cl * which
limited active oxygen and NO should be gradually exhausted by Hg0 assembled with C to generate C–Cl group. As both NH3 and NO existed in
O2 was cut off [137]. However, excessive NO (~400–800 ppm [126 flue gas, the Hg removal capacity was lower than the case that the two
was also reported to cover the active sites and consume surface oxygensgases presented alone, owing to NO would be depleted with NH3 to
on biochar, suppressing the adsorption performance of Hg0. Li et generate N2 and H2O (Equation (14)). When the NH3 and SO2 were
[127] reported that 100 ppm SO2 had a greater influence in Hg0 captureco-existed, SO2 inhibited Hg removal through competitive adsorption,
than 100 ppm NO. In the co-presence of SO2 and NO, SO2 consumedthe formed sulfates and sulfites were more likely to block the biochar
active oxygen and generated sulfates, leading to irreversible damage pores and occupied the active site (Equation (59)), thus deteriorating the
active sites on the biochar, therefore, the activation of NO and theefficiency of Hg removal [131].
following reaction between Hg0 and NO2 were hampered by SO Under oxyfuel (O2/CO2) combustion atmosphere, on one hand, the
limiting the Hg0 removal performance. It can be observed that no ho-amount of chemisorbed oxygen on biochar was decreased as the high
mogeneous oxidation reactions between gaseous Hg0 and individual gas
concentration of CO2, hence inhibiting the production of HgO on bio-
component of NO, O2, or SO2 occurred [101]. The SO2 together with
char in comparison to air atmosphere. On the other hand, the abundant
as well as NO2 with or without O2 were the major gas combination types
CO2 at oxyfuel combustion atmosphere caused the formation of much
in charge of the homogeneous oxidation of gaseous Hg0 [101].
C––O groups, which accelerate the electron transfer to generate Hg-OM
Although it is difficult for gaseous HCl to homogeneous react with
(Equation (32)). In oxyfuel combustion condition, the heterogeneous
Hg0 owing to the high energy barrier [101,137], HCl had positive
oxidation of Hg by biochar was noticeably promoted [143]. Besides, the
fluences in Hg0 removal, even low HCl concentration of 20–30 ppm
Fe3+(t) coordination also performed as Hg active site in oxyfuel atmo-
could substantially enhance the Hg0 removal performance [107,137
sphere. The 8% H2O apparently inhibited the Hg removal by biochar,
The decomposition of adsorbed HCl produced active species Cl* which
owing to the water occupied active sites helpful to the adsorption of Hg.
was aided by the active O* that was supplemented by O2 [64,137], the 1
O2 →H2SO4 (ad) + H2O
reaction path between gas-phase (or weakly bonded) Hg0 and adsorbed H2SO4 (ad) + Hg0(ad) + 2 (46)
HCl via E-R mechanism might dominantly form HgCl2 (Equations (55)
and (56)). As the reaction temperature raised from 150 ◦C to 250 ◦C, the 1
chemical reaction between Hg0 and Cl* was promoted, therefore facil-Hg0 + SO3 + 2
O2→HgSO4 (47)
itating the capture of Hg0 [137]. SO2 somewhat inhibited the active
influence of HCl in the removal of Hg0 as the formation of metal sulfateCoO + O*+ SO2 →Co2+ SO2 4
(48)
which hinds the chlorine species [137].
At the relative low H2O concentration, the decomposition of water2MnO2 + 3SO2 + O2→Mn2(SO4)3
(49)
molecules onto the biochar produces the OH radicals, which could
enhance the electron transfer processes and effectively oxidize Hg0 2CeO2 + 3SO2 + O2→Ce2(SO4)3 (50)
form HgO (Equations (57) and (58)), thereby promoting the Hg removal
[54,103]. The interactions between H2O and C–O complexes may alsoHg0 + 2NO2 + O2→Hg(NO3)2 (51)
promote the electron transfer processes to enhance the adsorption of Hg
[30]. When the H2O concentration was high (~3–5% [54,109,127]), 4Hg0(g) + 4NO2 (g) + O2 (g) →Hg2(NO3)2 + Hg2(NO2)2 (52)
excessive water vapor may not only cause the competitive adsorption
with Hg0 onto the active sites but also coagulate on the surface of bio-Hg0(ad) + NO2 (ad) →HgO(ad) + NO(ad) (53)
char to form water film which separates active sites from Hg0, both
which prevented the efficient contact between Hg0 and biochar, andHg0(ad) + NO2 (g) →HgO(ad) + NO(g) (54)
thereby suppressed Hg0 removal [64,85,108,126,128]. The positive Eley-Rideal mechanism:
fect of the formed oxygenic functional groups might partially counteract
the negative role of H2O competitive adsorption, leading to only a mild O*+ 2HCl(ad) → 2Cl*(ad) + H2O (55)
reduction in the removal capacity of Hg0 [30]. The water vapor can also
combine with the Cu–Fe mixed oxides and SO3 to generate sulfates,
C. Wen et al.

Hg0 + 2Cl*(ad)→HgCl2 (56) 3.4.2. Activation conditions of biochar

Many efforts have been carried out to increase the CO2 adsorption
H2O→OH + H (57) capacity of biochar through treatments of physical modification with
carbon dioxide activation [26,39,150,156,159–161], air activation
OH + Hg0 →HgO + H (58) [147], steam activation [36,162–164], H2O2 activation [165], and
on chemical activation treatments with KOH [48,145,148,149,165–169],
NH3 (ad) + H2SO4 (ad)→NH4HSO4 (ad) (59)
capture
consume
s 20–30
3.4. Adsorption performance of CO2 wt% aq
ueous M
globalEA and
mospheleads to
ric an 80%
entratio
in-
n of crease i
has n the
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aroundHowever
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mv adsorpti
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9 ppmvsing soli
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currently
nts capa
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CO2
current
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e- streams
post- is a pro
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ure 1]. Table
CO S4 of
e their
the Sup
espectiv
plement
e advan
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tageserials su
nd mmarize
tations.
s the pr
The eparatio
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ure and the
CO typical a
adapted
dsorptio
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gasificati
optimu
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binedption
cle performa
C) nce of
s, while
CO2 by
the biochars.
-
combusti
3.4.1.54]. By
eatmentcontrast,
condition
Huang e
s of t al. [15
char 5] prese
nted that
Thermal550
treatmen
◦C was t
t conditi
he optim
ons al temp
biomasserature
for for pyrol
aring ysis bet
ocharween 25
- 0 ◦C an
fluenced 600
he ◦C. Gen
rptionerally, hi
apacitygh temp
of erature
including
pyrolysis
the resulted
pertiesin struc
f the tural ev
starting
olu-
biomasstion and
material,
defect
the creation
mal of bioch
cessingar to de
measurevelop th
s (pyroly
e surfac
sis, e area
oxidatio
and
n [ micro-
44– porosity
147 [153]. T
TC he simil
148 ar size
152 of micro
he pores a
essing s CO2
empera-molecule
ture,
gas (with ki
rate, netic di
heatingameter
rate, of 0.33
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ime, es from
so 0.4 to 0.
9 nm an
the d is thus
lysis
mperatuadvanta
re geous t
d upo CO2 a
600 dsorptio
◦C, n [156].
CO Howeve
adsorpti
r, as th
on e tempe
cities rature
biochars
increase
were d, the m
dely ore dras
ortedtic reacti
be ons acc
ved elerated
graduall
the gas
y [153 diffusion
 rate, cause p
whichore dest
no ruction
r desira
and dec
ble rease th
generati
e adsor
ng ption ca
porespacity d
56]. ue to th
e physis
microwaorption c
ve apacity
ysis of CO2 w
capableas greatl
of y releva
ng nt to the
biochar BET sp
with ecific sur
savedface are
onsumpti
a of bio
on char.
st, The HT
and C pretre
gy atment
mparison
of biom
to ass is s
en- ometime
tionals import
yrolysis.
ant as
Huang oxygen
et function
55] alities o
rted f biocha
t ther decre
aximum ased si
CO gnificant
adsorpti
ly comp
on ared wit
unt h con-
biocharventiona
prepared
l pyroly
by sis treat
ventiona
ment, bi
l pyroly
ochar t
sis hus refl
550 ects the
was hydrop
s than hobic
hat propertie
microwas makin
ve g them
ysis favorabl
~321 e as an
, whichadsorben
possesse
t for the
d the hydroph
ghestobic
ecific and non
face -polar C
a betweO2 [21,
en 48]. The
◦C
pyrolysi
04 s assist
The ed by a
her typical t
er ernary
and carbona
mperatur
te molt
es
en based
(K nanofib
3– ers (~5
Na2 79 nm)
– through
Li2CO
under
electros
different
pinning
[158], it
inducing
s adsor
atmosph
ption ca
eres pacity o
ir or f pure
gen CO2 at
used 20 ◦C
abricate
reached
the 426 mg/
us g becau
hierarchi
se of a
cal high surf
har ace area
7]. and por
biochar
osity.
r had
O2 adsor
ption
pacity
of
2 mg/g,
which
depends
on
combina
tion
he
oved
micro-
pore
face
a and
he
ssible
spersed
basic
sorption

sites
g.,
metal
ecies
d the
rface
and
ontaining
func-
tional
oups)
biochar.
Poultry
litter
s used
for
hesizing
the
biochar
and
n the
ochar-
H3POthat high
50], er tempe
O4+ rature wa
[170 s favorab
CO le to the
39, productio
ZnCl n of mic
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However,
Activatio
some m
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char might b
h COe coa-
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lesced to
t burn-form mes
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studiedes at hig
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t al. erature a
160 nd then
CO weakene
rptiond the ads
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hanced apacity o
as f CO2. Gonz
asingalez ´ et
e burn-al. [156]
off studied
from the effec
% t of holdi
% ng time
ecreased
(0.5–8 h)
at during C
burn-off
O2 activa
rate tion, the
0%, y found
led that at t
e narrow
oo long
micropore
activation
s widen.
time of
Zhang6 h, the
et al. walls of a
3] report
djacent
ed micropor
mpacts es
f COcollapsed
ivationto produc
mperatur
e wider p
e on ores, cau
sing a de
CO creased
orptionCO2 upta
apacity,
ke at 25
hey ◦C. Rashi
d thedi et al. [
sorption
26] desig
uptake ned the
f biochar
Taguchi
experime
improved
nts and
significa
presented
ntly
500 that the
to 800 processin
C and g temper
ecreased
ature ha
slightly
d the mo
after st import
◦C. ant effect
believed
s on CO2
 ting gas
adsorptio
was repo
n rted to
ity achieve
iochara similar
s effects w
d ith the
develop
CO2 or
mentsteam a
ctivation
micro-at lower
porosity,
followed
activatio
by n temper
ss atures [1
sors, 44]. Acti
ding vation by
, gas5% O2 at
w 500 ◦C re
rate, sulted in
cle biochar
and with com
ng parable
micropor
steame volume
ctivated
as air acti
biochar
vation at
exhibited
the same
a narrow
micro-
temperat
porosity
ure, mea
of nwhile t
0.3 he incre
nm ase in a
indicated
ctivation
evident
temperat
positive
ure from
correlatio
n with500 ◦C t
gh o 650 ◦C
adsorpti
reduced
on the mean
ity [ micropor
Besides,
e size a
the nd impro
r proporti
ved the
on micropor
O, a e volume
, presenti
functiona
ng the n
l group,
arrowest
was range of
rted 0.3–0.4 n
rm m which
steam showed
tivation
a sufficie
nd nt potent
ial for a
resultdsorbing
stronger
CO2 [14
electrost
4]. Only
atic one stud
ydrogen
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bonding
treated t
interactio
he bioch
n withar with
acidicH2O2 for
O2 improvin
The g the C
of O O2 adsor
the ption, mo
re (Table S
oxygenic
4) [151,
functiona
167]. A
l groups
mong a
and variety o
owerf prepara
ro- tion con
porosity
ditions, t
werehe
ievedactivatio
[165n time, th
e mass ra
activation
tio of KO
process
H/C and
ntroduce
the activ
d moreation tem
icropores
perature
onto may have
surfaceobvious
of biocha
impacts
r althoug
on bioch
h it ars for t
introduce
he adsor
d moreption of
oxygenCO2 [14
toms 5,
present
166]. Bio
acidicchar pro
1,162duced at
he the activ
impact
ation tim
f porosity
e of 1–
in 1.5 h sh
arKOHowed the
sented
higherlargest m
dsorption
icropore
capacity
volume a
of nd the o
than ptimum
char adsorptio
and n of CO
har 2 [145,
Several
166]. Se
tudiesvilla et
ve al. [148]
the indicate
sing d that th
uptakee biocha
r biochar
rs attain
KOH
ed under
low
sure milder c
ditions
onditions
at mimic
(KOH/bio
the char =2
capture
) showed
nvironme
the high
nt of micro-
porosity
from of
mbustion
>80% co
flue mposed
up of narrow
–2.0 micropor
ol/g es of <1
5 ◦ nm. The f
0.15 raction of
narrowKOH/C
micro-mass rati
porosity
o
depends
and activ
significa
ation te
ntly mperatur
n e of bioc
ctivation
har were
degree2 and 70
o 0 ◦C. Th
whiche optimu
omass m
nderwent
, indicati
ng
od
adsorptio
n perfor-

mance.
Wei
. [166
eported
hat
optimal
activation
tempera-

ture
amboo
ochar
for
dsorption
was
◦C
range
of
850
nd
ved
adsorptio
n amount
of
rst

and
reduced
with
enhance
ment
KOH/C
mass
o from
to
5,
he
of
biting
e maxim
um
rption.
owever,
other
earch
51,
reported
that
optimal
C. Wen et al.
KOH/C ratio of 1:1 and activation temperature of 800 ◦C were also re-
ported to exhibit the maximum CO2 capacity because of its higher pore
volume and BET surface area, as well as higher basic oxygenic functional
groups and oxidized sulfur content [169]. The acidity of sulfur causes
oxygen to be negatively charged, which is conducive to attracting CO2
[169]. Therefore, the optimum KOH/C ratio and activation temperature
for biochars prepared from different precursors should be carefully
selected to create desired narrow micropores of biochars for favorable
CO2 adsorption [145,166,167], which have strong adsorption potentials
at atmospheric pressure [148]. Igalavithana et al. [52] indicated that the
activation of KOH plus CO2 could not further increased the
micro-porosity derived from KOH activation, the further activation with
CO2 even might enlarge the micropores forming mesopores due to the
overreaction of biochar with CO2 [21].
K2CO3 is chosen to replace the KOH sometimes as it can avoid the
high temperature corrosion and environmental hazard of KOH effec-
tively [38,39]. The micropore volume and surface area generally
increased with raising the activation temperature (600–800 ◦C), the
narrow micropores abundant in biochar was the determining factor of its
good CO2 adsorption capacity. The adsorption amount was also reported
to improve as the increase of K2CO3 loading up to 20% [171], indicating
the efficient chemisorption forming KHCO3 as both the pore volume and
surface area decreased (Equations (60)–(62)). Heidari et al. [170] pre-
pared the biochar activated by H3PO4+KOH and ZnCl2, they found the
lowest impregnation ratio (0.75 g/g) of ZnCl2 into biochar had the 100%
micropore structure and the most CO2 adsorption amount, presenting
better efficiency than H3PO4 activation, while the adsorption ability of
CO2 increased and then rapidly decreased as increasing of the impreg-
nation ratio of H3PO4 from 1.5 to 2.5 g/g, attributed to the formation of
more mesopores as well as low micro-porosity.
On the whole, the adsorption of CO2 using biochar is mainly asso-
ciated with micro-porosity, large surface area, and surface chemical
properties. The narrow micropores enhance their filling by the CO2
molecules and thus have stronger adsorption potentials than larger
micropores and mesopores [150]. Wei et al. [166] observed that the
pore size of ~0.55 nm contributed dominantly to CO2 adsorption at 1
bar, as it supplies enough spaces for the CO2 molecules with kinetic
diameter of 0.33 nm to adjust their orientation and accommodate itself
onto the pore wall. Coromina et al. [151] indicated that the energy of
adsorption was optimized when the pore size of biochar was 2–3 times
than the size of CO2 molecule, the optimum pore size was thus between
0.7 and 0.9 nm for the excellent adsorption of CO2 at 1 bar. Deng et al.
[167] reported the linear correlation between the amount of CO2
adsorbed at 25 ◦C and 1 bar and the pore volume in the range 0.33–0.63
nm, as well as the effective adsorption performance of the narrow mi-
cropores of 0.33–0.48 nm at 25 ◦C and 0.15 bar. Evidently, the narrower
micropore is mainly responsible to CO2 adsorption under the practical
flue gas conditions with lower pressure, which will be further discussed
in Section 3.4.4. For the physisorption mainly controlled by the narrow
micropores, there is possibly no influence of biomass precursors and
preparation method on the linear correlation between the micropore
volume of biochar and the adsorption amount of CO2 [166]. Besides,
Feng et al. [164] found the mesopores volume and adsorption capacity
were also correlated positively, the channel role of mesopores for the
diffusion and transport of gas molecules into abundant micropores
appeared to be important to the adsorption performance of CO2 as well.
Noteworthy, the high content of aromatic structures in biochar might
increase the van der Waals forces between carbon structure of biochar
and CO2, which would also improve the physisorption of hydrophobic
CO2 [21,163].
K2CO3 ↔ K2O + CO2
(60)
K2O + H2O→2KOH
KOH + CO2→KHCO3
3.4.3. Impacts of functionalization
3.4.3.1. Ammonia/amines. Fig. 3 presents the ammonia and amine
functionalization on biochar for adsorption and reaction of CO2 together
with SO2. The basic amines are nucleophilic and play as electron-donors
due to the occurrence of a lone pair of electrons, allowing them to
interact effectively with the acidic CO2, which is weak Lewis acid as
electron-acceptor because of the strong electron negativity of oxygen
atoms [56]. The strong pole-pole interactions occur between the polar
sites associated to nitrogen functional groups and the large quadrupole
moment of CO2 molecules to form covalent bonding [46]. The ammonia
modification of biochar is thus a promising method for promoting the
adsorption capacity of CO2 [159,160], it is generally attached with
biochar through impregnation or grafting [57]. Samanta et al. [1] listed
the name and structure of widely used amines for sorbents functionali-
zation. HNO3+ammonia gas [31], gaseous ammonia [58,159,160,165,
173–175], ammonia solution [164], urea [168,176], organic ammoni-
ated chemicals [56,57,152,177] were reported to functionalize the
biochars.
Both the porous texture and nitrogen amount and types affect the
CO2 adsorption performance of N-doped biochars [165,178]. On one
hand, the ammonia decomposes at high temperature forming atomic H
and NH2 and NH radicals that react with the carbon, the gasification at
high temperature produces the high BET surface area and narrow
micro-porosity that promotes physisorption of CO2 [174]. On the other
hand, nitrogen can interact with the carbon matrix by reaction between
surface oxides or active sites in biochar and ammonia to generate
ammonium salts and amine groups and then produce various nitrogen
functional groups [159]. Zhang et al. [173] elaborately discussed
chemical reaction and mechanisms between amine and CO2. On one
hand, C–OH and C–O–C respectively reacted with ammonia to form
amines, and then react with CO2 to generate N–COO (Equations (63) and
(64)). On the other hand, the formation of pyridine C––N and C––O was
caused by the dehydration reaction of ammonium carbamate or carba-
mic acid, providing more active sites for nitrogen functionalities. The
type of the nitrogen functional groups, e.g., pyridine-like functionalities,
apart from their amount, was reported by Shafeeyan et al. [58] to affect
the CO2 uptake, meanwhile pyrrolic-N (N-5) should be more favorable
for CO2 adsorption than pyridinic-N and quaternary-N (N-Q) [38,152,
168,178]. Feng et al. [164] adopted quantum chemistry simulation on
the CO2 adsorption by biochar first time, they confirmed the strong in-
teractions between pyridine-N and CO2 molecules. Zhang et al. [179]
revealed the adsorption mechanisms using in-situ DRIFTS to monitor the
interfacial reactions between biochar and CO2, they discovered the hy-
droxyl, amines, primary amide, secondary amide groups, N––N and
aliphatic C–N/C–O were all useful active sites to interact with CO2 at the
adsorption temperature between 30 ◦C and 60 ◦C, while the secondary
amide group showed decreased effects on CO2 adsorption when the
temperature raised to 120 ◦C. The ZIF-8 (zeolitic imidazolate frame-
works) was grafted onto biochar to form nitrogen-enriched modified
biochar [180], the results showed that the in-situ synthesis method
improved the dispersion of ZIF-8 nanoparticles containing high nitrogen
content of >10%, and the modified biochar contained more micropores
centered at 0.8–1.5 nm and abundant pyrrolic nitrogen. The DFT
calculation indicated that on one hand, the van der Waals effect mainly
dependent on the pores ranged from 0.62 to 0.72 nm is decisive in the
CO2 adsorption performance, on the other hand, the nitrogen and oxy-
gen functional groups, especially C–O/C––O and graphitic-N, have an
apparent synergistic effect on CO2 adsorption [181]. Thermal treating
biochar with ammonia gas at temperature from 400 ◦C to 900 ◦C was
studied, it can be observed that the formation of new micro-porosity of
＜1 nm [58] and the nitrogen content in biochar was maximum at 600
◦C [173] or capacity
800 ◦C [59,159,160], respectively,
gasificationleading
(61) The to improved CO2
adsorption of biochar. with carbon increased
at higher temperature to produce higher BET surface area and narrow
(62)
C. Wen et al.
micro-porosity, however, the gasification was too severe above 800 ◦C at
which the narrow micropores were decreased owing to the collapse of
adjacent pore structures, causing the decreased adsorption of CO2 at
high temperature [58,59,177].
The important role of nitrogen functionalities in CO2 adsorption was
demonstrated by the lower textural development but similar adsorption
capacity of biocharNH3 compared with biocharCO2 [159]. Zhang et al.
[173] prepared the CO2-ammonia modification biochars from 500 ◦C to
900 ◦C, they found that the presence of CO2 generated a number of
functional active sites that prompted the production of the nitrogen
functional groups, implying that the modification of CO2-ammonia
combined the advantages of those two treatments. The N-doped biochar
decreased in nitrogen content after KOH activation [165,178], which
was probably due to the formed nitrogen groups during ammoxidation
were low thermal stability. Meanwhile, the doped nitrogen can addi-
tionally activate biochar upon KOH treatment, which belonged to the
depth activation and increased the narrow microporous textures of
biochar [178]. Chen et al. [168] activated the coconut shell at 650 ◦C
with KOH and urea, they observed that both high porosity and sufficient
nitrogen amount worked together in the great CO2 adsorption of formed
biochar. At too high temperature, coarser pore sizes were developed
because of the gasification caused by the decomposition of potassium
salts. It is noteworthy that a deashing treatment on biomass was re-
ported to promote the porous texture of N-enriched biochar and the
introduction of nitrogen functional groups by increasing the number of
active sites [175].
Ultrasonic irradiation at a short time of 30 s can leach the minerals
from biochar and making space for amine groups to attach, meanwhile
not only expedite the mass transport inside the pores due to increased
turbulence but also hinder the generation of an agglomerated graphitic
layer by exfoliation of biochar, thus the process can prevent the blocking
of pores and aid in enhancing surface area that supplies active sites
capable of amine groups functionalization, and then benefited to CO2
adsorption arriving 2.79 mmol/g at 70 ◦C and CO2 partial pressure of
0.15 atm [56] and 1.91 mmol/g at 70 ◦C and 0.10 atm CO2 [57], as
shown in Table S4. However, too long sonication time foiled the pro-
duction and collapse of microbubbles and would reduce ultrasonic ef-
ficiency and adsorption performance of CO2. The ball-milling method
has also been applied to produce N-doped biochars eco-friendly [46].
The volumes of total pore and micropore as well as BET surface area of
biochars increased after ball milling, strengthening the beneficial effect
of earlier doped N on CO2 adsorption. The existence of acidic oxygen
functional groups is generally not benefit to CO2 adsorption, however, it
is a good idea to develop some oxygenated anchoring sites as an effective
intermediate stage to introduce nitrogen functionalities onto the biochar
[58,59]. The pre-oxidation of biochar was thus considered to enhance
the nitrogen incorporation during ammonia treatment, and displayed
enhanced adsorption ability of CO2 at relatively high temperature [58].
H2O2 treatment was also carried out to increase oxygenic functionalities
and further enhance the amount of nitrogen functional groups in bio-
char, it meanwhile had a favorable influence in promoting the narrow
micro-porosity of N-doped biochar, leading to an impressive CO2
adsorption performance of 4.47 mmol/g at 25 ◦C (Table S4) [165].
OH + NH3→ NH2 + H2O
(63)
2R NH2 + CO2 →R NH+3 + R NH COO
3.4.3.2. Metal modification. Xu et al. [182] found that the chemisorp-
tion induced by CO2 mineralogical reactions was promoted by high
temperature. They separated the inorganic fraction of biochar for indi-
rectly determining the role of the chemisorption induced by reactions
mineral components (Ca, Fe, Mg, K, etc) in CO2 adsorption [182], whichFeOOH + HCO 3 (ad)→Fe(OH)2CO3 (s)
accounted for 17.7%–50.9% of CO2 adsorption when assuming without
interactions occurred between the organic and mineral portions Mg O + CO2 →Mg O…CO2(ad)
biochar. Metal oxyhydroxides commonly possessed basic, thus was
likely to interact with CO2 when polar surfaces are in contact. Cotton-
wood was treated with metal ions (AlCl3, FeCl3, and MgCl2 hexahydrate)
and then pyrolyzed to prepare biochar-based composites with metal
oxyhydroxide crystalline nanoparticles. The composites especially the
biocharAl had better adsorption uptake of CO2 than the unmodified
biochar [183]. As the concentration of Al increased, the adsorption of
CO2 of biocharAl increased as well, mainly contributed by the process of
surface adsorption. In this work, the Mg(OH)2 particles rather than MgO
particles were introduced, possibly caused by too much water input
leading to the transformation of MgO into Mg(OH)2. Mg(OH)2 particles
can chemisorb CO2 only under high temperatures of 200–315 ◦C and
high pressure conditions [183]. The biochar-based composites loaded
with Fe oxyhydroxide nanoparticles was further studied [184]. The
dominant mechanism of CO2 adsorption was physisorption for the bio-
char composites with low Fe content. As the increase of Fe content,
biocharFe showed enhanced CO2 adsorption capacity come from chem-
isorption contributed by the collapse of the crystalline structures and the
structure disordering enhancing the mineral carbonation of CO2
(Equations (65) and (66)). Several basic metals were also loaded to the
biochar skeleton by the methods of wet impregnation and heat treat-
ment, the introduction of basic metal sites enhanced the CO2 adsorption
performance of biochars with 5 wt% metal loading in the sequence of
Mg > Al > Fe > Ni > Ca > raw biochar > Na via the synergistic physical
and chemical interactions [153]. The basic O2 in MgO was the main
CO2 capture sites, which was generated from thermal decomposition of
anhydrous magnesium nitrate and reacted with CO2 to form carbonate
(Equation (67)). Sodium incorporated biochar presented worse capacity
than raw biochar due to the incorporated Na failed to form Na2O, thus
not only failed to promote the chemisorption, but also hampered the
physisorption performance caused by pore blockage.
The impregnation of Mg onto the biochar structure was reported to
improve the capture of CO2 in the order of magnesium acetate ＜
magnesium chloride ＜ magnesium sulfate ＜ magnesium nitrate [154].
The worst capacity of acetate was attributed to the applied calcination
temperature of 500 ◦C may insufficient to generate oxides which should
be decomposed by the acetate salt, as a contrast, the decomposition of
magnesium nitrate towards magnesium oxide initiates at around 400 ◦C.
Too high Mg impregnation of 7%–20% on biochar would cause the pore
blockage, thus reducing the advantage of chemisorption from metal
loading [153,154]. The fast pyrolysis MgCl2-loaded biomass were syn-
thesized to form biochar stabilized with MgO nanoparticles, achieving a
favorable CO2 capture amount of 5.45 mmol/g at 80 ◦C (Table S4)
[185]. Pyrolysis at 800 ◦C presented the highest pore volume and sur-
face area, in comparison to other temperature and raw biochar without
MgO, confirming that the dehydration and decomposition of magnesium
chloride hexahydrate changed the decomposition pathway of biomass,
promoted the release of volatile matter, and thus promoted the porous
properties and CO2 capture capacity [185]. The basic O2 in oxides
around the edges and corners of crystal surfaces is frequently more basic
than those near the planes. The MgO nanoparticles present more edges
and corners per unit weight because of their small size, thus containing
more basic O2 and providing more active sites for CO2 chemisorption
[153,185]. A dependable mechanism of CO2 capture by biochar was
plotted by Luo et al. [186].
Furthermore, the hydrogen bonding produced from the interactions
of the OH groups and CO2 molecule can boost the CO2 capture capacity,
however this weak bonding may be (64)
destroyed at high temperature
[185]. The S-containing function groups were also reported to benefit
the adsorption of CO2 [21,52].
CO2 (ad) + OH →HCO 3 (ad) (65)
(66)
(67)
C. Wen et al.
3.4.4. Adsorption conditions
3.4.4.1. Temperature. For the physical interaction, the adsorption ca-
pacity of CO2 drops as the elevation of adsorption temperature outlined
by Le Chatelier principles, however, with regard to the chemical inter-
action, the capacity increases with an increase in adsorption tempera-
ture firstly but declined with a more increase in temperature [185].
Creamer et al. [187] reported that when the adsorption experiments
were performed at 25–100 ◦C, the adsorption capacity of CO2 by biochar
declined linearly with increasing the temperature. The similar tendency
was also found in the biocharKOH work at 0–100 ◦C [48,148,162,169,
170], biocharCO2 at 0–120 ◦C [26,39], biocharNH3 at 20–105 ◦C [31,58],
and bicharMg at 25–70 ◦C [153]. The exothermic characteristics of
physisorption would be increased at higher temperatures, which in-
dicates the increase of the diffusion rate of gas molecule and the energy
of surface adsorption and further leads to the increment of thermal en-
ergy of CO2 molecules and the decrease of adsorption force onto the
biochar [48,175]. As increasing the temperature, only the narrowest
pores mainly acting as the most energetic adsorption sites maintain
occupied, more pores in biochar are useless for the adsorption of CO2 via
pore-filling mechanism [156]. Plenty of CO2 adsorbed at low tempera-
ture would obtain sufficient energy at higher temperature to get over the
van der Waals forces and get back to the gas phase [59]. Deng et al.
[167] reported that when the adsorption temperature raised from 25 ◦C
to 75 ◦C at 1 bar, the range of micropores effectively for the adsorption
of CO2 narrowed from 0.33-0.63 nm to 0.33–0.52 nm. For the ammonia
treated biochar, the observed CO2 adsorption performance of biochar
was linear correlated with the micropore volume at low adsorption
temperature of 20–30 ◦C. However, at higher temperature of 105–120
◦C, it was noticeable to be dependent on the existence of basic nitrogen
functional groups of biochar [58,172,173]. The porosity development
became no longer important as the adsorption temperature increased,
but the regeneration of chemisorption active sites will be more difficult
as the promoted chemisorption at high temperature [175]. The in-
teractions of both physical and chemical adsorption controlled the CO2
capture by the MgO loaded biochar, with a best removal capacity at 80
◦C between 50 and 300 ◦C [185]. Xu et al. [182] also found the transition
of CO2 adsorption mechanisms by biochar from physisorption to
chemisorption as the increase of reaction temperature, causing the
removal of CO2 enhanced from 50 ◦C to 75 ◦C. To sum up, the capture of
CO2 can be carried out at relative high temperature when the developed
biochar has more ultra-micropores or enhanced chemisorption capacity.
3.4.4.2. Flue gas. The research on the CO2 partial pressure with ~15%
of CO2 in N2/CO2 atmosphere were widely proceeded to simulate the
flue gas condition of coal-fired boiler [31,153,156,159,160,168,174],
and other CO2 concentrations were also concerned as it can represent
different types of post-combustion flue gases, such as that produced by a
natural gas fired plant of 8% CO2 and by a cement plant of 30% CO2
[147]. When inlet concentration of CO2 increased, the diffusion velocity
of CO2 increased through the pores of biochar, thus promoting the
adsorption capacity of CO2 [39,56,162,169]. The CO2 adsorption ca-
pacity of biochar at 25 ◦C and 1 bar in CO2/N2 = 15%:85% was thus
lower than that in pure CO2 flow [160]. A new machine learning study
on the carbon materials from biomass revealed both the volumes of
mesopores and micropores played an important role at 0.1 bar according
to the random forest model [188]. At the pressure up to 1 bar, the uptake
of CO2 was dominantly controlled by the pore size and accordingly the
interactions between the pore walls and gas molecules, wherein biochar
with narrow micropores had the higher CO2 uptake [151]. As the
decrease of CO2 partial pressure, the occurred nitrogen functional
groups or a narrower pore size distribution in biochar appears to become
important, instead of the surface area [159]. Linear correlations of
narrow micropore ranges of biochar adsorbed at 0.15 bar were calcu-
lated [146,167], 0.33–0.40 nm was indicated to be mainly responsible
for the adsorption of CO2, obviously narrower than 0.33–0.52 nm at 75
◦C and 1 bar [167]. The improved texture and functionalities charac-
teristic of the biocharamine presented an impressive CO2 uptake up to
8.89 mmol/g in CO2/N2 = 20%:80% at 20 ◦C and 1 bar (Table S4) [31].
The CO2 uptake rose rapidly as the pressure increased (0.01–1 bar [36,
166,167], 0.5–4 bar [161], and 1–16–20 bar [59,151,170]). Biochars
with high surface area was able to have better performance at higher
pressure of 20 bar which mimics the pre-combustion CO2 capture [151],
the removal mechanism is more dependent on surface area or space
filling, therefore, pore diffusion is the major governing mechanism and
wider pores become more relevant for the CO2 adsorption [36]. Lahijani
et al. [153] observed the influence of CO2 gas flow rate in the adsorption
uptake of biochar, they found that the adsorption and surface saturation
were speeded up to signify the CO2 capture under a high gas flow rate
but the ending adsorption amount remained almost unchanged if
providing sufficient time.
Multi gas component adsorption experiments simulating the real flue
gas were conducted to observe the CO2 capture performance by biochar
[189,190]. The adsorption of H2O was a very slow process in compari-
son with the adsorption of N2 and CO2, the occurrence of typical flue gas
compositions, including N2, O2, and H2O, hardly hampered the
adsorption of CO2 for relatively short adsorption time of less than 60 min
[189]. However, another research indicated that the breakthrough
curves over the biochar initially almost saturated with H2O, which
implied the adsorption performance of CO2 was highly reduced by the
moisture input [190]. Furthermore, Xu et al. [182] indicated that the
addition of 50% moisture presented a positive influence in the CO2
adsorption. The sewage biochar containing much inorganics is alkaline
and thus favors the interactions with acidic CO2 dissolved in the alkaline
water membrane on the biochar surface to form insoluble inorganic
carbon and improve the chemisorption. Murge et al. [171] observed that
the CO2 capture capacity of biochar initially enhanced and then dropped
as the enhancement of H2O concentration, too much H2O formed a
thicker layer of water and/or KHCO3 precipitation come from K2CO3
activation, which offered a resistance to CO2 gas to access the other
active sites and pores.
When 4% O2 was introduced into 15% CO2/N2 stream at 75 ◦C, a
deteriorating effect was observed to CO2 adsorption by Thote et al.
[172], they speculated it was attributed to the competitive adsorption
for the micropores between CO2 along with O2 at 75 ◦C. Other study
reported that the O2 concentration up to 8% affected little on the
adsorption of CO2 at 25 ◦C in the simulated flue gas [169], ascribed to
that the nonpolar O2 molecules were very stable at 25 ◦C, which made
the attraction between O2 and biochar very weak. In the flue gas com-
ponents, the increase of SO2 concentration up to 1500 ppm slightly
inhibited the CO2 adsorption performance, as these two acid oxides
would compete for the active cites. NO is not an acid oxide and its input
up to 800 ppm presented unchanged influence in the adsorption of CO2
[169].
The reported maximum adsorption uptake shown in Table S4 for the
adsorption of pure CO2 using biochar was 10.15 mmol/g at room tem-
perature of 20–30 ◦C and atmospheric pressure [31], and 5.2 mmol/g at
flue gas temperature (~70–120 ◦C) [185]. In the research reports of
actual or simulated flue gas, the maximum adsorption uptake of CO2 was
8.89 mmol/g at 20 ◦C and 20% CO2 as well as 2.84 mmol/g at 75 ◦C and
20% CO2 [31]. More effects are necessary to match the requirement at
flue gas conditions and completing with other technologies of CO2
capture.
3.4.4.3. Selectivity of CO2. An effective biochar adsorbent for practical
applications in the CO2 capture systems requires an adequate selectivity,
i.e., it should be easy to remove the CO2 component in industrial flue gas
with minimal interference from other major gaseous species such as N2
and O2 [48,153]. The adsorption of CO2 was generally easier than that of
N2 for all pressures and biomass samples. The equilibrium selectivity of
C. Wen et al.
CO2/N2 is defined as the ratio of the molar fractions at equilibrium in
adsorbed phase to those in gas phase, the ratio of adsorbed amount of
pure CO2 to N2 is generally calculated to receive an equimolar CO2 and
N2 at a typical pressure. However, selectivity is better evaluated from
the measurements of multicomponent adsorption, because the adsorp-
tion of the weaker adsorbate (N2) is significantly suppressed when it
co-exists with the stronger adsorbate (CO2), causing the conservative
estimates of the CO2-over-N2 selectivity in CO2/N2 equilibrium calcu-
lation [156]. The CO2/N2 selectivity for the binary gas mixtures can be
calculated and predicted using the ideal adsorption solution theory
(IAST) [31,36,156,165,168].
For selectivity based on the main physical adsorption, the separation
of the gas molecules relies on their different physical properties, e.g.,
polarizability and quadrupole moment, causing the different gas
adsorption enthalpy [48]. The polarizability and quadrupole moment of
CO2 (29.1 × 10 25 cm 3, 13.4 × 10 40 cm 2, respectively) are higher
than those of N2 (17.4 × 10 25 cm 3, 4.7 × 10 40 cm 2, respectively), it
is thus expected that CO2 is able to interact stronger with the electrical
field gradient of biochar and has higher affinity of the pore surface
leading to a high selectivity [48]. Lahijani et al. and Zubbri et al. [153,
154] showed that the profound affinity of Mg-loaded biochar towards
CO2 compared with other gases (N2 and O2) may be ascribed to the
higher quadrupole moment and polarizability of CO2, inducing a larger
polar bonds and stronger interaction with the biochar surface. The gas
selectivity is also affected by the kinetic diameter of the gas molecule,
which is directly proportional to the diffusion process, however the af-
finity of gas molecule towards biochar should not be ascribed to the
diffusivity due to the similar kinetic diameters of O2 (3.46 Å), N2 (3.64
Å) and CO2 (3.30 Å) [154]. Servilla et al. [148] observed that the
adsorption of CO2 was very fast with around 95% in the first 2 min, but
N2 adsorption was slower which took around 60 min to reach the
maximum adsorption uptake, therefore, high CO2/N2 selectivity can be
achieved for short adsorption time, which was apparently beneficial to
practical applications. The narrower micro-porosity and improved
functional group properties arised from the aminated biochars also
presented high selectivity of CO2/N2 at low CO2 partial pressures [31,
150,160,174], but may increase the preparation cost and regeneration
difficulty. Manya et al. [146] reported that the selectivity notably
decreased at 75 ◦C compared to 25 ◦C, revealing that the CO2 phys-
isorption by biocharKOH was more temperature dependent than N2
adsorption.
3.5. Adsorption performance of VOCs
As defined by the U.S. EPA, the volatile organic compounds (VOCs)
are “any compound of carbon, excluding carbon monoxide, carbon di-
oxide, carbonic acid, metallic carbides or carbonates, and ammonium
carbonate, which participates in atmospheric photochemical reactions”
[10]. Most of them are toxic and can lead to severe environmental
hazard, e.g., greenhouse effect, stratospheric ozone depletion, and
photochemical smog, to seriously damage the human health. VOCs in
atmospheric environment are characterized by low molecular weight,
high saturated vapor pressure, low boiling point, easy decomposition,
volatile, and so on. The specific industrial combustion activities are one
of the important sources of VOCs [49]. Some common types of VOCs
include toluene, benzene, chlorobenzene, chloroform, acetone, formal-
dehyde, xylenes, ethylbenzene and halogenated hydrocarbons [191].
Adsorption removal by biochar can be an efficient technology for flue
gas streams containing low concentrations of VOCs. However, the
removal availability varies with not only biochar properties but also
different VOC types. The real-time monitoring of removal capacities of
trace VOCs such as formaldehyde, acetone, xylene, toluene and benzene
by wood biochar was reported to be 1.46, 28.24, 0.71, 433.83, 0.35
mg/g, respectively [192]. Table S5 of the Supplementary Materials
summarizes the preparation conditions of biochar, and the typical
adsorption conditions and optimum adsorption performance of VOCs by
biochars.
Adsorption of VOCs onto biochar is a physicochemical interactions
generally affected by physical process such as van der Waals forces and
pore-filling [49]. The attractive forces between biochar material and
VOC molecules can be affected by polarity and hydrophobic effect of
biochar. The atomic ratios of biochar provide an indication of its hy-
drophilicity (O/C), aromaticity (H/C) and polarity ((O + N)/C), which
can affect the adsorption capacity of polar and non-polar VOCs [49],
although polarity of biochar is usually expressed by O/C ratios roughly
[35,50]. The biochar containing much polar compounds (e.g., cellulose,
lignin, and fatty acids) can elevate its polarity [49]. The VOCs adsorp-
tion by biochar involves both adsorption to the carbonized fraction and
partitioning to the non-carbonized organic matter (NOM) fraction [35].
The presence of oxygenic functional groups onto biochar is generally
responsible for surface acidity of biochar and the increased adsorption of
polar and hydrophilic VOCs [193], but it has negative impact on the
adsorption of hydrophobic VOC by suppressing the interactions between
p-electron rich regions of biochar and hydrophobic VOCs [40]. Chemical
functional groups influence both electrostatic and dispersive in-
teractions between VOCs and biochar with the foundation of Van der
Waals interactions [191], the π-π dispersion interaction and hydrogen
bonds are both the attractive forces affecting the adsorption capacity of
biochar [194]. Therefore, a balance between the features of the pore
properties, chemical functional groups of biochar and characteristics of
VOCs needs to be considered to reveal the adsorption performance of
typical VOCs [191]. Fig. 7 illustrates the main adsorption mechanism of
onto biochars.
3.5.1. Effects of biochar properties
Many research reported the physisorption as the dominating mech-
anism of VOCs. An appropriate mesoporous and macropore network is
necessary to enhance the diffusion of the VOC molecules into the mi-
cropores, although VOCs would be hardly adsorbed dynamically in
mesopores and macropores. The adsorption capacities of toluene [195]
and limonene [196] were found to linear correlate with mesopore vol-
ume of biochars. Further, when the dynamic diameter of VOCs is close to
the micropore size of biochar, the van der Waals potential fields pro-
duced by the pore wall overlaps lead to higher adsorption energy for
VOCs [197], a low kinetic diameter of VOCs can thus react with more
active sites and access finer pores/canals [49]. As a result, a stronger
linear correlation between micropore volumes or BET surface area of
biochars and adsorption capacities of VOCs were widely observed [40,
191,194,196,198]. The narrow micro-porosity was reported to be
dominant at low concentrations of toluene with the kinetic diameter of
0.67 nm [191,196] and P-xylene of 0.58 nm [198]. The more micropores
of ~0.8 nm benefited the adsorption performance of chlorobenzene
(0.78 nm) than toluene [197].
The Grand Canonical Monte Carlo (GCMC) simulation can be con-
ducted to predict and guide the optimal adsorption pore size of VOCs
adsorption. It can be found that with the increase of pore size, the
adsorption capacity of cork biocharKOH for acetone firstly increased,
then stabilized, and finally rapidly declined through GCMC simulation
[199]. When the pore size was less than 0.8 nm, acetone molecules with
the dynamics diameter of 0.46 nm were limited by the insufficient pore
volume. Then, the acetone molecules adsorbed not only on the pore wall
but also on the adsorbed acetone molecular layer when the pore size
increased to 1.6–2.8 nm, forming an optimal multilayer adsorption
strengthened by an interaction force among the acetone molecules.
However, this interaction was greatly weakened when the pore size was
further enlarged [199]. Similarly, the optimal pore with 3.5 nm and 3.0
nm were reported for methanol and acetone adsorption, respectively
[200].
As indicated by the GCMC simulation, the nitrogen and oxygen atom
doping can improve the adsorption capacity of oxygenated VOCs
(methanol) at relatively low pressure, while the adsorption capacity at
high pressure mainly depended on the pore structure. By contrast, the
C. Wen et al.

Fig. 7. VOCs adsorption mechanism diagram of biochar, referring to physical adsorption including surface adsorption, pore filling and partitioning to noncarboniz
ed
organic matter and intermolecular forces including electrostatic attraction, π-π interaction, CH-π bonding, etc. The molecular size, molecular weight and boiling po
int
of VOCs also impact the adsorption behaviors.

influence of nitrogen and oxygen groups on adsorption capacity of above-mentioned NOM [198]. The activation of KOH or K2CO3
omatic VOCs was limited, and the adsorption capacity was mainlyenhanced textural properties of biochar and resulted in a high toluene
determined by the pore structure at both low and high pressures [201 adsorption capacity which was conditioned by its small molecules size
The multilayer adsorption of p-xylene onto mesopores were found readily to access the inner micropores [191]. The biochar which was
enhance the adsorption capacity by activated carbon dramatically when activated without a prior pyrolysis or applying for a low weight ratio of
the pressure was high enough [202]. activating agent showed much chemical (oxygenated) functional groups
As raising the pyrolysis temperature, the BET surface area of biochar which can improve the adsorption of hydrophilic VOCs [191]. H3PO4
increased generally and the ratio of O/C decreased which reflects hy-activated hydrochar was reported to possess higher surface area, O/C
drophobicity, reduced polarity, and raised aromaticity of biochar, bothratio and polarity than hydrocharKOH [40]. On one hand, the higher
effects were benefit to adsorb hydrophobic VOCs [35,50]. Besides, thesurface area of hydrocharH3PO4 provided more adsorption sites for VOC
NOM of biochar, which can sorb VOCs through partitioning into themolecules. On the other hand, the H3PO4 activation produced plentiful
organic phase, would decrease due to more volatiles were decomposedoxygenic functional groups onto hydrochar. Therefore, the adsorption
and released at higher pyrolysis temperatures [35,198]. Therefore, capacity of polar acetone was improved by hydrocharH3PO4 while
increasing pyrolysis temperature of biochar may present opposite in-hydrocharKOH possessed a slightly better adsorptive capacity of
fluence in VOC sorption via an adsorption-partition combined mecha-non-polar cyclohexane than hydrocharH3PO4 [40].
nism. The adsorption would be the leading mechanism for the biochars
The adsorption performance of toluene from a N-doped biochar with
formed at higher temperature with high porosity, whereas partitioning
the hydrophobic properties could reach up to 223 mg/g [205]. N-doping
is the dominant mechanism for the biochars from lower pyrolysis tem-
promoted π-electron polarization and produced π-electron enrichment
perature with the relatively enough surface area for VOC molecules
sites on the biochar surface, which generated π-π dispersion with the
diffuse into biochar [35,50,193,203]. Note that the physisorption was
more sensitive to the adsorption temperature between 20 ◦C and 40 ◦ benzene ring in toluene to promote adsorption. Besides, pyrrole N had
and had faster kinetic than the partition mechanism which was mainlythe strongest promoting effect to toluene adsorption by electrostatic
governed by pore diffusion process [35,50]. Ball milling treatment interaction. Cu-BTC@biochar was synthesized by a facile solvothermal
biochar can reduce the particle size of biochar, not only increasing thesynthesis method from the bamboo-based biochar [206]. The intro-
exterior surface area but also opening its interior pore to improve inte-duction of biochar is crucial for the construction of composites with
rior surface area. The ball-milled biochar had higher specific surfacecontrolled morphology. Its adsorption capacity of toluene reached 501.8
area and O/C ratio which could increase the acidity, polarity and and 88.8 mg/g at 60 ◦C and 150 ◦C, respectively. The van der Waals
drophilicity of biochar, meanwhile, the oxygen in air can introduce theforce generated by the micropores and toluene molecules and the syn-
oxygenic functional groups onto biochar and increase the content ergy (electrostatic interaction) of Cu ion metal sites and
volatile organic matter during ball milling [50,198]. Therefore, theoxygen-containing groups in Cu-BTC@biochar both played important
adsorption of VOC onto ball-milled biochar was also dominated by the roles in improving the toluene adsorption capacities at relatively high
combined mechanisms of surface adsorption and partition [50]. Besides,temperature.
sludge biochar was reported to contain much oxygenic functional3.5.2. Effects of VOC types and properties
groups, therefore could be used for polar VOCs [204].
The polar VOCs tend to adsorb onto biochar containing rich polar
Activation methods on biochar affect the adsorption of VOCs. The
groups, while nonpolar VOCs prefer to adsorb on the biochar without
adsorbed amount of VOCs increased with elevating the activation tem-
polar groups. There are three forms of intermolecular forces for the polar
perature in CO2, may be ascribed to the larger porosity [194]. Oxidizing
VOC molecules (e.g., acetone, chloroform, ethanol), namely dipole-
agent such as H2O2 can react with biochar’s unsaturated ring sites, and dipole, induced dipole-induced dipole, and dipole-induced dipole
then introduce oxygen into biochar which affected the formation forces. By contrast, only induced dipole-induced dipole force is
C. Wen et al.
dominant for nonpolar VOC molecules (e.g., cyclohexane, benzene,
xylene). The induced dipole-dipole and dipole-dipole forces reinforcing
polar molecular forces are analogous to the hydrogen bond with
medium-strength, which are more powerful than the induced dipole-
induced dipole force. The polar acetone thus demonstrated greater
adsorption than nonpolar cyclohexane onto a hydrochar with polar
surface [194]. The oxygenic functional groups were introduced and the
polarity was enhanced during the ball milling treatment to biochar, the
adsorption of polar acetone, chloroform, and ethanol was thus promoted
by forces of dipole-dipole and hydrogen bonds [50]. Both chlorobenzene
and toluene contain benzene ring. The larger polarization of Cl (2.18) in
substitutional group of chlorobenzene led to stronger interaction po-
tential than C (1.76) in toluene, thus making chlorobenzene readily
adsorbed by biochar [197]. Besides, the polarizability of VOCs increased
with the relative molecular mass because of the participation of more
polarized electrons, the larger relative mass of chlorobenzene can be
also effective to result in a greater adsorption potential than toluene
[197].
Biochar contains much of carbon atoms having π-electron orbit,
which can be coupled with VOC molecules having π-electrons (e.g.,
acetone) to generate π-π dispersion interaction with face-to-face or offset
face-to-face orientations [40]. The π-electrons in the aromatic ring of
VOCs can interact with the electron-rich regions locate in graphene
layers of biochar via π-π argument, the higher degree of graphitization
thus likely promoted the adsorption with aromatic toluene and chloro-
benzene [197] and xylenes [203] on biochar due to π-π conjugated ef-
fect. However, no extra orbital is available to generate the π-bond for
cyclohexane, which thus was impossible to present π-π dispersion
interaction onto the hydrochar [40]. The carbonyl (C––O) groups on the
biochar surface are electron-withdrawing groups, therefore lowering the
electron density of biochar and weakening the π-π conjugated effect
between VOCs and biochar, the electron density in the π-system from
aromatic ring in toluene decreased rapidly compared with that in
chlorobenzene [197]. The low adsorption capacity of hexane on biochar
was related to its specific molecular arrangements, it can interact with
carbon molecules of biochar only through CH-π bonding, as a contrast,
other aromatic VOCs, such as p-xylene and toluene, utilized not only
CH-π bonding but also π-π stacking and other functionalities interacted
with carbon surfaces [49]. The interaction of chemical functional groups
in biochar with the p-electrons of aromatic ring in VOCs (e.g., toluene)
may also act on the donor-acceptor mechanism involving oxygen or
nitrogen atoms of biochar as the electron-donors and aromatic rings in
VOCs as electron-acceptors [191]. The adsorption of chlorobenzene on
biochar exhibited greater affinity (i.e., Lennard-Jones potential) than
toluene, it was considered that the substituent groups of VOCs made a
deviated charge distribution, resulting in adsorption capacity of chlo-
robenzene higher than toluene [197].
VOC inherent properties, e.g., molecular size, molecular weight and
boiling point, also impact their adsorption behaviors besides the surface
adsorption mechanisms of biochars [40,50,198]. The higher adsorption
of acetone could be relevant to its finer kinetic diameter (0.46 nm) than
toluene (0.67 nm) and cyclohexane (0.60 nm) [35]. Benzene had higher
diffusion rate than other xylene VOCs, this may be attributed to the
small molecular size (0.58 nm) of benzene that could prompt its diffu-
sion into the micropores and access adsorption sites [198]. P-xylene
presented better adsorption onto biochar than M-phenyl and O-xylene,
which should also be derived from the P-xylene’s smallest kinetic
diameter (0.58 nm) [198,203]. Liu et al. [207] reported the adsorption
affinity of several VOCs by biocharKOH was negatively correlated with
the difference value between kinetic diameter of VOCs and average pore
width of biocharKOH, suggesting characteristics of the pore filling
mechanisms. The larger diameter of VOC molecules, the closer to the
pore walls of biocharKOH, and ultimately resulted in higher adsorption
affinities which are preferentially adsorbed at low relative pressure.
The diffusion coefficient of VOCs with higher molecular weight is
apparently larger than that of VOCs with lower molecular weight,
indicating the better adsorption of cyclohexane (84.16 g/mol) than
acetone (58.08 g/mol) [40]. The high boiling point properties of VOCs
suggests the stronger intermolecular forces with biochar, it would be
beneficial to the adsorption process. Therefore, the cyclohexane had
larger adsorption amount on hydrochar than acetone as its higher
boiling point of 80.74 ◦C than 56.53 ◦C of acetone [40]. The toluene,
cyclohexane, and ethanol with high boiling points (110.6 ◦C, 80.7 ◦C,
and 78.2 ◦C, respectively) presented greater adsorption on the
ball-milled biochar [50]. Much higher boiling point (138.36 ◦C) of
P-xylene facilitated its adsorption on biochar than benzene (80.09 ◦C)
[198]. The isosteric heat of chlorobenzene was generally larger than that
of toluene, which expressed the stronger binding force derived from the
higher boiling point of 131.72 ◦C of chlorobenzene [197]. However, it is
noteworthy that the desorption of VOCs with high boiling points would
be more difficult.
3.5.3. Effects of adsorption conditions
Current understanding of adsorption conditions such as adsorption
temperature and multi-component of VOCs which could mimic actual
combustion conditions is very scarce. As the physical exothermic pro-
cess, the sorption capacity of acetone dropped by 73.1–98.2% as the
adsorption temperature raised from 20 ◦C to 40 ◦C [35]. Benzene uptake
[42] and xylenes
enhancement sorption [203]
of temperature from 25by ◦Cbiochar alsoAt dropped
to 45 ◦C. the rangewith
of
20◦C–60 ◦C, a slightly higher adsorption temperature of 40 ◦C presented
the benefited adsorption for cyclohexane in comparison to the best ca-
pacity in 20 ◦C for acetone [194]. They explained that the size of
cyclohexane is larger than acetone, the relative high adsorption tem-
perature can achieve the transport of cyclohexane into the larger pores
on hydrochar and thus facilitate the adsorption when the rate-limiting
step is determined by intrapore diffusion. Cheng et al. [205] found the
fair adsorption performance of toluene for N-doped biochar in 40% and
80% humid environments. DFT results manifested that the biochar
containing abundant N-containing functional groups on surface could
achieve strong interaction with toluene and weak interaction with water
vapor.
During the multi-component adsorption, the partially adsorbed
toluene was replaced by chlorobenzene gradually when the biochar
approached adsorption saturation, may be relevant to lower volatility of
chlorobenzene and stronger adsorption of chlorobenzene onto the bio-
char [197]. The dynamic adsorption equilibrium of toluene was prior to
that of phenol onto the biochar, revealing the simultaneity of phenol and
toluene adsorbed onto the biochar in the gas phase. The competition of
various VOC species for adsorption sites onto the biochar led to a less
absolute adsorption amount of each species during a multi-component
adsorption, however, the overall adsorption performance of biochar in
multi-component tests was generally alike to the sum of the single gas
tests, indicating that nearly all active sites was occupied during the
competitive adsorption process [49]. The order of adsorption amount
for the studied four VOC species appeared to be consistent for both
single and multi-component tests, and the higher individual adsorption
amount of acetone should be attributed to the effective roles of finer
pores in capturing acetone, owing to a large amount of acetone was
replaced by larger molecules of p-xylene, toluene, and hexane during the
competitive adsorption process [49]. However, the reduction amounts
between individuals and mixtures in adsorption capacity were more
obvious for light VOCs (e.g., acetone) than heavy VOCs (e.g., hexane,
p-xylene, and toluene), which should be relevant to stronger van der
Waal’s forces between heavier VOCs containing more carbon atoms and
the carbon surface of biochar.
3.6. Adsorption performance of multi gas components
3.6.1. Synergistic adsorption of SO2 and NOx
Table S6 of the Supplementary Materials summarizes the preparation
conditions of biochar, and the adsorption and removal performance of
C. Wen et al.
multi gas-components by biochars. The simultaneous removal of SO2
and NOx was tried by the biochars impregnated with the metal oxides,
with the sorption capacity increased in the following sequence of CeO2
> V2O5 > NiO > Fe2O3 [208]. The metal oxides having powerful
oxidizing and oxygen storage capacity can introduce new oxygenic
functional groups such as C––O, C–O, and COOH onto the biochar,
which benefited the oxidation reaction of SO2 to SO3 and NO to NO2,
positively contributing to the high synergistic removal of SO2 and NOx
[208]. Zhang et al. [79] revealed that the SO2 removal uptake of Bio-
charamine during the atmosphere of co-presence of SO2 and NO was
apparently higher than that during the atmosphere without NO, and the
SO2 removal uptake first increased and then dropped as the concentra-
tion of NO increased, with the maximum amount of 216.19 mg/g at 120
◦C and 500 ppm NO. SO2 and NO themselves occur interaction reaction
especially at the N-containing adsorption sites of biochar during the
adsorption process, possibly contributing to the formation of the (NO2)
(SO3) intermediates [79].
The competitive adsorption between SO2 and NO on the active sites
of biochar was also reported. It is understood that molecules with higher
boiling point possess more Van der Waals attractive forces and inter-
molecular interactions, hence SO2 is readily adsorbed by the biochar
compared to NOx as the higher boiling point of SO2 than NOx [53,208].
Increasing SO2 concentration (up to 2500 ppm) would thus strongly
replace and desorb the NO from the active sites on biochar and thus
restrict NO adsorption [209]. Furthermore, higher concentrations of NO
(up to 700 ppm) compared to SO2 in the flue gas caused the much more
catalytical bonding of NO on the active sites of biocharCe. Therefore, it
reduced the active sites for the catalytical removal of SO2 [209].
With the presence of 15% H2O, more NO2 molecules was found to
present in the water layer due to NO2 is more soluble in water and a
much stronger oxidant than NO and O2, and the oxidations of HSO3 and
SO32 with NO2 to form SO42 were promoted, accordingly more SO2
molecules were captured into the water layer, and the overall removal of
SO2 was increased compared to the case without interference of the
simultaneous removal of NO [84].
3.6.2. Synergistic adsorption of SO2, NOx and Hg0
The biocharCe/Co yielded prominent Hg0 removal efficiency of 96.8%
and NO removal efficiency of 84.7% at 230 ◦C (Table S6) [98]. The
synergetic effects between Co and Ce oxides not only cause the unsat-
urated chemical bonds and imbalance charge as well as generate more
chemisorbed oxygen and oxygen vacancies, but also form amorphous
surface species which is beneficial to catalytic reactions. More active
oxygen species would be in favor of the reduction of NO and the
oxidation of Hg0 to produce HgO. The NO reduction reactions mainly
corresponded to the L-H mechanism (Equations (23)–(27)), and the Hg0
oxidation reactions were assigned to the Mars-Masson mechanism
(Equations (42)–(45)) [98]. The removal of NO presented a slight
decrease with addition of 100 μg/m3 Hg0, indicating that Hg0 showed an
adverse effect on the removal of NO, due to the formed HgO might be
accumulated to cover some adsorption sites. By contrast, NO appeared
to boost Hg0 removal when O2 was presented, as some weakly absorbed
NO could produce NO2 by reacting with the surface oxygen, which was
generally beneficial to the oxidation of Hg0 (Equations (51)–(54)) [43,
85,98,103,127,137]. However, as mentioned in section 3.2, excessive
NO (~400–800 ppm) was reported to cover the active sites and exhaust
the surface oxygens onto the biochar [126], which suppressed the
adsorption performance of Hg0. The removal efficiencies of NO and Hg
increased when the adsorption temperature increased and afterwards
decreased since 260 ◦C and 230 ◦C, respectively [98]. O2 could appar-
ently facilitate the removal of Hg0 and NO due to gaseous O2 could offset
the consumed chemisorbed oxygen and lattice oxygen of metal catalyst.
The presence of H2O may negatively influence the removal of Hg0 and
NO because of the competitive adsorption.
The simultaneous removal efficiencies of NOx, SO2, and Hg0 on
biochar varied with the increase of carbonization temperature which
affects the porous properties and surface defects of biochar. Carbon-
ization at 700 ◦C made the graphitization degree, rich pore structure and
surface defect content of biochar much higher than other temperatures,
which was benefit to the loading and dispersion of active components of
Fe species and in turn impacted the activity of biochar for the simulta-
neous removal [87]. The DFT calculation presented the strong adsorp-
tion between Fe and Mn species and the adsorbates of SO2, NOx, Hg0,
indicating that biocharFe/Mn possessed high simultaneous removal effi-
ciency of ＞80% at 300–350 ◦C [87]. When the biochar sorbents for Hg
was injected in coal-fired flue gas at 150 ◦C at an entrained-flow reactor,
about 80% gaseous mercury was removed and the SO2 and NO con-
centration decreased 35.6% and 36.0% respectively [87]. SO2 and NOx
had extremely limited effects on Hg capture by biocharNH4Br. 6% O2 and
10% H2O acted positively in the oxidation of SO2 to SO3 and H2SO4 and
oxidation of NO to NO2 [99]. A discrepant influence of SO2 was found on
the removal of Hg0, i.e., low concentration of SO2 facilitated its removal
apparently whereas high concentration of SO2 (＞~700 ppm) presented
inhibited effect [127]. In the co-presence of SO2 and NO, SO2 consumed
active oxygen and generated sulfate, leading to irreversible damage of
active sites onto the biochar, therefore, the reaction between Hg0 and
NO2 formed from NO were hampered by SO2 [137]. Gao et al. [98] re-
ported that the adsorbed SO2 may competitively inhibit the adsorption
of NO, NH3 and Hg0. The more deteriorative effect was resulted from the
joint influence of SO2 and H2O, as the competitive adsorption and the
formed ammonium sulfates could ruin the porous texture and cover up
the activated sites on biochar.
As mentioned in Section 3.4.4, the effects of SO2 and NO input on
CO2 adsorption was observed [169]. The increase of SO2 concentration
up to 1500 ppm slightly inhibited the CO2 adsorption performance, as
these two acid oxides would compete for the active cites. NO is not an
acid oxide and its input up to 800 ppm presented unchanged effect on
the CO2 adsorption.
3.6.3. Synergistic adsorption of VOC and Hg0
The composite of Mn–Fe oxides and biochar effectively removed Hg0
and aromatic o-xylene via the process of adsorption and catalytic
oxidation from simulated flue gas of power plant. The highly dispersed
metal oxides having high valence states provided more Lewis acid sites
derived from unsaturated metal sites and more adsorbed oxygen, they
would effectively facilitate the catalytic conversion of VOC to CO2 and
H2O and Hg to Hg2+, respectively. Similarly, biocharCu/Mn presented the
good removal efficiencies of HCHO (89%) and Hg0 (83%) shown in
Table S6, which were ascribed to the large specific surface area and
much chemisorbed oxygen and lattice oxygen promoted by the highest
molar ratio of Mn4+/Mn3+ [32]. The electron transfer between Cu and
Mn played the crucial role in the capture of HCHO or Hg0.
The Hg0 and o-xylene removal capacities firstly dropped with the
temperature increased to 200–250 ◦C and then enhanced with the
further increase in temperature up to 350 ◦C [11]. The formaldehyde
conversion and Hg0 removal efficiency also presented the lowest value
at 175 ◦C between 100 ◦C and 300 ◦C [32]. At low temperatures, the
exothermic removal via adsorption should be dominant, while the
extent of catalytic oxidation should be enhanced at high temperatures
[11]. On the biocharMn/Fe composite, the competitive adsorption be-
tween Hg0 and o-xylene and the catalytic reactions occurred simulta-
neously. Owing to the catalytic oxidation dominated pollutant removal
at high temperature, the competitive inhibitory effects were intensified
at high temperature as the Hg0 and o-xylene molecules battled for the
limited catalytic sites. Similarly, another study also found that the
removal efficiency of HCHO without Hg0 was a little bit higher than that
with Hg0, meanwhile the addition of HCHO had a decreased influence in
the removal efficiency of Hg0 from 95 to 83% at 175 ◦C as the compe-
tition adsorption and oxidation with Hg0. Fortunately, the removal ef-
ficiency of Hg0 can be recovered after withdrawing HCHO, due to the
activated cites can be released after HCHO transforming to CO2 and
gaseous O2 can replenish the surface active oxygen consumed by HCHO
C. Wen et al.
[32].
As the concentration of O2 increased from 0 to 12%, both the
removal efficiencies of HCHO and Hg0 increased, as the lattice oxygen
and the chemisorbed oxygen were regenerated by the gas phase O2. The
addition of SO2 and NO revealed inhibited influence in the removal of
HCHO, while NO presented an observed positive effect but SO2 had an
adverse influence for the Hg0 removal [32]. The adverse influence of
SO2 in the two pollutants should ascribe to not only the competitive
adsorption of SO2 but also the formation of metal sulfates onto the
biochar which made the content of active Cu/Mn components decreased
[32]. It was speculated that NO occupied the active sites faster than
HCHO because of its small molecular, implying the inhibited influence
of NO in the HCHO removal. Besides, NO would consume oxygen to
form NO2 and nitrate, the above-mentioned discussion indicated the
promoted capacity on Hg0 oxidation [32].
4. Adsorption isotherm, kinetic, and energy analysis
4.1. The adsorption isotherm models
The gas-phase adsorbates requires to diffuse into the interior of
biochar driven by the radial concentration gradient, and the adsorption
generally takes place in the void interior surfaces of biochar. Equilib-
rium relationships received by the modelling of adsorption isotherm
data in a wide temperature and pressure range correlating the amount of
adsorbate adsorbed on biochar with the applied gas pressure is crucial to
the design and optimization of biochar performance. The adsorption
isotherm models can indicate how the adsorbate and adsorbent (bio-
char) interact and the equations are described in Table S7 of the Sup-
plementary Materials. The Langmuir and Freundlich isotherm models
were widely applied to the research of biochar adsorption on gas pol-
lutants [48,59,161]. Langmuir equation assumes a simplified model
describing that the biochar surface has homogeneous distribution of
active sites and the gas molecule is adsorbed by active sites one by one
without interactions [28]. As a result, Langmuir model indicates a
saturated monolayer adsorption while operating at low partial pres-
sures. In the equation shown in Table S7, b as the Langmuir affinity
constant is proportional to the adsorption heat, it determines the
strength that the gas is bonded onto the biochar surface, i.e., higher b
values express a more powerful adsorption [28]. Freundlich model is the
empirical equation describing non-ideal and reversible adsorption on
heterogeneous surfaces with diverse adsorption sites, while adsorbate
occupied the higher affinity sites initially and as the surface coverage
accumulates, the adsorption strength declines. The model can thus be
applied to express multilayer adsorption, implying that the affinity
distribution and non-uniform adsorption heat throughout the hetero-
geneous surface. The Freundlich constant KF indicates the adsorption
capacity of biochar. The value of parameter 1/n is normally between
0 and 1, lower 1/n value indicates stronger interaction and the value of
n > 1 represents a beneficial adsorption condition between gas and
biochar. It is based on the assumption that the adsorption sites are
distributed with the adsorption heat exponentially. The Temkin
isotherm also expresses the adsorption behaviors on heterogeneous
surfaces, and supposes that the binding energies are uniform distributed
and the adsorption heat of all molecules in single layer reduces linearly
with coverage owing to the interactions between adsorbate and
adsorbent.
Atanes et al. [28] observed a heterogeneous surface indicated by
Freundlich equation for the biocharCO2 and biocharKOH. The most acidic
biochar presented the weakest affinity for SO2, while the biochar with
more basic surface increased its affinity. The Langmuir isotherm was
reported to match the experimental data of SO2 adsorption by bio-
charCO2 well over a temperature range of 25–100 ◦C [83]. Sumathi et al.
[209] found that the adsorption capacity of biocharCe at different input
concentration of SO2 or NO well matched the Langmuir adsorption
isotherms in comparison to Freundlich model. The above-mentioned
three models could well fit the experimental data of Hg adsorption
with correlation coefficients R2 > 0.90 for biochar prepared at 500–900
◦C [27]. Igalavithana et al. [52] and Nasri et al. [161] indicated that
both Freundlich and Langmuir models were fitted accurately with R2 >
0.99, implying that the CO2 adsorption of gasification biochar can be
described as monolayer or multilayer. Parshetti et al. [48] reported that
the Freundlich model could well fit the adsorption equilibrium of CO2
from biocharKOH, while the Temkin and Langmuir isotherms failed to
match satisfyingly with the equilibrium experimental data. Manap et al.
[210] revealed that the adsorption of formaldehyde by biochar was
distinctly determined by the Langmuir surface adsorption mechanism.
The Sips isotherm shown in Table S7 presents a comprehensive effect
of the Langmuir and Freundlich isotherms. The Sips predicts the typical
monolayer adsorption characteristic of the Langmuir isotherm at higher
pressures, whereas describes the Freundlich isotherm at relative low
pressures [20]. The sips model was reported to reproduce the tested
adsorption isotherms of CO2 fairly well [156,174]. The pure CO2 and N2
adsorption equilibrium were described satisfactorily by the Sips model
in the studied temperature up to 50 ◦C and pressure range up to 100 kPa,
compared with Langmuir and Tὸth models [156]. The Tὸth isotherm
equation is deduced from the Polanyi’s potential theory and is also
effective to heterogeneous adsorption [197]. It can fit the adsorption
equilibrium of pure CO2 and N2 satisfactorily by biocharO2 [144]. Zhao
et al. [197] found that the Dubinine-Astakhov model, also depended
upon the potential theory, can favorably describe the adsorption equi-
librium compared to the Langmuir and Tὸth models at different tem-
peratures, it can imply a stronger interaction for the adsorption of
chlorobenzene compared to toluene. Besides, the linearized isotherm
models matched the experimental data of benzene adsorption capacity
by biocharKOH in the order of: Langmuir > Dubinin–Radushkevich >
Freundlich [211]. An extended Jain and Snoeyink (JS) Langmuir model
was reported to well correlate with the mixtures of SO2 and NO at
different input concentrations [209], which considered the apparent
affinity and the adsorption on an active site of a particular gas can be
influenced by other gas, the maximum uptake thus did not remain
constant.
4.2. The adsorption kinetic models
The adsorption kinetic models shown in Table S7 provide valuable
insights into the mass transfer and controlling mechanisms of the
adsorption process. There are multiple steps in a typical adsorption
process, such as bulk diffusion indicating the mass transfer of adsorbate
to the surface of adsorbent, film diffusion indicating external mass
transfer, and the following surface diffusion and intra-particle diffusion
indicating the adsorption into the interior sites. The slowest step con-
trols the rate of a gas adsorption process. Gonzalez et al. [156] revealed
that the intra-particle resistance is more important than the external film
resistance to the overall mass transfer rate of CO2 under most
circumstances.
Pseudo-first order kinetic model (i.e., Lagergren model), with the
driving force expressed as a concentration difference, is good at
describing the early stages of adsorption with low surface coverage and
the amount of vacant available adsorption sites onto the adsorbent is
proportional to the gas adsorption rate [31,185]. Pseudo-second order
kinetic model (i.e., Ho and Mckay model) is derived from Langmuir
adsorption isotherms [61], it is more suitable to describe the adsorption
process involving chemical interactions [31], and the gas adsorption
rate is assumed to be proportional to the square of vacant available
adsorption sites number (Table S7) [154]. The pseudo-first order model
and intra-particle diffusion model (i.e., Weber-Morris) deduced from the
Ficks second law of diffusion focus on the process of external mass
transfer and interior diffusion respectively, while the Elovich kinetic
model and pseudo-second order model explore the surface chemical
reaction and catalytic reaction, i.e., chemisorption process [62]. The
Elovich model can describe the desorption process as the β value
C. Wen et al.

corresponds to the desorption rate of CO2 at different temperature [26].benzene accelerates its diffusion into biochar. The adsorption kinetic of
The CO2 adsorption onto the biochar at different operating temper-formaldehyde was best described by pseudo-first-order model for bio-
ature [26,31] or different pressure [161] can be modelled by usingchars treated by oil palm at 500–700 ◦C with high surface area and
several kinetic models. Lahijani et al. [153] reported that both the firstabundant extra vacant sites compared with other three mentioned
and second-order kinetic models had high fitted R2 coefficients, but the models, indicating the physisorption of formaldehyde [210]. In contrast,
fitted adsorption amounts were not well compatible for the experi-the biochar treated at 800 ◦C had lower surface area giving less vacant
site, however matched well with the Elovich kinetic model. Meanwhile,
mental results and usually overestimated the adsorption amount of CO2.
the intra-particle diffusion occurred within pores of the biochar,
Those four mentioned models were used by Rashidi et al. [26] and Nasri
contributing to a slow adsorption of formaldehyde [210]. The Elovich
et al. [161], they concluded that the pseudo-second-order model fitted
model presented the best fitting in both single gas and
the adsorption of CO2 well at various adsorption temperatures. The
multi-compositions adsorption experiments for toluene onto biochar
adsorption of CO2 complying with the pseudo-second-order adsorption compared with other three models [49], implying that chemisorption on
kinetics was also reported by others [155,183,187]. Rashidi et al. [26]heterogeneous adsorbing surfaces via hydrogen bonding and electro-
observed that the experimental data was deviated from the linear curve,static attraction is the dominant mechanism for the pyrolyzed biochar.
implying that the intra-particle diffusion was not the only major Another kinetic model shown in Table S7, namely Avrami model
rate-controlled step during the CO2 adsorption, while Nasri et al. [161] [153,154], is applied to explain the adsorption kinetic when the
observed that the pore diffusion was the dominant reason for the CO2adsorption process is affected by both physical and chemical in-
adsorption at pressures
Johari et above 1 bar
al. [27] observed thatusing intra-particle diffusion
the pseudo-second order model.
modelsteractions, especially for some functionalized sorbents. The Avrami
presented the optimum performance to the chemisorption of Hg0 over model was used to obtain better agreement of CO2 capture by biocharMg
the adsorption and breakthrough periods of biochar, in comparison between calculated and experimental values than the pseudo-first-order
the pseudo-first order model and Elovich model. Shen et al. [123 and second-order models [153]. Furthermore, the Fickian diffusion
divided the modeling into two steps and found that the first step was model analyzes the experimental results from breakpoint to equilibrium
controlled by the pseudo-first order model and the second step by the
time and describe the breakthrough curves [27], and the adsorption rate
pseudo-second order model. The modeling results revealed the path
coefficient can be received when the interior diffusion including surface
mass transfer from gaseous Hg0 to biochar surface during the first stage
diffusion and pore diffusion dominates the adsorption process. Johari
of Hg0 adsorption, while the overall Hg0 adsorption process of biochar
et al. [27] found that increasing the pyrolysis temperature resulted in
was obviously controlled by chemisorption. Zhao et al. [136] observed
reduced the effective diffusivity as well as Fickian adsorption rate co-
that the pseudo-first order and pseudo-second-order models were
compatible strongly to the Hg adsorption process, implying the combi-efficient, presenting a slower kinetic process. The deactivation model
nation effects of physisorption and chemisorption. The initial reaction(DM) was used by Zhang et al. [78] to simulate the breakthrough curves
rate appeared to be controlled by external mass transfer and surfaceof SO2 adsorption and investigate the SO2 adsorption kinetics, they
adsorption, while the dominant rate-limited step should be chemisorp-found that the CO2 activation promoted the incipient adsorption rate of
tion for the whole adsorption process [103]. Li et al. revealed that theSO2 by biochar at 30 ◦C probably due to it was mainly physisorption.
Hg0 adsorption rate of biocharH2O could be mainly governed by the Hg
mass transfer from flue gas to surface adsorption sites and followed 4.3. Adsorption energy evaluation
the pseudo-first order model [60], while the biochar activated at H The heat of adsorption, which is the negative adsorption enthalpy,
and modified by NH4Cl followed to the pseudo-second model, verifying elucidates the strength of adsorption. It is relevant to the interaction
the chemisorption process [61]. Shi et al. [104] observed the curvesbetween the adsorbent surface and the various adsorptive molecular
fitting to the pseudo first-order kinetic model, it showed the greaterforces including van der Waals, hydrogen bonds, hydrophobicity,
exterior mass transfer caused by the extensive hierarchical porous chemical bands, and dipole-dipole interactions [59]. Using the
structure of biochar fabricated with CaCO3, in comparison, the lack Clausius-Clapeyron equation (Table S7), the adsorption isotherms can
porous structures of un-fabricated biochar would limit Hg0 intraparticle be measured at different temperatures to assess the isosteric heat of
diffusion indicated by the intraparticle diffusion model. Furthermore,adsorption (i.e., differential heat of adsorption) [42,146,165,178],
Hsi et al. [116] found that the surface functional groups, especially thewhich indicates the temperature dependency of adsorption isotherms
S-containing groups, presented much more influence in adsorption [42]. The degree of coverage of adsorbate can also be determined, and
equilibrium than kinetics, while the porous properties of biochar maythe isosteric heat generally decreases with the increase of surface
affect the Hg adsorption kinetics more than equilibrium. In general, thecoverage [42,146]. The higher heat values during the initial adsorption
above-mentioned kinetic models were widely utilized to discuss the Hg of CO2 can be ascribed to the large amounts of narrow micropores [146,
adsorption onto the biochars [55,103–105,114,136]. 165,167] and surface chemistry such as nitrogen content [165,178], and
Kumar et al. [193] reported that the pseudo-second-order modelthe slight decrease in isosteric heats at higher coverage was attributed to
fitted better to the first-order model for the experimental results of VOCthe weak repulsive interactions for the CO2 molecules adsorbed on the
adsorption by pyrolyzed biochar. By contrast, the pseudo-first-modellarger pores of biochar [48,146]. It is noteworthy that the adsorption
isosteric heats by biocharKOH remained almost unchanged regardless of
worked better than the pseudo-second-model for the adsorption
the surface coverage, suggesting the adsorption occurs on relatively
phenyl VOCs, indicating its more homogeneous adsorption led by
homogeneous surfaces [146]. The isosteric heat of CO2 adsorption pre-
ball-milled treatment of biochar [198]. The second-order model per-sented a slow declining trend as the accumulation of CO2 adsorption
formed better than first-order model for the adsorption kinetics of polar amount [150,156,167,168], as was expected for indicating the hetero-
acetone, while opposite for nonpolar cyclohexane [194]. Zhang et geneity nature of adsorption sites in the internal surfaces of biochar. At
[40] found that both the pseudo-first-order and pseudo-second-orderlow CO2 pressure, the biochar has abundant vacant micropores benefi-
kinetics models can not predict the adsorption very well, indicating
that the adsorption of cyclohexane and acetone by hydrochars were cial to the pass of CO2 molecules into biochar, but the micropores in
biochar were occupied at higher CO2 pressure, the heat of adsorption
affected by multiple rate-controlling steps [35]. Besides, the adsorption
thus decreased due to the weak interaction between biochar and CO2
of phenyl VOCs onto biochar were governed by the interior diffusion,
[59].
according to the intra-particle diffusion model [198]. On one hand, the
In order to further investigate the adsorption mechanism of biochar
fine molecular size of benzene makes it diffuse into the micropores easily
and then access adsorption sites, on the other hand, the high concen- sorbents, the thermodynamic parameters such as enthalpy change (ΔH),
tration gradient and large driving force caused by high vapor pressure ofchange of gibbs free energy (ΔG) and entropy change (ΔS) were applied
C. Wen et al.
to describe the thermodynamic behavior of gas adsorption on biochars
at different temperatures [103,127]. In this case, ΔH determines the
endothermic or exothermic characteristics of the adsorption reaction
and the effects of adsorption temperature. ΔH is equal to the energy
released during the exothermic reaction at constant pressure, including
the energy lost to the surroundings and retained in the adsorption. For
an endothermic reaction, ΔH expresses the absorbed energy, including
the energy lost by adsorption and gained from surroundings [209]. Note
that the physisorption is exothermic while chemisorption can be both
exothermic and endothermic. The adsorption reaction of NO was
endothermic at temperatures below 300 ◦C as the ΔH was positive, the
NO molecules thus needed more energy to be adsorbed by biocharCe and
the NO adsorption was more favorable at higher temperature [209]. Li
et al. [127] reported that the Hg0 adsorption process was exothermic
implied by the negative ΔH, indicating that raising temperature was
adverse to the adsorption reaction. Yang et al. [103] observed the pos-
itive ΔH during Hg0 removal process, indicating that it was endothermic
for the biocharNH4Br, and the higher reaction temperature was favorable
to the adsorption of Hg. The adsorption of toluene, cyclohexane and
acetone on biochar was reported to be an exothermic process, observed
by the typical differential scanning calorimetry curve [40].
Other calculation or simulation methods were also applied to acquire
the adsorption of heat. If the heat of adsorption was supposed to be
irrelevant to temperature, it can also be evaluated by fitting the Lang-
muir isotherm equilibrium constant into the van’t Hoff equation
(Table S7) [83,209]. The activation energy of adsorption involves the
minimum required energy to prompt the normal molecule to become
activated molecule, which is able to reflect the active sites properties
and the adsorption mode [103,127,136]. The Arrhenius equation is
applied to calculate the activation energy (Table S7) [26], the negative
activation energy is derived from the reaction’s exothermic character-
istics and the reaction rate constant decreases when the adsorption
temperature raises [153]. Some study imply that the activation energy is
generally linearly relevant to the adsorption heat for surface diffusion
[212,213]. Note that the physisorption of gas molecules does not require
activation energy. Furthermore, the sorption heat of CO2 onto biochar
was reported to be calculated by integrating the sorption appearance
from the TGA diagram during a pre-defined time range [182].
To sum up, the heat of adsorption is normally between 5 kJ/mol and
800 kJ/mol. Physisorption typically produces an adsorption heat of
5–40 kJ/mol, most of experimental data showed that the adsorption of
CO2 by biochars was chiefly via physisorption [144,149,187]. These
values are much lower than the energy necessary to break covalent
bonds, suggesting a readily reversible desorption and regeneration of
adsorbent at a low energy penalty [168]. Whereas, chemisorption is
typically between 40 and 800 kJ/mol [59,187]. By contrast, the
adsorption isosteric heat of N2 (~16 kJ/mol) is alomost half than that of
CO2, which should be caused by its lower quadrupole moment.
Accordingly, it benefits the selectivity of CO2/N2 [156]. The adsorption
heat is critical to the cost profile of gas pollutants with biochar. The
higher isosteric heat of adsorption represents the stronger adsorption
and greater selectivity, meanwhile the regeneration of sorbent will be
harder as higher energy consumption is needed. It appears that an in-
termediate level of heat of adsorption is preferred. That is, from an en-
gineering point of view, the recommended values for post-combustion
capture of gas pollutants are between 30 and 60 kJ/mol [36].
4.4. Assistance from computational simulation methods
With the rapid development of computer technology, various
computational simulation methods, such as density functional theory
(DFT), classic molecular dynamics (MD), and grand canonical Monte
Carlo (GCMC), have been widely applied to describe the biochar struc-
ture model and adsorption process recently. DFT is mainly used to
predict the lattice constant, crystal structure, adsorption energy, elec-
tron energy density, reaction path, etc, in biochar [214]. GCMC can
build pore models of carbon materials to predict the adsorption iso-
therms, adsorption heat and electrostatic interactions of flue gas.
Zhao et al. [215] built a DFT model of biochar surface with or
without inherent potassium to uncover the mechanism of NO reduction,
they found that the bonding of K atoms (-O-K) to carbon atoms on bio-
char surface enhanced NO chemisorption through charge transfer,
reducing the energy barrier from 173.7 kJ/mol to 31.6 kJ/mol. Shi et al.
Hg
[65]0 on biochar prepared
established from model
the surface straw to
andsimulate
PVC, thetheunsaturated edge on
reaction process of
period graphite like the cluster model was applied to simulate the sur-
face active site, and the adsorption energy was calculated based on the
DFT calculation. The model of biocharCl doped with di-chlorine was
obtained to build the active sites of C–Cl bond. The results presented the
loading of dichloride atoms and carbonyl groups on biochar model
enlarged adsorption energy, would directly facilitate the adsorption
process of Hg0. The HgCl was confirmed to be an intermediate in a re-
action pathway. Jia et al. [216] constructed a 3D molecular structure
model based on molecular mechanics, eight adsorption configurations
were studied according to the location and amount of the chosen
adsorption sites. They found that the chemisorption of Hg0 onto the
biochar occurred notably, with adsorption energy of higher than 40
kJ/mol at six configurations. If the adsorption site was negatively
charged and the charges number was large, the adsorption of Hg0 onto
the biochar was facilitated. The molecular structure of iron-based bio-
char was determined as C45H24O12NFe [141], and the adsorption energy
of oxygen-containing functional groups was carboxylic acid > lactone >
aldehyde, implying the adsorption effect on Hg0. Feng et al. [164]
constructed the DFT models of biochar including N-Q, N-5, N-6, –OH
and –CHO. The adsorption energies between CO2 and biochar with ni-
trogen functional groups, oxygenic functional groups and without
functional groups was 30.87 kJ/mol, 24.07 kJ/mol, 7.27 kJ/mol,
respectively, confirming that the N and O functionalities in biochar
apparently promoted the adsorption of CO2 molecules. Another DFT
calculations showed that the adsorption energies of CO2 on pure carbon,
graphitic N, pyridine N and pyrrolic N surfaces were 0.15, 0.25,
0.32, and 0.41 eV, respectively [186], confirming that the N loading
was beneficial to CO2 adsorption. Cao et al. [217] used N/P co-doped
biochar as acetone adsorber and revealed the adsorption mechanism
on biochar surface using DFT. It was found that the binding energy of
C––P functional group ( 70.567 kJ/mol) and acetone was stronger than
that of C–P–O ( 32.516 kJ/mol).
Li et al. [218] established different functional group modified carbon
structure for CO2 adsorption using a combination of DFT and GCMC.
They found that the combination of pore widths <0.6 nm and alkali
metal (Li/Na/K) modifications improved the CO2 adsorption amount
and CO2/N2 selectivity. The isosteric heats of chlorobenzene and toluene
were acquired by the simulation of GCMC, and the higher value of
chlorobenzene than toluene signified its stronger binding force on bio-
char [197]. Zhang et al. [206] used GCMC to reveal that van der Waals
interactions were the main mechanism of toluene physisorption,
accompanied by electrostatic interaction which can be attributed to the
synergy between oxygenic functional groups and Cu metal sites.
5. Engineering consideration
5.1. Biochar preparation
As discussed in Section 2.4, the treating conditions on the biochar,
such as raw materials, pyrolysis and activation temperature, flow rate of
activated gas, concentrations of chemical activation agents, ratios of
biochar to activating agent, and processing time, affect the biochar
characteristics and further removal capacities of gas pollutants. Never-
theless, it is noted that the conditions of thermal treatment, activation
and functionalization of biochar are related to the time and economic
expenses required for the preparation of biochar. Therefore, the prepa-
ration of biochar should pursue both superior removal capacities of gas
C. Wen et al.
pollutants and the time and cost-saving methods.
The increased particle size of biochar arouses a relatively longer time
required to achieve the same interior gas concentration [33]. Guo et al.
[41] toobserved
mm 4 mm, that
bothwhen the particle
the gas size of biochar
film resistance increaseddiffusion
CO2 internal
and the from 1
distance were intensified, leading to slower mass transfer and decreased
breakthrough time. However, the resulting adsorbed capacity of SO2
were similar compared with the different sizes of biochar, i.e., ~14
mg/g for dynamic and 76 mg/g for static conditions. Wei et al. [166]
also found that the bamboo biochar ranging from 0.075 to 2.0 mm had
almost the same adsorbed amounts of CO2, indicating the little effect of
particle size.
An increase in carbonization temperature generally increases the
microporosity, ash, fixed carbon, basic functional groups, pH of biochar,
accordingly, acidic and oxygenic functional groups, H/C and O/C molar
ratios, volatile, and yields of biochar decrease [219]. The high pyrolysis
temperature is benefit to promote the porosity of biochar and intensify
the adsorption ability of gas, but at higher temperature, the high ash
volumes in biochar from high temperature pyrolysis blocked the pores of
biochar and destructed the surface functional group, both of which ul-
timately hindered the adsorption process [73]. The decrease of the
organic functional groups (mainly C––O) [105,106], the decomposition
of C-halogen functional groups [105] and sulfur species [107] at
excessive high temperature would weaken the chemisorption and
removal performance for Hg0. As to the extended activation tempera-
ture, it was reported to accelerate the reaction between carbon and
activation agents, and may encourage the widening and collapse of
pores instead of pore development and meanwhile destroy the func-
tional groups. The oxygen functional groups were reported to increase
for biocharH2O but decrease for biocharKOH with increasing temperature
[92].
Generally, the carbonization process of biomass can occur at a suit-
able activation time and the prolonged time do not differ markedly [28],
the more prolonged activation time may even cause the damage to pore
surface [73]. Yavuz et al. [72] found that when the activation time in
H3PO4 extended from 30 min to 120 min, the pore size of biochars was
gradually increased and widened firstly, and then decreased within the
further 60 min. Wu et al. [74] reported that the pore volume and surface
area of biochar were promoted moderately when the activation time was
prolonged from 1 h to 2 h during the H2O activation at 800 ◦C, mean-
while, the reduction of activation time weakened the acidity of the
biochar catalyst.
During H2O2 activation, too higher concentration input may cause
much powerful oxidization and make the collapsed inner pores and
decreased specific surface area [85], as well as may promote the ester-
ification reaction between –OH and –COOH, which eliminated the
chemisorption sites of Hg and resulted in a worse removal [37]. The
different optimum KOH/biomass ratios and temperatures exhibiting the
maximum CO2 capacity were reported in Section 3.4.2, with the inde-
pendent activation effects on the higher pore volume and BET surface
area, as well as higher basic oxygenic functional groups and oxidized
sulfur content [169].
Microwave pyrolysis is capable of generating the biochar with saved
cost, time, and energy consumptions in comparison to the conventional
pyrolysis. The maximum CO2 adsorption amount of biochar formed by
microwave pyrolysis at ~321 ◦C was reported to be higher than by
conventional pyrolysis at 550 ◦C [155]. At higher power levels, the
adsorption performance weakened possibly due to the pore damage.
Besides, the ultrasound process is thought to increase the BET surface
area and improve gas removal efficiency by enhancing the further
functionalization effect including the dispersion and penetration of the
NH4Cl [109] and dispersion active ingredients such as Mn and Ce [109].
The functionalization of ammonia, halogen and metals presented in
Figs. 3–5 also should be accessed suitably. The high activation temper-
ature in NH3 improved the porous texture and then enhance the
The lab-scale studies
impregnation widely of
effectiveness usenitrogen
the fixed[79],
bed reactor (FBR),
however, if thethermo-
activation
temperature is too high, the NH3 modification resulted in the decom-
position of nitrogen functionalities [78]. The narrow micropore volume
was also reduced at high temperature owing to the collapse of adjacent
pore walls, causing decreased adsorption of CO2 [58,59,177]. The op-
timum NH4Cl loading was reported to be about 5% [109], and the Hg
removal efficiency no longer increased [127,128] or even decreased for
NH4Cl loadings >7% [109], might be caused by the biochar surface
saturation leading to pore blockage and diminution of surface area. The
excessive loading value of Cu/Fe oxides, e.g., 15 wt%, would lead to the
blockage of the partial pore structure and reduce the physisorption
performance of Hg, further inhibiting the oxidation or chemisorption
process and was not conducive to Hg0 removal any more. The removal
efficiencies of HCHO and Hg0 apparently dropped when the molar ratio
of Cu to Mn was decreased from 1:1 to 1:5 or enhanced from 1:1 to 3:1
[32]. The suitable molar ratio of bimetals is benefit to form the well
dispersed active ingredients and can promote the occurred redox cycle
to produce new oxygen vacancies, receiving good mercury removal
capacity [54]. Too excessive metal input would result in the decrease of
redox activity and a noticeable decline of surface area, it would further
led to the reduction of active sites of adsorption and oxidation, and
thereby inhibited the catalytic removal. During the ball-milling treat-
ment, extending the time from 1 to 4 h was reported to benefit the
magnetic properties of biocharFe/Mn and improve the Hg0 removal [11].
However, when the process time of ball-milling was prolonged to 12 h,
the surface energies elevated and the metal oxides began to aggregate, a
proper time thus needs to be considered to improve the dispersion of
metal oxides onto the biochar for better functionalized effects.
The balance between adsorption performance and yields of biochar
is particularly important in choosing the treatment methods to produce
biochar, considering that a satisfying adsorption performance at the
expense of reducing biochar yield might not be economical from the
industrial point of view [220]. Al-Rumaihi et al. [221] summarized that
the feedstock type, carbonization temperature, heating rate, residence
time, and reactor bed type and height, have the influence on the biochar
yield. Generally, biomass with higher ash content leads to higher bio-
char yield due to higher inorganic content [222], and lignocellulosic
feedstocks with larger lignin content show higher biochar yield and
lower volatiles. Besides, the biochar yields are inversely related to the
pyrolysis temperature and the heating time, possibly posing an opposite
effect on the adsorption performance [71,223]. The biochar yield de-
creases with the increase of temperature, which is attributed to the
dehydration of hydroxyl groups and thermal degradation of cellulose
and lignin structures [71]. Sessa et al. [224] also reported that the
biochar yield was mainly determined by the maximum temperature, but
heating rate and the particle size did not affect the biochar yield
significantly when uniform heating was assured. Meanwhile, biochar
yield was reported to increase with the increase of holding time [71].
As to some typical methods of activation, the biochar yield of mi-
crowave pyrolysis was reported to be lower than that of conventional
pyrolysis at the same processing temperature of 600 ◦C [155]. The
biochar yields from activation of steam, CO2 and KOH were reported to
be 59%, 55% and 35%, respectively [225]. The high CO2 activation
temperature reduces the surface functional groups, hydrophobicity, and
the production yield of biochar, although increasing the surface area and
porosity positively. After incorporating urea phosphate, the biochar
yield was significantly enhanced from 25.8% to 50% at pyrolysis tem-
perature of 600 ◦C [226]. It is caused by the fact that H3PO4 and its
polymers can combine with the organic components in sawdust to
generate phosphates and polyphosphate esters through crosslinking,
which avoids the escape of carbon atoms [226]. The impregnation ratio
of NaOH and urea phosphate did not affect the biochar yield apparently
[223,226].
5.2. Reactor conditions
C. Wen et al.
gravimetric analyzer (TGA) and static volumetric analyzer. FBR presents
the dynamic and volumetric sorption, the TGA presents a kinetic and
gravimetric sorption [20], and the static volumetric analyzer measures
the gas adsorption/desorption isotherms and equilibrium, generally at
different temperatures and a pressure range from 0 to 101 kPa. The
dynamic tests generate necessary data for calculating of adsorption ki-
netic and rate equation. Through the fixed bed, the gas adsorbate is
passed at a given flow rate and the experiment is terminated when the
outlet flow concentration is equal to inlet concentration, indicating the
breakthrough occurs. The adsorption capacity of biochar can be calcu-
lated via the breakthrough curve as a function of operation time, using
the area integration. In the TGA test, the gas adsorbate uptake is
weighted from the increased mass gained by the biochar during the
feeding of the adsorbate gas flow.
The understanding of influences of controlling parameters for FBR in
the adsorption performance is necessary to the further engineering
application of large-scale fixed adsorption bed device. The bed density of
reactor is calculated from the quality of adsorbent loaded into the vol-
ume of the reaction column. From a practical of view, the higher bed
density can decline the required volume of adsorbents [174]. The length
of mass transfer zone (MTZ) represents the active part where adsorption
occurs in the fixed bed, presenting a concentration gradient in adsorbate
from zero to equilibrium [41,162]. Guo et al. [41] observed that the
increase of column length retarded the breakthrough time and exhaus-
tion time, however, had an insignificant effect on the MTZ length.
Meanwhile, the diffusion is generally faster when the particle size of
biochar is smaller, the MTZ will thus be shorter and sharper [41].
The increase of feeding rate promotes the surface diffusion so that
the mass transfer rates increases, leading to steeper breakthrough curve
and correspondingly a relative lower adsorption capacity of SO2 [83].
The servicing time of the packed column was decreased due to a higher
loading factor [41]. An approximate linear correlation between the inlet
SO2 concentration and the adsorption amount of SO2 was observed by
Yavuz et al. [72]. Furthermore, Lua et al. [83] and Iberahim et al. [6]
revealed that the higher GHSV (gas hourly speed velocity) indicated by
higher gas flow rate would transfer more gases into the adsorption bed
per unit time and led to faster breakthrough. The contact time between
SO2 and biochar decreased, sometimes the equilibrium had not reached
when the breakthrough occurred, thereby reducing the treated and
adsorbed amount of SO2 [6,41,75]. At higher GHSV, the decline in
adsorption capacity of SO2 and NO was attributed to the insufficient
contact time or space between the sorbent and the simulated flue gas
[209]. The GHSV was also important to the Hg0 removal, the Hg0
removal capacity declined from 65.9% to 50.0% as the GHSV enhanced
from 260,000 h 1 to 520,000 h 1 [61]. Similar findings were given by
Shen et al. [109] and Xu et al. [105].
5.3. Adsorption rate
The dynamic breakthrough experiments of feed gas was generally
used to quantify the rate of adsorption and then the adsorption amount
of typical gas such as SO2, NO and CO2. The adsorption rate can be
calculated from the slope of the breakthrough curve of SO2, NO, and CO2
and the slope of accumulative adsorption curve of Hg0 and VOCs, which
are difficult to penetrate due to the very low concentration. The
breakthrough time is calculated between the initial feeding time and the
saturation time, which detects the non-zero gas concentration at the
outlet of the reactor column. Generally, the experimental data showed
that the breakthrough time decreased with increasing both feeding
concentration [33,83] and flow rate of gas or GHSV [6,41,83]. An in-
crease in gas feeding concentration improves the surface diffusion and
then the mass transfer coefficient, resulting in a relatively steeper
breakthrough curve and earlier breakthrough of SO2 [33]. Besides, it is
expected that the more flow rate of gas or GHSV will deliver high flux of
adsorbate into the reactor bed per unit time, which decreases the
breakthrough time of SO2 [6] and CO2 [153]. However, the ultimate
adsorption capacity may remain almost the same when sufficient time is
provided [153]. As the adsorption temperature increased, both the
breakthrough time of SO2 [79] and CO2 [186] were found to be
decreased, indicating that the increased adsorption temperature allows
for a faster transport of gas within the pores and then improves diffusion
and adsorption rate. The reported data of breakthrough time of typical
gas differ in several seconds to hundreds of minutes, depending on the
specific experimental conditions including gas type, gas feeding con-
centration, gas flow rate or GHSV, adsorption temperature, and loading
weight and shape of biochar. Therefore, it seems to be difficult to
compare the rate of adsorption from different publications.
Al-Rahbi et al. [88] reported that both increasing microporosity and
surface area of biocharKOH correlated directly with the increased NO
breakthrough, indicating a faster adsorption rate. Similarly, Jia et al.
[55] reported that the diffusion and then surface adsorption rate of Hg0
was greatly improved with the development of pore structure and sur-
face chemical properties. The physically biocharCO2 presented faster
adsorption rates of CO2 than chemically biocharKOH at 75 ◦C, indicating
that the more hierarchical pore structure of biochar can lead to a higher
diffusion rate of CO2 [146]. The N-doped hierarchical biochar showed a
high adsorption rate of 0.189 min 1 for toluene, which is benefited from
mesopores improving the mass transfer behaviors [227]. The VOC
adsorption rate constants of 600 ◦C pyrolytic biochar were higher than
that of biochars produced at 300 ◦C, which suggested that the physical
adsorption rate was slightly higher than partition rate [35]. The
adsorption saturation time of acetone from biochar after ball milling was
apparently shortened from 40 min to 20 min, as the BET specific surface
area and the oxygenic group content of biochars increased after ball
milling [228]. Generally, the surface adsorption is the main adsorption
form in the initial stage, which makes the surface adsorption rate faster
than the intraparticle diffusion rate owing to the large amount of
adsorption active sites existing on the surface of biochar [114]. For
example, the CO2 adsorption increased almost vertically as a function of
time within the first 5 min [229]. Subsequently, the adsorption rate
decreases gradually due to the depletion of active sites, which is
confirmed by the geometric logarithm increase of Hg adsorption rate
with time elapsed over 600 min, with an average adsorption rate of 1.40
μg/g ⋅ min 1 [138].
5.4. Cycle and regeneration
Regeneration of spent biochar is necessary to the successive
adsorption-desorption cycles in industrial applications, and a low
regeneration temperature and a short cycle time should be pursued. The
rapid kinetics process is benefit to shorten the adsorption cycle time. The
stronger chemisorption would make the regeneration of biochar sorbent
harder, this requires higher desorption/regeneration temperature with
high energy consumption [156].
Atanes et al. [28] found that the SO2 adsorbed by acidic biochar
adsorbents via physisorption would be readily to regenerate for more
adsorption cycles. Braghiroli et al. [76] reported that thermal treating
regeneration mostly affected the physical structure of the spent biochar,
H2SO4 adsorbed onto the biochar was removed along with the decrease
of carbon, whereas water treatment mainly dealt with the adsorption of
SO2 found in surface. These two types of treatments were tested by
Iberahim et al. [73] to find out that about half adsorption amount of SO2
was regenerated after the first cycle, and the lower treatment tempera-
ture may lead to higher residual sulfur which caused the decrease of SO2
adsorption. The SO2 adsorption efficiency decreased when the regen-
eration cycles increased to the third times, owing to the damage of pore
texture and active adsorption sites [6]. The regeneration efficiency of
biocharH2O was evaluated with 6 cycles by Braghiroli et al. [76]. They
found that the pore structure of biochar was changed after regeneration
cycles, which resulted in a moderate promotion in micropore volume
and surface area since the 4th cycles. Besides, the acid surface after SO2
adsorption was decomposed during desorption test at 600 ◦C, which can
C. Wen et al.
leave new basic surface and favor the further SO2 sorption capacity
possibly compared with the original biochar. These two reasons sur-
prisingly made the SO2 adsorption capacities from the 4th-6th cycles
higher than those from the 1st-3rd cycles.
The Hg captured by the stable sites is relatively difficult to re-release,
whereas the Hg retained by the physisorption and catalytic sites is
readily to desorb by heating [230]. Fan et al. [114] showed that the
physisorbed Hg0 onto the biochar initially desorbed at 160 ◦C, the
desorption peak temperature of the organic Hg-OM species formed by
the heterogeneous reaction of Hg0 with carbonyl and carboxyl groups
was 210 ◦C, while the corresponding temperature of HgO happened at
300 ◦C. Tang et al. [230] reported that Hg desorbed at 200 ◦C was
caused by the oxidation of Hg by catalytic sites, and that desorbed at
280 ◦C was attributed to the adsorbed Hg onto the surface functional
groups. Yang et al. [43] reported that the biocharCu/Fe exhibited a good
regeneration performance and still had a high Hg0 removal efficiency of
76.33% after 6 regeneration cycles, compared with the efficiency of
90.58% by original biochar. Shan et al. [108] reported that the average
Hg0 removal capacity was 10% lower than the original 87.1% after the
5th cycle for biocharMn/Fe. The average Hg removal capacity of the re-
generated biocharMn/Ce just decreased by 16.1% after 10 cycles, owing
to the destruction of porous properties and active site [54]. Besides, the
Fe impregnated biochar maintained above 90% after 6 cycles [119].
Two main types of adsorption technologies are deemed as feasible in
post-combustion capture of CO2 and can match the adsorbent regener-
ation: temperature swing adsorption (TSA) and pressure swing adsorp-
tion (PSA) or even vacuum swing adsorption (VSA) [174]. The biochar
can be readily regenerated by increasing the temperature in TSA process
and/or reducing the system pressure in PSA process [144]. However, it
would be uneconomical and difficult to compress the flue gases with
high flowrate for a conventional PSA process. Plaza et al. [144] reported
that 5 kPa seemed a reasonable low pressure level during the depres-
surization desorption step of CO2 in order to maintain the low operation
costs. By contrast, the CO2-rich adsorbent was regenerated by raising the
reactor temperature in TSA process, this can be easily achieved by
harnessing a heat steam from the running industrial plant via adding the
heating exchanger [174]. Because of the weak interactions between CO2
and biochar determine the requirement of low energy, its regeneration is
relatively simple and has been observed widely [148,149,174], and
most of reported biochars can be rapidly and simply regenerated over
multiple cycles without distinct drop of adsorption capacity via TSA
process [31,48,153] or PSA process [31,48,148,150,153,166,185]. The
high reusability of the biochar sorbent elucidates that physisorption
process was the predominant mechanism. The decline in capture ca-
pacity of CO2 with cyclic process may be due to loss of surface activity,
agglomeration and incomplete regeneration of sorbent [171]. It should
be mentioned that the spent biochar captured CO2 could be utilized as
the soil amendment and carbon storage directly, as CO2 would not leak
under normal soil/atmospheric temperatures [187], in this case it is no
need to regenerate the biochar for a long time.
For the renewable potential of VOCs, Zhang et al. [40] indicated that
the desorption temperature of acetone on biochar was lower than that of
cyclohexane, affected by both the high porosity and abundant functional
groups onto biochar as well as the properties of VOCs. The VOCs
adsorbed in the narrow micropores generally required higher desorption
temperatures, and the abundance of oxygenic functional groups onto the
hydrocharH3PO4 would strengthen the adhesion force with hydrophilic
acetone. Besides, the high boiling point adsorbate has strong affinity to
the sorbent, therefore the higher boiling point of cyclohexane compared
to acetone explained its more difficult desorption. Nearly 90% of the
adsorption capacity of acetone was remained at the end of the 5 cycles,
while it had 83.30% capacity remaining for cyclohexane [194]. Another
study presented that there were merely 2.5% and 0.9% decline in
cyclohexane and acetone respectively during the last four cycles [40]. A
large decrease of adsorption capacity of VOCs primarily happened in the
first cycle [35], should be attributed to the incomplete desorption of
VOCs derived from either strong affinity between VOC and biochar, or
the formed permanent bonds requiring higher temperature to break
them [198].
5.5. Biochar selection consideration
Some viewpoints that can reflect the commonality and personality of
adsorption characteristics of various pollutants are summarized in this
section, which can be used to help guide the selection of biochar. The
high BET surface area and developed micro-porosity characteristics in
biochar are necessary to provide sufficient physisorption sites for
enhancing the gas adsorption [48], while an appropriate mesoporous
and macropore network works to enhance the diffusion of the gas
molecules into the micropores. The high carbonization temperature
generally increases the micropore volume and surface area of biochar,
however, some micropores might be coalesced to form mesopores or
macropores at the overhigh temperatures. Similarly, the mild conditions
of activation, microwave, ultrasonic and plasma are all able to develop
the porous properties of biochar. The physisorption would be intensified
when the pore distribution of biochar matches the molecular dynamic
size of gas adsorbates [19,37]. SO2, NO, Hg, CO2 have the kinetic
diameter of 0.364 nm, 0.3 nm, 0.32 nm, 0.33 nm, respectively. The
typical VOCs, such as toluene and chlorobenzene, have the kinetic
diameter of 0.46 nm and 0.78 nm, respectively. Therefore, they tends to
collide and adsorb on micropores effectively due to their kinetic diam-
eter much less than 2 nm [30]. For example, Coromina et al. [151]
indicated that the adsorption energy was optimized when the pore size
of biochar was 2–3 times than that of CO2 molecule, the optimum pore
size was thus between 0.7 and 0.9 nm for CO2 adsorption.
The adsorptive capacities of SO2 were reported to be approximately
linearly proportional related with the micropore volumes of bio-
charH3PO4 and biocharCO2 [72,75]. Al-Rahbi et al. [88] reported that the
best NO removal efficiency was related to the increase in micropore
volume and BET surface area of biocharKOH. The linear correlation be-
tween the amount of CO2 adsorbed at 25 ◦C and 1 bar and the pore
volume of 0.33–0.63 nm, and the correlation between narrow micro-
pores of 0.33–0.48 nm and adsorption amount at 25 ◦C and 0.15 bar
were reported [167]. Evidently, the narrower micropore is mainly
responsible to CO2 adsorption under the practical flue gas conditions
with lower pressure of ~15% CO2. Furthermore, the capture of CO2 can
be carried out at relative high temperature when the biochar contains
more ultra-micropores, owing to only the narrowest pores mainly acting
as the most energetic adsorption sites maintain occupied as increasing
the temperature [156]. Accordingly, The CO2 or VOCs adsorbed in the
narrow micropores generally required higher desorption temperatures.
The strong linear correlation between micropore volumes or BET surface
area of biochars and adsorption capacities of VOCs were also widely
observed [40,191,194,196,198]. The narrow micro-porosity was re-
ported to be dominant at low concentrations of toluene with the kinetic
diameter of 0.67 nm [191,196] and P-xylene of 0.58 nm [198], while the
more micropores of ~0.8 nm benefited the adsorption performance of
chlorobenzene (0.78 nm) than toluene [197]. The small molecular size
(0.58 nm) of benzene could prompt its diffusion rate into the micropores
and Itaccess adsorptionthat
is noteworthy sites,
the compared to other
functionalized xylene VOCs
treatments [198].metal
including
and halogen modification would block the biochar micropores and
occupy the active site. The physisorption performance of NO or Hg
should not be destroyed by the too drastic treatments, otherwise the
further chemisorption or catalytic oxidation process would be inhibited.
Some above-mentioned treatments especially the physical activation
of O2, H2O, H2O2, and CO2 could introduce some oxygenic functional
groupss (mainly C––O, –OH) onto biochar, affecting the chemisorption
performance of various gaseous pollutants. The metal oxides having
powerful oxidizing and oxygen storage capacity can also introduce new
oxygenic functional groups onto the biochar, and the ball-milling pro-
cess helps to further increase the oxygenic functional groups effectively.
C. Wen et al.
However, the oxygen functionalities on the biochar surface could
decompose at overhigh treatment temperature [51].
The surface oxygenic functional groups, e.g., carboxyl, lactone, and
phenolic hydroxyl, are closely related to the acidic character of biochar,
accordingly may favoring the polarity and hydrophobicity of biochar.
Therefore, they are benefit to the sorption of polar and hydrophilic VOCs
[193]. On the contrary, biochar reflects the hydrophobic properties
making them favorable as an adsorbent for the hydrophobic and
non-polar CO2 and VOCs [21,48]. It should be noted that certain surface
oxygenic functionalities such as ketone, chromene, and pyrone, and
nitrogen containing groups can contribute to the basicity of biochar
[51]. The higher proportion of alkaline C–O groups in biochar could lead
to stronger electrostatic or hydrogen bonding interaction with acidic
CO2 and SO2 [52,169]. The strong adsorption is related to the oxygen-
ated groups onto the biochar, which are believed to be catalytic centers
for SO2 oxidation to SO3 and then from H2SO4 [68]. The acidic
oxygenated anchoring sites are also the effective intermediate stage to
introduce the nitrogen functional groups, which are generally effective
for acidic SO2 and CO2 adsorption especially at the adsorption temper-
ature higher than ~100 ◦C.
The oxidation treatment introduce large number of oxygenic func-
tional groups on the metal catalyst. They serve as active sites and pro-
duce the high-valence state (e.g., Ce4+, Mn4+) through electron transfer.
C––O groups generally serve as electron acceptors and facilitate the
electron transfer for the oxidation of Hg0 into HgO during this process
[61,123]. Meanwhile, they can not only help to adsorb NO but also
improve the dispersion of active phase to generate more adsorption sites
for NH3 [90], which can be beneficial to the oxidation of NO to NO2 and
the following L-H mechanism or “fast SCR” reaction to form N2 [90,96,
97]. Besides, the oxygenic functional groups onto biochar increase the
content of volatile organic matter during ball milling [50,198]. There-
fore, the adsorption of VOC onto ball-milled biochar is also dominated
by the combined mechanisms of surface adsorption and partition [50].
5.6. Field tests
In the field scale coal-fired unit, only the adsorption removal of Hg0
using biochar was reported. The biochar can be injected into the flue gas
stream to capture Hg0 before dust remover, then the spent biochar is
captured by precipitator and recycled to re-inject into the flue gas after
regeneration by high temperature desorption [54]. De et al. [117]
evaluated the performance of the biocharH2O in Poplar River, Coronach,
Canada. It is a 562 MW power plant firing lignite, and the stack gas
temperature for this test was 120–130 ◦C. The biocharH2O can attain
more than 90% Hg capture when the biochar feeding rate was higher
than 25 kg/106 m3 of flue gas amount, while 80% of Hg removal rate
from 12 kg/106 m3. The ratio of biochar to Hg can be chosen to arrive
the suitable operating cost of Hg capture process. Tang et al. [125]
carried out an onsite sampling in the 660 MW demonstration pulverized
coal unit to compare the effects of Hg removal monitoring from the
biocharHBr traps methods and the existing Ontario Hydra Method. The
parallel Hg sampling results of biochar sorbent traps and the OHM
showed 13.21 and 12.63 μg/Nm3 respectively in the sampling sites of
boiler outlet, indicating satisfactory Hg removal and collection by the
biocharHBr traps.
6. Challenges and perspectives
6.1. Research gap on exploring the adsorption mechanisms of biochar
The advanced quantitative analyzing methods. Various character-
(1)
ization technologies have been applied to measure the pore
textural property and the occurrence of surface functional groups
of biochars before and after use. Shafeeyan et al. [51] and
Abdulrasheed et al. [53] systematically described the typical
methods including chemical titration, X-ray photoelectron
spectroscopy (XPS), Fourier transform infrared spectroscopy
(FT-IR), temperature programmed desorption (TPD) and
temperature-programmed reduction (TPR). For example,
NH3-TPD can be applied to evaluate the surface acidic charac-
teristic of biochar, and H2-TPR measurement is used to observe
the redox property of metal oxides. However, the functional
groups of biochar are measured by those technologies off-line,
which may change when the spent biochar is cooled down.
Therefore, some in-situ advanced methods to quantitatively
analyze biochar should be developed to detect the adsorption
mechanisms of biochar
Further research demandcorrectly [19].
for typical gas pollutants. The metallic
(2) oxides with high basicity were reported to successfully improve
the removal capacity of SO2 of activated carbon support by
chemisorption, and even performed better than the amine group
[53]. However, little similar attempts on biochar have been car-
ried out at present. The existing research on CO2 adsorption using
biochar are mainly relied on simulated gas that consist of merely
several major gas compositions (e.g., N2, CO2, and H2O) or even
pure CO2. More studies are necessary to elaborate the competitive
adsorption by biochar in industrial flue gas containing some
impurities [21]. Many solid adsorbents were modified by noble
metals to improve the Hg adsorption capacity because of their
regeneration capacity and satisfying high temperature stability
[22], mainly including Ir, Pt, Pd, Rh, Ag and Au. From the sci-
entific view rather than economic view, the effects of noble
metals modification can be attended to check their Hg removal
performance after adding into biochar. The adsorption of VOCs
onto solid sorbent generally decreases with elevating the
adsorption temperature, mainly attributed to physical
exothermic interaction. Noteworthy, high temperature would
facilitate the molecular diffusion, catalytic oxidation and chem-
isorption, causing the complicated effects on VOCs adsorption
especially for the metal oxide modified biochar. Besides, hu-
midity can affect the adsorption of VOC onto carbon materials
due to the H2O molecules can competitively occupy the pore
sites. However, the influence of temperature and humidity in
VOCs adsorption
Further by biochar
research demand for were little studied
synergistic [10,231].
adsorption of multi gas
(3) components. As presented in Section 3.6 and Table S6, the
research on multi gas adsorption by biochar is very limited at
present and none of those tried more than three types of gas
pollutants at the meantime. Some hints can be considered for
further synergistic adsorption of multi gas components. The
oxygenic functional groups onto the biochar are generally acidic
and they are benefit to the sorption of polar and hydrophilic
VOCs, besides, they provide abundant amounts of active sites
onto which NH3 or Hg can be adsorbed, the higher NO and Hg
removal efficiency can thus be achieved. Meanwhile, the
oxygenated anchoring sites are the effective intermediate stage to
introduce the nitrogen functional groups (Fig. 3), which are
generally more effective than the pore properties for the
adsorption of acidic SO2 and CO2, especially at an adsorption
temperature higher than ~100 ◦C. The redox reactions of metal
catalyst in biochar (Fig. 4) and the improved adsorption ability of
NH3 and Hg mainly determine the NOx and Hg0 removal per-
formance of the biochar, and also able to promote catalytic
conversion of VOC to CO2 and H2O. The metal oxides may also
react with SO2 or CO2 to generate sulfates or carbonates at a high
adsorption temperature (Fig. 4). Furthermore, the development
of biochar capable of simultaneous removal of multi gas pollut-
ants at one-step process remains a challenge as the inevitable
competitive adsorptions.
C. Wen et al.

back the waste biochar into boiler as it is a fuel with better

6.2. Concerns on the industrial application
heating value and energy density than its parent biomass. As the
The requirement of industrial scale configurations loading biochar. As disposal demand of CO2 having much higher concentration than
(1)
mentioned in Section 5.2 and 5.4, nearly all studies on gas pol- other gas types, the biochar specifically adsorbing CO2 can be
lutants adsorption of biochar were performed in lab scale reac-
buried as a type of carbon sequestration before it loses the
tion systems until now. However, it should be difficult to present
effective adsorption capacity. In this case, biochar plays as the
as good adsorption capacity at industrial complicated conditions
carbon-sequestering soil amendment.
as those received in lab scale systems, due to the particle char-
acteristics of biochar sorbents and reactor bed configurations 6.3. Economy, energy and environmental analysis
need to be considered. The possible layout types for interacting
It is worth noting that many of modification processes onto biochar
biochar sorbents with combustion flue gas streams are injection
adsorbent may add extra synthesis costs and cause harmful environ-
systems, fixed-bed, moving-bed, and fluidized-bed [232]. The
mental implication. For example, the common treatment of acid solvent
multiphase reactor may efficiently promote the mass transfer and
activation is time and energy consuming in the applications of industrial
diffusion of gases which should be the major rate-controlled steps
scale [11]. Therefore, the green and simple activation and/or doping
of gas adsorption, thereby improving the adsorption efficiency methods, such as ultrasonic, plasma, microwave, and ball-milling,
[135]. The efficient utilization of the biochar sorbent in typical should be attempted in order to achieving the large scale commercial
industrial scale will determine the feasibility and economy of production. Huang et al. [155] indicated that microwave pyrolysis can
biochar adsorption technology for the removal of gas pollutants achieve a near-zero emission of CO2 according to the mass balance
from combustion offlue
The requirement gas. sorbent in industrial scale. The biochar
biochar relationship between the CO2 adsorption of biochar and the microwave
(2) pyrolysis. The biochar sorbents lack of ample capabilities of recycling
adsorbents should satisfy the following criteria under industrial
condition for an economic and idea capture of gas pollutants: (a). and regeneration would increase the costs of production, operation, and
be produced via inexpensive and energy-save processes, e.g., post-processing and lead to environmental issues because of the inevi-
microwave, plasma, ultrasonic and template; (b) present large table solid waste treatments [23]. The magnetically separation can be an
adsorption capacity and high selectivity with N2, and should be important assistance to the cyclic utilization of biochar, Yang et al.
tolerate to other flue gas compositions (e.g., SOx, NOx, H2O and [233] notified that the recyclability of magnetic separation adsorbents
led to only a 1/4-1/5 utilized cost compared to traditional AC adsor-
light hydrocarbons) and it is better to remove multi gas pollutants
bents. However, the effectiveness of these methods for the modification
simultaneously; (c). fast adsorption and desorption kinetics, low
and application of biochar on an industrial scale is still unclear [21].
energy requirements for desorption, and good mechanical
The biochar costs and prices depend on local raw material avail-
regeneration stability are necessary to achieve long-term
ability, thermal treatment conditions, process flow, reactor availability,
adsorption-desorption cycles operation; (d). the separation for recovery, service life and markets [234]. Praveen et al. [235] presented
the recovery of biochar adsorbents from the magnetic impurities that the worldwide mean price of biochar up to 2018 was ₹185.5 kg 1
is a challenge, and the magnetically separable biochar should be (¥15.5 kg 1, China’s RMB Yuan), with the data source of a total of 91
considered [23]. These problems are important for developing companies reporting the sales of biochars across the world. They esti-
the candidate biochar sorbents being and designing the gasmated that the cost of biochar of 1 kg was ₹45.4, ₹42.7 and ₹42.5
Theremoval
optimumsystem, they
adsorption still needThe
conditions. to be boardly
cost and and
of biochar deeply studied.
capture (¥3.5–3.7 kg 1) for coconut shell, rice husk and groundnut shell in India,
(3)
efficiencies of gas pollutants should be balanced in order to work respectively [235]. Dai et al. [234] stated that the average price of
in the typical engineering parameters [159], and the adsorption biochar in the United States from a survey of 23 biochar sellers in 2014
capacity and kinetics of the same biochar adsorbents will differ was $2512.0 ton 1 (¥15.9 kg 1) and the cost of biochar production in
apparently under various flue gas parameters. For instance, CO China was reported to be only about 15% of other similar foreign
in the flue gas streams of the energy and industry facilities, such products. Alhashimi et al. [236] evaluated the economic performance
as power plants, lime production, or steel plants have different and found the mean cost of AC and biochar were $5.6 kg 1 (¥35.5 kg 1)
concentrations up to 35%, affecting the choice of optimum and $5 kg 1 (¥31.7 kg 1), respectively, however, they recommended
adsorption removing technology [189]. The SCR catalyst is that the prices should be considered cooperatively with adsorption ca-
promising to simultaneous remove NOx and Hg0, and the low pacities to evaluate the bulk cost of pollutant capture. For economic
temperature catalyst working in ~150–200 ◦C should be devel- performance, Tarka et al. [237] chose a baseline of $10 kg 1 (¥63.5
kg 1) for solid sorbents in the sensitivity analysis, and they found that a
oped. The most acceptable location for a CO2 capture unit is after
cost of $5 kg 1 presented a good performance and a cost of $15 kg 1
FGD with temperatures of 50–105 ◦C in the nearby location, and
(¥95.2 kg 1) was not economical for the CO2 capture sorbent. The re-
the low CO2 partial pressure of ~15 kPa in high gas flow rate is
ported cost of seeweed biochar, i.e., $13.19–13.43 kg 1 [122], appears
the main challenges of capturing post-combustion CO2, causing
to be around this range.
that only the very narrow micropores in biochar positively
Economic benefits are secondary to the application value of biochar,
affected CO2 adsorption [167]. Besides, the adsorption efficiency
the environmental benefits of biochar are more important [234]. The
of low boiling VOC needs to be increased while the difficulty and
biochar production and its use for adsorption of pollutants present lower
necessity of high temperature during high boiling VOC desorp-
environmental impacts than AC [238]. Alhashimi et al. [236] reported
tion should be solved. It should also keep in minds that the useful
that the energy consumption value to generate 1 kg biochar was
operation conditions found in experimental research are gener-
calculated to be 6.1 MJ/kg, in comparison to 97 MJ/kg for AC, and the
ally in a narrow range or even far from the representative con-
biochar presented negative GHG emissions of 0.9 kg CO2eq./kg
ditions of post-combustion
Recommended capture.of spent biochar. The priority in
disposal strategy
(4) because of its capacity to sequester carbon, while AC showed a positive
industry is regenerating the used biochar for many times until the emission of 6.6 kg CO2eq./kg. If the energy demand of biochar pro-
removal capacities of gas pollutants are invalid, mainly via duction is too high, it would penalize the environmental profile of bio-
thermal regeneration at about 200–300 ◦C which can be supplied char, but the function of heat generation of biomass for biochar systems
by heat transfer with a circulating flue gas in plants. The desorbedwith the highest environmental credits can provide an offset [238]. In
gas pollutants such as SO2 and NOx can be intensively collected order to harness the biochar adsorbents, the techno-economic and
and disposed to as chemical feedstock. Then, it is prior to send environmental feasibility should be evaluated from a life-cycle
perspective. The techno-economic assessments of biocharKOH were
investigated to compare the utilization potentiality with MEA and
PEI/silica at the post-combustion capture technology integrated with a
solar-assisted coal-fired power plant [239]. The corresponding values of
COA (cost of CO2 removed) for the system using MEA, PEI/silica and
biocharKOH were $31.53 ton CO2 1, $329.93 ton CO2 1 and $14.12 ton
CO2 1, respectively, indicating the best performance of biocharKOH.
Comprehensive life cycle analysis can indicate the environmental foot-
prints including carbon, energy, water and toxic emissions [25]. The
following life cycle stages should be included: biomass collection,
transportation to pyrolysis facilities, pre-treatment processes, pyrolysis
stage, adsorption process, and final use of co-products [238]. The po-
tential disposal methods include soil amendment, solid fuel for energy
generation together with syngas and bio-oil, and filler material in con-
struction materials. However, until now little studies paid attention to
the life-cycle analysis of biochar adsorption [235,236,238], and none of
them concerned the adsorption of gas pollutants.

7. Conclusions

This review highlights the potential of biochar as an efficient and

low-cost for removing the gaseous pollutants in combustion flue gas,
including SO2, NOX, Hg, CO2 and VOC. The physical activation, chem-
ical activation, and the novel modification methods including micro-
wave, ultrasonic, plasma, ball-milling, and molten salt, were introduced
as their improvement in the micropore properties and the active surface
functional groups of the biochar sorbents. The relevant treating condi-
tions were attended as their influence on the biochar characteristics,
such as pyrolysis and activation temperature, flow rate of activated gas,
concentrations of chemical activation agents, ratios of biochar to acti-
vating agent, and processing time. Furthermore, the functionalization
for engineering biochar, including addition of the oxides of transition
metals, basic sites capable of interacting with acidic gas, and halogens or
sulfur species on activated biochar were reviewed to observe the further
improved adsorption performance of biochar, for the possible engi-
neering application.
The adsorption conditions, mainly include the adsorption tempera-
ture, the humidity and impurities concentrations in simulated flue gas,
and the selectivity and synergistic adsorption of typical gases, were
related to the adsorption rate and removal performance of various
gaseous pollutants. Additionally, the study examines the cycle and
regeneration capacity of biochar to guarantee satisfactory practical
removal performance. The adsorption isotherm models and the
adsorption kinetic models are helpful to predict the adsorption amount
and controlling mechanism and from them the adsorption energy can be
calculated to determine the strength and potential of adsorption and
desorption. The advanced computational simulation methods such as
DFT, MD and GCMC were also discussed for helping with the description
of physisorption and chemisorption. At last, the challenges on improving
the adsorption performance of biochar, the synergistic adsorption in
industrial application, and the evaluation of economy and energy saving
analysis were presented.
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adsorption isotherms. Colloids Surf A Physicochem Eng Asp 2005;262:139–49. 2 from the Department of Thermal Power
[213] Gilliland E, Baddour R, Perkinson G, Sladek K. Diffusion on surfaces. I. Effect of Engineering, Huazhong University of Science &
concentration on the diffusivity of physically adsorbed gases. Ind Eng Chem Fund Technology, China. He is a Chair Professor
1974;13:95–100. of “Cheung Kong Scholar” of China. He has be
[214] Jeyasubramanian K, Thangagiri B, Sakthivel A, Raja J, Seenivasan S, en elected as Fellow of the Combustion
Vallinayagam P, et al. A complete review on biochar: production, property,
Institute for excellent research on solid fuel co
multifaceted applications, interaction mechanism and computational approach. mbustion, as applied to the formation and
Fuel 2021;292:120243. control of particulate matter and trace elements,
[215] Zhao S, Xun C, Xu W. Density functional theory study on the catalytic reduction of
and he currently works as the associate
nitric oxide over the bio-char surface during biomass reburning: the influence of editor for Energy & Fuels, ACS. His research f
inherent potassium. Fuel 2023;342:127923.
ields include pulverized coal combustion,
[216] Jia L, Yu Y, Guo J, Qin S, Wang Y, Shen X, et al. Study of the molecular structure
and elemental mercury adsorption mechanism of biomass char. Energy Fuel 2020; advanced utilization of biomass, CCUS, energ
y storage, industrial application of com-
34:12743–56.
[217] Cao D, Ji Y, Liu L, Li L, Li L, Feng X, et al. A facile and green strategy to synthesize bustion technology, comprehensive modeling
N/P co-doped bio-char as VOCs adsorbent: through efficient biogas slurry on pulverized coal combustion. He has
treatment and struvite transform. Fuel 2022;322:124156. published 3 monographs and 200+ academic pa
[218] Li Q, Xu W, Liang X, Liu B, Wu Q, Zeng Z, et al. Specific alkali metal sites as CO2 pers. He received the distinguished paper
traps in activated carbon with different pore size for CO2 selective adsorption:
in the Stationary Combustion colloquium of th
GCMC and DFT simulations. Fuel 2022;325:124871. e 33rd International Symposium on Com-
[219] Zhao Z, Wang B, Theng BK, Lee X, Zhang X, Chen M, et al. Removal performance,
bustion in 2010 and also won more than 8 Sc
mechanisms, and influencing factors of biochar for air pollutants: a critical ience and Technology Awards of National
review. Biochar 2022;4:30. Ministry or Provincial Government.
[220] Shafawi A, Mohamed A, Lahijani P, Mohammadi M. Recent advances in
developing engineered biochar for CO2 capture: an insight into the biochar Chang Wen received his PhD degree in 2013
modification approaches. J Environ Chem Eng 2021;9:106869. from State Key Laboratory of Coal Com-
[221] Al-Rumaihi A, Shahbaz M, Mckay G, Mackey H, Al-Ansari T. A review of pyrolysis
bustion, Huazhong University of Science & Tec
technologies
optimum and feedstock:
biochar a blending
yield. Renew Sustain approach for 2022;167:112715.
Energy Rev plastic and biomass towards hnology, China. He is currently an Asso-
ciate Professor at Department of New Ener
[222] Mamaghani Z, Impact
Review of the Hawboldt K, MacQuarrie
of gas mixtures andS. water
Adsorption of CO2 using
on adsorption. biochar-
J Environ Chem gy Science and Technology, Huazhong
University of Science and Technology. He w
Eng 2023:109643.
[223] Saeed A, Harun N, Nasef solution
M, Al-Fakih A, Ghaleb rice
A, Afolabi H. Removal of as an Endeavour Visiting Scholar in the
cadmium from aqueous by optimized husk biochar using response
Department of Chemical Engineering at Curtain
surface methodology. Ain Shams Eng J 2022;13:101516. University, Australia from 2012 to 2013
[224] Sessa F, Merlin G, Canu P. Pine bark valorization by activated carbons production and a post-doctor in State Key Laboratory of
to be used as VOCs adsorbents. Fuel 2022;318:123346. Coal Combustion, Huazhong University of
[225] Shahkarami S, Azargohar R, Dalai A, Soltan J. Breakthrough CO2 adsorption in Science & Technology, China from 2013 to 201
bio-based activated carbons. J Environ Sci 2015;34:68–76. 6. His research fields include energy uti-
[226] Ma Q, Chen W, Jinbiochar
nitrogen-doped Z, Chenfor
L, Zhou Q, Jiang
efficient X. One-step
removal of CO2 synthesis
and H2S. ofFuel
microporous
2021;289: lization of biochar materials and PM2.5 emissio
n control during solid fuel combustion. He
119932. has published more than 40 academic journal
[227] Yang Y, Sun inC, food
mechanism Huang Q, Yan
waste J. Hierarchical
component derived porous
N-dopedstructure
biochar: formation
application in papers. He received the Australian Gov-
ernment Endeavour Research Fellowship Awa
VOCs removal. Chemosphere 2022;291:132702.
[228] Zhuang Z, Wang L, Tang J. Efficient removal of volatile organic compound by rds in 2011 and the Excellent Doctoral
ball-milled biochars from different preparing conditions. J Hazard Mater 2021; Dissertation Award of Hubei Province, China, i
406:124676. n 2015.
[229] Li K, Niu X, Zhang D, Guo H, Zhu X, Yin H, et al. Renewable biochar derived from
Hanping Chen currently is a Professor and head
mixed sewage sludge and pine sawdust for carbon dioxide capture. Environ Pollut of Department of New Energy Science and
2022;306:119399.
Engineering at Huazhong University of Science a
[230] Tang R, Yang W,
bamboo-shell Wangblack
carbon H, Zhou
andJ, its
Zhang Z, Wuremoval
mercury S. Preparation of fly-ash-modified
performance in simulated nd Technology (HUST). He also serves as
flue gases. Energy Fuel 2016;30:4191–6. deputy director of State Key Laboratory of Coa
[231] Liu H, Yang B, Xue N. Enhanced adsorption l Combustion, and deputy director of Na-
activated carbon under humid conditions due toof shifts
benzene vapor on granular
in hydrophobicity and total
tional Energy R&D Center of Biomass Gas Prepar
micropore volume. J Hazard Mater 2016;318:425–32. ation & Utilization Technology. He was a
[232] Raganati F, Miccio F, Ammendola P. Adsorption of carbon dioxide for post- visiting scholar in the Department of Chemical
combustion capture: a review. Energy Fuel 2021;35:12845–68. and Biological Engineering at University of
[233] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue gas by British Columbia, Canada from 2000 to 2001
recyclable CuCl2 modified magnetospheres catalyst from fly ash. Part 1. Catalyst characterization and performance and a senior visiting fellow in the Depart-
uation. Fuel 2016;164:419–28. ment of Mechanical Engineering at University
[234] Dai Y, Zhang N, Xing C, Cui Q, Sun of Sheffield, UK in 2011. He has been
The adsorption, regeneration and devoted himself to fundamental research, te
engineering applications of biochar chnology development and engineering
removal organic pollutants: a review. application of high-efficiency conversion and hi
Chemosphere 2019;223:12–27. gh-value added comprehensive utilization
[235] Praveen S, Gokulan R, Pushpa TB, for biomass. He has been the manager of 30+ k
[236] Alhashimi HA, Aktas CB. Life cycle environmental and economic performance of
n J. Techno-economic feasibility of ey national research projects and has also
biochar compared with activated carbon: a meta-analysis. Resour Conserv Recycl biochar as biosorbent for basic dye led 60+ industry-supported projects. As the lea
2017;118:13–26.
questration. J Indian Chem Soc 2021;98: ding investigator, he won a Second-Class
[237] Tarka Jr TJ, Ciferno JP, Fauth DJ. CO2 capture systems utilizing amine enhanced
Award of National Science and Technology Pr
solid sorbents. Abstracts of Papers of the American Chemical Society. 100107. ogress. He also won more than 10 other
Science and Technology Award of National Min
istry or Provincial Government, a National
Overseas Chinese Contribution Award (Innova
tion Project), and a Blue Sky Award of
Global Top Investment Scenarios to Apply Ne
w Technology for Renewable Energy Utili-
zation. He has published 3 monographs and 150
+ academic papers and he also holds 10+
Chinese patents.
Guangqian Luo received his PhD degree
09 from the department of Thermal Power
Engineering, Huazhong University of Science
& Technology, China. He is currently a
Professor at Huazhong University of Science
nd Technology. His research fields include
transformation mechanism and control technol
ogy of heavy metals (Hg, Se, As, Pb), NO
SOx, VOC and other pollutants, and applicati
on of image recognition and artificial intel-
ligence technologies in the energy area. He
published more than 100 academic papers
indexed by SCI. He was awarded the
ent Doctoral Dissertation Award of Hubei
Province, China, the Distinguished paper
he 33rd International Symposium, the Best
Paper for the 9th International Symposium
Coal Combustion and the ESI Highly Cited
Papers. He also applied for 53 Chinese patents
and 32 patents have been authorized.

Zijian Zhou received his PhD degree in

from State Key Laboratory of Coal Com-
bustion, Huazhong University of Science
chnology, China. He is currently an Asso-
ciate Professor at State Key Laboratory
Coal Combustion, Huazhong University
Science and Technology. He was a post-
doctor in State Key Laboratory of Materials
o-
cessing and Die & Mould Technology, Huazh
ong University of Science & Technology,
China from 2017-2020. His research fields
de coal-fired flue gas pollutants control via
carbon-based adsorbents and metal oxides-
based catalysts. He landed on Forbes 30 Under

30 in Energy for China in 2019. He has publis

hed more than 40 academic journal papers,
and authorized 7 patents.

Tianyu Liu is now a Ph.D. candidate in

tate Key Laboratory of Coal Combustion at
Huazhong University of Science and Technolog
y. His current research focuses on the high-
value utilization of biochar. His main contribu
tion in this paper are the acquisition and
curation of data, including the conceptualizatio
n of mechanism and abstract.

Dapeng Wang is now a postgraduate

ofessor Minghou Xu’s group at Huazhong
University of Science and Technology, China.
His main contribution in this paper is in the
part of Hg. It includes the arrangement of
ble, drawing the picture of the mechanism.