Fuel 289 (2021) 119932

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

One-step synthesis of microporous nitrogen-doped biochar for efficient

removal of CO2 and H2S
Qiuxu Ma a, Wenhua Chen a, b, Ziheng Jin a, Lin Chen a, Qiying Zhou a, Xia Jiang a, b, *
a
College of Architecture and Environment, Sichuan University, Chengdu 610065, PR China
b
National Engineering Research Centre for Flue Gas Desulfurization, Chengdu 610065, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: It is still a great challenge to prepare an ideal adsorbent for the removal of CO2 and H2S from biogas efficiently. In
Biochar this study, urea phosphate (UP) was selected as both activator and nitrogen (N) source to prepare the biochar
Desulfurization adsorbent from plant biomass with microporous structure and N-rich functional groups through “one-step”
Urea phosphate
synthesis. The results show that the yield of biochar increased from about 20% to 50%, and the SBET and Vmic of
N-doping
the obtained biochar were 1189 m2/g and 0.433 cm3/g, respectively, which was much higher than those without
CO2 adsorption
UP addition (524 m2/g and 0.17 cm3/g). Moreover, N was successfully doped on the surface of biochar, and the N
content was up to 4.24 at.% with the majority of basic species such as pyridinic and pyrrolic N. This could be
attributed to a large amount of N-containing functional groups and phosphoric acid released gradually at the
presence of UP during the heating process. The prepared biochar exhibited good CO2 and H2S adsorption ca­
pacities up to 1.34 mmol/g and 54.8 mg/g, respectively, which was much higher than those without UP addition
(0.958 mmol/g and 0.24 mg/g). The excellent adsorption properties of CO2 and H2S were tightly related to the
improved microporous structure and surface basic N-containing functional groups on the biochar.

1. Introduction
Biogas is an efficient and clean renewable energy, which is mainly
composed of CH4 (55–70%) and CO2 (45–30%), and also contains trace
of H2S (100–10,000 ppmv) [1]. Only CH4 is the effective energy sub­
stance in biogas, while CO2 will severely reduce the calorific value of
biogas and cause the greenhouse effect. The presence of H2S will not
only stink biogas, but also cause potential safety problems due to the
corrosion and the generation of SO2 causing acid rain, haze and other
hazards [2]. Thus, the removal of CO2 and H2S from biogas is of great
practical significance for clean and efficient utilization of biogas.
Adsorption is considered to be the most promising method for the
removal of CO2 and H2S due to its high removal efficiency, simple
operation, low cost and easy regeneration [1–5]. Traditional adsorbent
is activated carbon derived from coal, asphalt and petroleum residues,
etc., which are non-renewable [6], leading to the increase of preparation
cost with the depletion of resources. Recent years, researchers prefer to
use waste biomass materials to prepare carbon materials, such as wood
particleboard, jackfruit peel [7], sugarcane bagasse [8], which are
renewable, sustainable and relatively cheap with large availability.
Among them, plant-based biomass such as sawdust, straw, contains high
content of volatile matters (70–80%) and low ash content (<10%) [9],
which is conducive to produce biochar with developed pore structure
and rich surface chemical properties. Therefore, plant-based biomass
waste can be considered as a suitable alternative for carbon precursor.
The pore structure and surface chemical properties are the key fac­
tors affecting the adsorption of CO2 and H2S by porous carbons [10,11].
Usually, KOH and other basic reagents were used as the activation
agents to obtain well-developed microporous structure of biochar,
which have high removal efficiency of H2S and CO2 [12]. However, the
biochar prepared by KOH has relatively low yields, i.e., <15% [13],
resulting in high cost. Moreover, KOH also severely corrode equipment
and cause secondary pollution. The high cost and safety problem greatly
limit the industrial application of KOH for the preparation of porous
carbon from biomass. Therefore, it is urgent to develop a green and mild
activator to prepare biochar with developed porosity.
On the other hand, basic functional groups on carbon surface are
beneficial to the adsorption of acidic gases such as CO2 and H2S. The N-
containing functional groups can provide effective basic sites to enhance
the interactions between carbon with acid gases [11,14,15]. Moreover,

* Corresponding author at: College of Architecture and Environment, Sichuan University, Chengdu 610065, PR China.
E-mail address: xjiang@scu.edu.cn (X. Jiang).

https://doi.org/10.1016/j.fuel.2020.119932
Received 23 May 2020; Received in revised form 13 November 2020; Accepted 30 November 2020
Available online 15 December 2020
0016-2361/© 2020 Elsevier Ltd. All rights reserved.
Q. Ma et al.
N-doping can promote the electron transfer on the surface of carbon
materials to enhance the reaction activity [16]. Generally, N-containing
reagents like NH3, urea, melamine, etc. are used to treat activated car­
bon through the “post-treatment” process [10,15,17]. However, there
are some problems in the “post-treatment” method, such as low N con­
tent, high cost, complex process and high toxicity, etc [18]. Therefore, it
is necessary to develop a simple and effective method to prepare the N-
doped carbon materials.
Urea phosphate (UP), as a typical organic N-containing phosphate,
can be decomposed into phosphoric acid and NH3 during pyrolysis [19],
which can be used as both activator and N source to realize “one-step”
activation and N-doping. First, phosphoric acid can promote the cata­
lytic dehydration and cross-linking of cellulose [20], which expands the
biomass structure and creates pores [21]. The free generated N-con­
taining radicals will not only further form N-containing functional
groups such as pyrrole, but also etch the surface of carbon materials to
increase porosity [19,22]. In addition, the nonflammable gases will be
released from the pyrolysis of UP, which was beneficial to the flame
retardance of gas phase, resulting in the increase of carbon yield
[23,24]. On the other hand, “one-step” activation and N-doping can
improve the retention of N in the matrix, which reduce the N loss caused
by “post-treatment”. Moreover, compared with KOH and other aggres­
sive activators, UP is much milder and more environmentally friendly,
less toxic and less corrosive to equipment. However, very few studies
have been found on the preparation of N-doped porous carbon from
plant-based biomass using UP.
In this study, we incorporated UP to improve the porosity and surface
N-containing functional groups of biochars from sawdust for the
removal of CO2 and H2S. The effects of UP addition ratios and the
activation temperature on pore structure and N-containing groups of
biochar were investigated. The integral mechanism of carbonization,
activation and N-doping using UP were also explored for the preparation
of N-doped porous carbon from plant-based biomass. The results show
that the prepared biochar had effective removal performance for CO2
and H2S.
2. Materials and methods
2.1. Materials
Sawdust came from a furniture factory in Sichuan Province, China.
The results of element analysis and industrial analysis of sawdust are
shown in Table S1, and the main elements of sawdust were carbon and
oxygen. UP was purchased from Guangdong Wenjiang Chemical Re­
agent Co., Ltd. Specifically, and the N and phosphate contents of UP
were 17.7% and 19.5%, respectively. The UP used in this study was of
analytical grade.
2.2. Preparation of biochar
The sawdust through 30 mesh sieves was impregnated in the UP
solution (0.5, 1 and 2 g UP/g sawdust), and then the mixture was kept at
room temperature for 24 h. The UP molecules are water-soluble, and UP
solution can easily diffuse into the overall sawdust because of the
aligned tubular pore structures of sawdust [7,10]. The mixture was
heated to the target temperature (600–900 ◦ C) in the tubular furnace
under the atmosphere of N2 (flow rate of 150 mL/min) and kept for 2 h.
After that, the sample was washed to neutral using the hot deionized
water (100 ◦ C). N-doped biochar can be obtained after drying and
passing 200 mesh sieves. These samples were denoted as NC-X-Y, where
X represented the heat treatment temperature and Y represented the
proportion of UP to sawdust. The sample without UP was denoted as C-
X.
2
Fuel 289 (2021) 119932
2.3. Characterization
The pyrolysis curves of sawdust, UP and the mixture of sawdust and
UP were measured by TG (STA 8000, PerkinElmer, USA). The flow rate
of N2 was 20 mL/min and the heating rate was 10 ◦ C/min. The pore
structure of the samples was determined by specific surface area
analyzer (ASAP 2460, micromeritics, USA) at 77 K, and the sample was
degassed at 180 ◦ C for 8 h before characterization. The BET specific
surface area (SBET) and micropore volume (Vmic) of the samples were
calculated by BET and t-plot method, and the total pore volume (Vtot)
was measured by N2 adsorption–desorption curve at P/P0 = 0.99, while
the mesopore volume (Vmeso) was defined as the difference between
total pore volume and the micropore volume. The surface morphology of
carbon materials was observed by scanning electron microscopy (SEM)
(JSM-5900LV, JEOL, Japan). Element analyzer (DRI 2001A) was used to
determine the contents of C, H and N elements in materials. The ele­
ments and functional groups on the surface of carbon materials were
analyzed by ESCALAB 250 (Thermo Scientific, USA), and the peaks were
fitted by least square method. The infrared (FTIR) spectrum of the
samples was obtained on Nicolet 6700 (Thermo Scientific, USA) with the
wave number at 4000–400 cm− 1.
2.4. CO2 adsorption
The CO2 adsorption–desorption of sample was performed on a
thermogravimetry analyzer (STA 8000, PerkinElmer, USA). Prior to the
adsorption experiment, 10 mg of the sample was placed in a crucible and
dried in a N2 atmosphere (20 mL/min) at 120 ◦ C for 1 h to remove excess
moisture and impurities. The sample was cooled to 30 ◦ C, and N2 was
switched to CO2 (100 mL/min), then constant adsorption was main­
tained for 1 h. The weight change during CO2 adsorption was recorded
to evaluate the CO2 uptake capacity. Subsequently, the sample was kept
at 120 ◦ C for 1 h and the flow was switched to N2 to regenerate the
sample. The CO2 adsorption test for each sample was repeated for three
times and then the average value was calculated.
2.5. H2S adsorption
The dynamic adsorption of H2S by fixed bed was adopted. 150 mg
sample was put into a glass reactor with a diameter of 10 mm and a
length of 16 mm. Subsequently, a N2 flow containing 100 ppmv of H2S
was passed through the column of the samples at a total flow rate of 200
mL/min. The adsorption temperature was set at 30 ◦ C by constant
temperature circulating water flow. The H2S in outlet gas was removed
through the solution containing NaOH for neutralization treatment
before discharging into atmosphere. In all tests, the H2S concentration in
the gas at the outlet of quartz reactor was measured by gas detector
(MSA Tianying 5x, China), and the minimum detection limit was 1
ppmv. In this test, the breakthrough concentration of H2S was defined as
C/C0 = 10%. The test was stopped when reached the breakthrough
concentration. The breakthrough sulfur capacity (mg H2S/g) was
calculated by using Eq. (1):
( ∫t )
qv Ms × C0 ts − 0s C(t)d(t)
Q= (1)
1000mVL
where, Q is adsorption capacity (mg H2S/g carbon), qv is total flow rate
of mixed gas (L/min), Ms is H2S molecule weight (34 g/mol), C0 is the
inlet H2S concentration (ppmv), ts is the adsorption time (min), C(t) is
the outlet H2S concentration at t moment (ppmv), m is adsorbent mass
(g), VL is gas molar volume (L/mol).
2.6. Isotherm model
Langmuir isotherm model can be expressed as:
Q. Ma et al.
qm KL P
qe =
1 + KL P
qm and qe are the equilibrium adsorption capacity and the maximum
adsorption capacity [25], respectively, P is the partial pressure of CO2
(bar), KL is the Langmuir adsorption constant (atm− 1).
Freundlich isotherm model can reflect the multi-layer adsorption of
heterogeneous surface, which can be expressed as follows:
qe = KF P1/n
Kf and n are Freundlich constants, indicating adsorption capacity and
adsorption strength, respectively. When n > 1, the adsorption process is
easy to occur.
For Sips isotherm model, the expression is as follows:
(KS P)γ
qe = qm
(1 + KS P)γ
The nonuniformity coefficient, γ is used to characterize the nonuni­
formity between the adsorbent interfaces. When γ = 1, the expression of
Sips model is equivalent to Langmuir model, and the adsorption process
is uniform adsorption. The larger the deviation of γ from 1, the higher
the heterogeneity of the adsorbent interface.
3. Results and discussion
3.1. TG and TG-FTIR analysis
3.1.1. TG analysis
The TG and DTG curves of sawdust, UP and their mixture with a
weight ratio of 1:1 are shown in Fig. 1a and b. The pyrolysis process of
sawdust can be divided into three stages: (1) Under 110 ◦ C, a slight
Fig. 1. (a) TG and (b) DTG curves of sawdust, UP, sawdust + UP at the weight ratio of 1, and the fitting curves of sawdust + UP, respectively; (c) Typical FTIR spectra
for the gaseous products of sawdust + UP at different temperatures.
Fuel 289 (2021) 119932
weight loss of about 3.7% occurred, which was the volatilization of
(2)
adsorbed water and capillary water in sawdust [26]. (2) In the tem­
perature range of 110–600 ◦ C, the maximum weight loss rate appeared
at about 364 ◦ C. The sawdust decomposed rapidly and the weight was
significantly reduced, with the weight loss up to 72.38%, accounting for
85% of the total weight loss. This stage was mainly the decomposition of
cellulose, hemicellulose and lignin [27]. (3) Above 600 ◦ C, the weight
loss was only 5.34%, indicating that the volatiles of sawdust were
(3) completely volatilized and a stable carbon structure was formed.
From Fig. 1a and b, there were three mass loss stages in the pyrolysis
process of UP: (1) In the range of 115–200 ◦ C, there was a large weight
loss peak at 160–170 ◦ C, and the weight loss was approximately 47.5%.
It could be mainly due to the thermal decomposition of UP into H3PO4
and urea, and the urea can further be decomposed into small molecules
such as CO2 and NH3. (2) At 200–700 ◦ C, the weight loss was about
(4) 32.74%, and the maximum decomposition rate occurred at 622 ◦ C,
which could be the dehydration of phosphoric acid and the formation of
metaphosphoric acid and P2O5. (3) Above 700 ◦ C, the weight loss
reduced as low as about 2.5%.
In order to further investigate the possible interactions between
sawdust and UP during pyrolysis process, the fitting curves of the
mixture by calculating their own TG curves (1:1) were also plotted, as
shown in Fig. 1a and b. The results showed that the fitting and experi­
mental curves were not exactly coincided, indicating that there were
certain reactions happened between sawdust and UP during pyrolysis
process. Compared with the fitting curve, the weight loss of the mixture
was higher in the range of 100–267 ◦ C, indicating that the presence of
UP accelerated the decomposition of cellulose and hemicellulose at this
stage. When the temperature increased from 267 to 700 ◦ C, the weight
loss of the mixture was clearly lower than that of the fitting curve,
suggesting that H3PO4 generated from the pyrolysis of UP was cross-
3
Q. Ma et al. Fuel 289 (2021) 119932

linked with lignocellulose in biomass. The product from cross-linking, i.
e., macromolecular phosphate esters, can inhibit the decomposition of
carbon, which slow down the weight loss of biomass [19]. At about
858 ◦ C, there was a small weight loss peak for the mixture. This could be
the occurrence of some reactions involving nitrogen, phosphate com­
pounds and carbon in this process [19].
3.1.2. TG-FTIR analysis
In order to better understand the preparation process of biochar with
the addition of UP, the gaseous products generated during the pyrolysis
of the mixture were detected by TG-FTIR analysis. Based on the results of
TGA analysis, the infrared spectra were selected at some characteristic
temperatures, i.e., 164, 242, 364, 622 and 858 ◦ C (Fig. 1c). The ab­
sorption peaks at 3750 cm− 1, 2388–2362 cm− 1 and 1510 cm− 1 could be
attributed to the vibration of H2O, CO2, NH3 and other N-components
generated during pyrolysis process, respectively [28,29]. At 242 ◦ C, the
peak intensity of CO2 increased, indicating that a large amount of CO2
was released, which could be resulted from the reactions between UP
and sawdust. At the same time, cellulose in the sawdust began to py­
rolyze, releasing water, CO2, furan, alcohol, acid and carbonyl [27].
According to the results of TG, the weight loss of the mixture in the range
of 170–250 ◦ C was mainly attributed to the release of CO2, NH3 and
other small molecular gases during the pyrolysis of UP and sawdust. In
the medium temperature range (240–700 ◦ C), there was also a strong
peak of CO2 decomposition at 364 ◦ C. However, at 622 ◦ C, only a small
amount of CO2 could be detected, indicating that the chemical reactions
between UP and sawdust prevented the release of carbon. As shown in
Fig. 1a and b, the weight loss of the mixture in this temperature range
was much lower than the value through fitting calculation. At high
temperature (>700 ◦ C), in addition to the release of CO2 and NH3, the
bands at about 2100–2000 cm− 1 can be ascribed to CO [27], which was
also the main reason for a small weight loss peak after 800 ◦ C (Fig. 1a
and b).
Furthermore, it was worth noting that NH3 was released gradually
from the mixture during the whole pyrolysis process. The generated NH3
can be decomposed into free radicals, which can attack the carbon
matrix to form N-containing functional groups on the surface of the
biochar [17]. When the temperature was over 600 ◦ C, more N species
can be transformed into some basic functional groups such as pyridine N
and pyrrole N [30]. Moreover, Some N atoms can enter the internal
structure of carbon to form graphite N with higher thermal stability
[19]. In addition, it is possible that the generated NH3 during the whole
pyrolysis process can further develop pores through diffusion in the
carbon layer.
3.2. Characterization of biochar
3.2.1. Yield of biochar
Fig. S1 shows the yields of the samples prepared at different pyrolysis
temperatures (600–900 ◦ C) and with various UP ratios (0–2). The yields
of biochars without UP addition ranged from 14.1% to 25.8%, and
decreased with the increase of pyrolysis temperature. The biochar yield
was significantly enhanced after incorporating UP, which was as high as
50% at 600 ◦ C and gradually decreased with increasing pyrolysis tem­
perature. When the temperature rose to 700 ◦ C, H3PO4 and its polymers
can combine with the organic components in the sawdust to form
3.2.2. Textural properties
The N2 adsorption–desorption isotherms of the prepared biochars are
shown in Fig. S2. It can be clearly seen that in the whole relative pressure
range, the original biochar (C-700) and the biochar with low ratio of UP
(NC-700-0.5) can adsorb a small amount of N2, while the biochars with a
high proportion of UP (ratio at 1 or 2) exhibited a higher N2 adsorption
capacity. At the relative pressure of above 0.4, C-700 and NC-700-0.5
had the hysteresis loops, which belonged to type IV, indicating that
there are mesopores in the samples. The adsorption volume of other
samples increased sharply in the low relative pressure stage, which
belonged to type I, indicating that the samples are endowed with
obvious microporous structure. The formation of crosslinked structure
expanded the biomass structure to forms pores [31], and furthermore,
gases generated in pyrolysis process diffused, and then new pores will be
formed in the carbon structure [19]. The results showed that the bio­
chars with high ratios of UP were more favorable to form abundant
micropores.
The pore structure parameters of prepared biochars are summarized
in Table 1. The SBET and Vmic of the original sample (C-700) were rela­
tively small, at 524 m2/g and 0.172 cm3/g, respectively. After the
incorporation of UP, the SBET and Vmic of biochars were significantly
increased, up to 773 m2/g and 0.32 cm3/g for NC-700-1. With a pyrol­
ysis temperature of 700 ◦ C, the SBET and Vmic increased with the increase
of the UP ratio from 0.5 to 2, and reached the highest of 1189 m2/g and
0.433 cm3/g, respectively. While, the Vmeso was significantly lower than
C-700, and the Vmeso increased with the increase of UP ratio, indicating
that UP can be helpful to form abundant micropores and certain meso­
pores. At the same ratio of UP, the SBET, Vmeso and Vtot of the prepared
biochar increased with increasing the pyrolysis temperature from 600 ◦ C
to 900 ◦ C. However, the excessive high pyrolysis temperature (900 ◦ C)
induced the decrease of the Vmic and a significant increase in the Vmeso,
which could be due to the collapse of micropores at high temperature.
3.2.3. Surface functional groups
The samples were analyzed by XPS to explore the specific forms and
the distribution of N-containing functional groups in the prepared bio­
char, as shown in Table 2. The relative contents of carbon (C) for the
biochars with UP (80.21–88.16 at.%) were lower than that of blank C-
700 (89.79 at.%), indicating that more non-carbon substances are
introduced into the carbon surface after adding UP. In addition, the N
content of biochars with UP increased significantly to up to 4.24 at.%,
indicating that N was successfully introduced to the surface of biochars.
Moreover, with the increase of the UP ratio, the N contents gradually
increased, while with the increase of temperature, the N contents
decreased gradually.
The N 1 s high resolution diagram of the prepared biochar is shown
in Fig. 2. The XPS spectra of N 1 s were convoluted into three main peaks
at 398.5 eV, 400.5 eV and 401.6 eV, which were assigned to pyridine N
(N-6), pyrrole N (N-5) and graphitized N (N-Q), respectively [32]. It can
be seen from Table 2 that N-5 was the main N species of prepared
Table 1
Pore structure parameters of the prepared biochars.
Sample Surface area Smic/SBET Pore volume (cm3/g) Vmic/Vtot
(m2/g) (%) (%)

phosphates and polyphosphate esters through crosslinking [30]. This SBET Smic Vtot Vmic Vmeso
avoided the escape of carbon atoms, resulting in the high yield of bio­ C-700 524 351 67.0 0.445 0.172 0.273 38.7
char. When the temperature increased to 800 ◦ C and 900 ◦ C, the yields NC-700- 586 537 91.6 0.295 0.264 0.031 89.5
remained above 20%, which were still higher than that of the original 0.5
sample at the same pyrolysis temperature. However, there was no sig­ NC-700-1 773 637 82.4 0.420 0.320 0.100 76.2
NC-700-2 1189 872 73.3 0.625 0.433 0.192 69.3
nificant difference in the yield for the samples with different UP ratios, NC-600-1 721 610 84.6 0.374 0.306 0.068 81.8
suggesting that compared to temperature, UP ratio wasn’t the domi­ NC-800-1 1003 657 65.5 0.526 0.331 0.195 62.9
nating factor for the yield of biochars. NC-900-1 1615 467 28.9 0.854 0.206 0.648 24.1
NC-700- 665 571 85.9 0.343 0.280 0.063 81.6
1-S

4
Q. Ma et al. Fuel 289 (2021) 119932

Table 2 With the increase of the UP proportion from 0.5 to 1, the adsorption
Elemental analysis and relative contents of N-containing groups on the prepared capacity of CO2 increased gradually from 1.26 mmol/g to 1.34 mmol/g.
biochars and NC-700-1 after desulfurization. However, when the UP ratio further increased, the adsorption capacity
Sample C (at. O (at. N (at. S (at. N distribution (%) of NC-700-2 decreased slightly (Fig. 3b). The contrast was brought by
%) %) %) %)
N-6 N-5 N-Q
microporosity. For NC-700-2, although SBET was the highest, its micro­
pore proportion (69.3%) was lower than NC-700-1 (76.2%) (Table 1). It
C-700 89.79 10.21 – – – – –
was reported that micropores played an critical role in capturing CO2
NC-700- 87.46 8.63 3.16 – 30.60 46.69 22.71
0.5 molecules, especially those pore sizes below 1 nm, because of its rela­
NC-700-1 80.21 14.57 3.86 – 28.50 43.52 27.98 tively weak van der Waals force and capillary coacervation effect [34].
NC-700-2 85.32 4.24 4.24 – 26.81 48.55 24.64 On the other hand, the type of N was related to the improvement of CO2
NC-600-1 86.15 9.62 3.90 – 28.97 51.03 20.00 adsorption capacity as well [16]. For instance, N-6 was more conducive
NC-800-1 87.47 8.61 3.36 – 29.17 49.70 21.13
NC-900-1 88.16 9.36 1.81 – 23.76 49.17 27.07
to CO2 absorption than other N species, owing to its stronger polarity
NC-700- 78.19 11.76 2.41 0.47 28.70 50.43 20.87 [10].
1-S Among all the samples, NC-700-1 had the highest CO2 capture ca­
pacity (1.34 mmol/g), which was about 40% higher than C-700 (0.958
mmol/g). Compared with C-700, NC-700-1 had higher SBET, Vmic
biochars. With the increase of UP ratios, from NC-700-0.5 to NC-700-2,
(Table 1) and higher N content together with richer N functional groups
the contents of N-6 decreased and those of N-5 was almost invariable,
(Table 2), which should be responsible for its higher CO2 adsorption
while the contents of N-Q slightly increased. With the increase of py­
capacity. It was reported that the adsorption of CO2 was related to the
rolysis temperature, from NC-600-1 to NC-900-1, the contents of N-6
synergistic effect of SBET, Vmic and N-containing functional groups [10].
and N-5 decreased, while the proportion of N-Q increased. High tem­
Specifically, N-6 can significantly improve the acid-base reaction ac­
perature has a great influence on N species, which may lead to a more
tivity with CO2, while N-5 can promote the hydrogen-bond interaction
stable N-Q transformation [33].
between carbon surface and CO2 [35].

3.3. CO2 adsorption 3.3.2. Adsorption isotherm

3.3.1. CO2 adsorption performance
Fig. 3a and b shows the CO2 adsorption capacity of the prepared
biochars at 30 ◦ C. It can be clearly seen that the CO2 adsorption capacity
of N-doped biochars were higher than that without UP (C-700). With the
temperature increased from 600 ◦ C to 700 ◦ C, the CO2 adsorption ca­
pacity was raised, since the SBET and Vmic were improved by the higher
temperature. When the temperature further increased to 800 ◦ C and
900 ◦ C, the CO2 adsorption capacity was lower than that of other sam­
ples (Fig. 3a). This could be attributed to lower N content of NC-900-1
(1.81 at.%) (Table 2) due to high temperature. In addition, at high
temperature, some N groups were transformed into aromatic N-con­
taining species and constructed into carbon matrix, the alkalinity was
also weaken [30].
The static adsorption property of NC-700-1 for CO2 at 25 ◦ C was
investigated, and the corresponding adsorption isotherms are shown in
Fig. 3c. With the increase of pressure, the adsorption capacity of CO2
increased, indicating that more CO2 molecules entered the porous car­
bon channel and are easily adsorbed in the high-pressure range. The
adsorption capacity of NC-700-1 for CO2 was 2.42 mmol/g.
The study of isotherms is of great significance to explain the
adsorption mechanism of adsorbents. In this study, Langmuir, Freund­
lich and Sips models are used to fit the above adsorption isotherms, and
the results are shown in Fig. 3c and Table S2.
y1: y2 = 15:85, y1: CO2 ratio in the mixture of CO2 and N2, y2: N2 ratio
in the mixture of CO2 and N2.
According to the correlation coefficient (R2) in Table S2, the fitting

Fig. 2. N 1S high resolution diagram of prepared biochars.

5
Q. Ma et al. Fuel 289 (2021) 119932

Fig. 3. CO2 adsorption performance of the prepared biochars at (a) different temperatures and (b) different UP ratios; (c) CO2 static adsorption isotherms, inset: CO2/
N2 selectivity values; (d) Cycle-regeneration performance of NC-700-1.

degrees of the three models to the experimental results were all higher
Table 3
than 0.99, indicating that they can provide the good description on the
Comparison of CO2 adsorption capacity and CO2/N2 selectivity values with some
adsorption process. The n value of Freundlich model fitting was 1.59
literatures.
(≥1), which proved that the adsorption process of CO2 was spontaneous.
In addition, among the three models, Sips model had the highest R2, Material Adsorption capacity (mmol/g, 1 bar 298 SCO2/ Ref.
k)
which can describe the adsorption process more accurately. The value of N2

γ in Sips model was about 0.76, showing the adsorption sites wasn’t N-TC-EMC 4.00 14.0 [36]
IBN9-NC1 A 4.50 25.0 [37]
uniformly distributed on biochar. The result showed that the adsorption
HCM-DAH-1 2.60 27.8 [38]
process of CO2 was not a monolayer sorption, which was the reason why sOMC 2.00 11.3 [39]
the correlation coefficient was relatively low when using Langmuir CNFWS-600- 4.42 26.0 [40]
model to fit it. Moreover, N-containing groups evidently improved the 2
adsorption sites on the surface of biochar. NC-700-1 2.42 41.2 This
study

3.3.3. CO2/N2 selectivity

Based on the parameters of the Sips model and the ideal solution of CO2 during 4 cycles of test, which can be regarded as a stable CO2
adsorption theory (IAST), the CO2/N2 selectivity of NC-700-1 under the adsorbent.
simulated flue gas condition (CO2: 15%, N2: 85%) was calculated. The
selectivity of NC-700-1 for CO2 was up to 41.2 is shown in Fig. 3c.
3.4. H2S removal
Compared with the adsorbents reported in other literatures [36–40]
(listed in Table 3), the N-doped biochar prepared in this study had
3.4.1. H2S removal performance
higher CO2 selectivity with similar adsorption performance. This high
The removal capacity of the prepared biochars for H2S is shown in
selectivity can be attributed to the presence of N-containing functional
Fig. 4a and b. Blank biochar (C-700) had poor removal capacity for H2S
groups on the NC-700-1 with N content at about 4.24 at.% and high
at 0.24 mg/g. Compared with C-700, the removal capacity of all bio­
relative contents of basic functional group (N-5 and N-6). This demon­
chars with UP were increased significantly. With increasing the pyrolysis
strates that the N-doped biochar can be endowed with a broad appli­
temperature from 600 ◦ C to 700 ◦ C, the removal capacity increased from
cation prospect in the separation of CO2 in flue gas [41].
44.88 to 54.80 mg/g (Fig. 4a). However, a significant decline occurred
For the practical application of CO2 adsorption, the cyclic stability
when further increasing the pyrolysis temperature to 800 ◦ C. However,
was an important index to evaluate the performance of adsorbents [25].
the H2S removal performance for NC-800-1 showed a decreasing trend
As shown in Fig. 3d, NC-700-1 maintained the stable adsorption capacity
from NC-600-1, even though the pore structure of NC-800-1 and NC-

6
Q. Ma et al.
Fig. 4. Sulfur removal capacity of prepared biochars at (a) different temperatures and (b) different UP ratios. (c) XPS survey spectra before and after desulfurization
and (d) high-resolution of S 2P spectra after desulfurization of NC-700-1.
900-1 became more developed (Table 1). This was mainly attributed to
the decomposition of N substances and the reduction of N content at
high temperature above 800 ◦ C, especially for NC-900-1, only 1.81 at.%,
as shown in Table 2. N can introduce the basic site into carbon, and then
improving the chemical reactivity of acid-base chemistry [11]. More­
over, the N-6 was supposed to be responsible for the catalytic activity in
the H2S oxidation [11]. However, the N-6 contents of NC-800-1 and NC-
900-1 were very low, which will affect their H2S removal capacities.
With the increase of UP content, the removal capacity of the biochar
increased gradually (Fig. 4b). The increase of H2S removal capacity from
C-700 to NC-700-2 was mainly attributed to the development of pore
structure, especially micro-porosity, from 0.172 cm3/g to 0.433 cm3/g
(Table 1). Micropores in biochar can effectively adsorb H2S [42]. From
the perspective of environment and cost, NC-700-1 was regarded as the
best sample.
3.4.2. Physical-chemical characteristics of biochar after desulfurization
NC-700-1 was chosen to study the physical and chemical properties
after desulfurization. As shown in Table 2, the sulfur content of NC-700-
1 increased to 0.47% after desulfurization. In order to further determine
the desulfurization products, XPS analysis was carried out for NC-700-1
after desulfurization, as shown in Fig. 4c. After desulfurization, two
extra peaks were observed on the surface of NC-700-1, which belong to S
2P and S 2S, respectively. There were three peaks at the binding energies
of 163.82, 165.2 and 167.86 eV (Fig. 4d) which can be ascribed to sulfur,
sulfite and sulfate, respectively. This indicated that the desulfurization
products were S, sulfite and sulfate. From the peak areas in S 2P spec­
trum of desulfurized sample, S was the main product of desulfurization,
the proportion was 50.65%.
In order to determine whether the adsorbed S is deposited in the
pores of biochar, the NC-700-1 after desulfurization was characterized
7
Fuel 289 (2021) 119932
by N2 adsorption and desorption. After desulfurization, the N2 adsorp­
tion capacity of NC-700-1-S decreased (Fig. S3). Compared with NC-
700-1, the SBET, Vmic and Vmeso of NC-700-1-S reduced to 665 m2/g,
0.28 cm3/g and 0.063 cm3/g, respectively (Table 1).
Based on the results obtained above, it can be assumed that H2S can
be adsorbed on the active sites of carbon, while micropores and meso­
pores can provide certain alkaline active sites. H2S can be decomposed
into HS-, and oxygen diffuses into the pores, which oxidizes HS- into
elemental sulfur. Sulfur will be deposited in micropores or mesopores of
biochar [43], reducing the pore volume, and gradually inactivate the
alkaline sites. In addition, at the presence of oxygen, elemental sulfur
was oxidized into sulfite and sulfate during the desulfurization process
(Fig. 4d), which will reduce the pH of the biochar surface. The acidity
and basicity of carbon surface will affect the type of desulfurization
products [44]. Under the surface with strong acidity, it was mainly
physical adsorption, and H2S was adsorbed on the inner surface of the
material in molecular form. Under the surface with neutral or weak
acidity, the yield of water-soluble substances was high, resulting in low
removal capacity [45]. On the alkaline surface, the alkaline active will
promote the ionization of H2S and the formation of sulfur, preventing
the continuous oxidation of sulfur. Therefore, the destruction of the
alkaline environment on the surface of the adsorbent will lead to a
significant reduction of the removal capacity. In short, the efficient
removal of H2S is tightly related to the adsorption and catalysis reaction
of the prepared biochar. More importantly, as shown in Table S3, the as-
prepared biochar shows a considerable level in CO2 and H2S removal to
these commercial materials [10,42,46–49].
4. Conclusions
In this study, UP was used as both activator and N source to achieve
Q. Ma et al.
the one-step carbonization, activation and N-doping from biomass pre­
cursor for the preparation of N-doped porous carbon for the removal of
CO2 and H2S. The results showed that the addition of UP significantly
improved the yield of prepared biochars as high as 50%. The porous
structure of the biochar with UP was more developed than that of blank
carbon, and the SBET, Vtot and Vmic of the obtained biochar were
increased to 1189 m2/g, 0.625 cm3/g and 0.433 cm3/g, respectively. In
addition, N can be successfully doped on the surface of the biochar, and
the N content of the biochar was as high as 4.24 at.% with the majority
of N-5 and N-6. The prepared biochar had good adsorption performance
for CO2 and H2S, and the adsorption capacity of CO2 and H2S by NC-700-
1 were 1.34 mmol/g and 54.8 mg/g, respectively. This could be
attributed to its rich microporous structure and N modified surface
alkalinity of the biochar induced by the addition of UP.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work is supported by the National Nature Science Foundation of
China (No. 51778383) and Sichuan Science and Technology Program
(20CXTD0096).
Author contributions
Q.X.M., W.H.C., Z.H.J., and X.J. wrote the main manuscript text and
prepared all figures and tables; Q.X.M. and W.H.C. designed and carried
out the experiments; Q.X.M., Z.H.J., L.C., and Q.Y.Z. discussed the
related results. All authors reviewed the manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2020.119932.
References
[1] Castrillon M, Moura K, Alves C, Bastos-Neto M, Azevedo D, Hofmann J, et al. CO2
and H2S removal from CH4-rich streams by adsorption on activated carbons
modified with K2CO3, NaOH, or Fe2O3. Energy Fuels 2016;30(11):9596–604.
[2] Belmabkhout Y, Bhatt PM, Adil K, Pillai RS, Cadiau A, Shkurenko A, et al. Natural
gas upgrading using a fluorinated MOF with tuned H2S and CO2 adsorption
selectivity. Nat Energy 2018;3(12):1059–66.
[3] Izquierdo M, Gasquet V, Sansom E, Ojeda M, Garcia S, Maroto-Valer M. Lithium-
based sorbents for high temperature CO2 capture: Effect of precursor materials and
synthesis method. Fuel 2018;230:45–51.
[4] Li H, Qu M, Hu Y. Preparation of spherical Li4SiO4 pellets by novel agar method for
high-temperature CO2 capture. Chem Eng J 2020;380..
[5] Hu Y, Guo Y, Sun J, Li H, Liu W. Progress in MgO sorbents for cyclic CO2 capture: a
comprehensive review. J Mater Chem A 2019;7(35):20103–20.
[6] Girods P, Dufour A, Fierro V, Rogaume Y, Rogaume C, Zoulalian A, et al. Activated
carbons prepared from wood particleboard wastes: Characterisation and phenol
adsorption capacities. J Hazard Mater 2009;166(1):491–501.
[7] Prahas D, Kartika Y, Indraswati N, Ismadji S. Activated carbon from jackfruit peel
waste by H3PO4 chemical activation: Pore structure and surface chemistry
characterization. Chem Eng J 2008;140(1):32–42.
[8] Chen C, Huang B, Li T, Wu G. Preparation of phosphoric acid activated carbon from
sugarcane bagasse by mechanochemical processing. BioResources 2012;7(4):
5109–16.
[9] Yahya MA, Al-Qodah Z, Ngah CWZ. Agricultural bio-waste materials as potential
sustainable precursors used for activated carbon production: a review. Renewable
Sustainable Energy Rev 2015;46:218–35.
[10] Zhang S, Zhou Q, Jiang X, Yao L, Jiang W, Xie R. Preparation and evaluation of
nitrogen-tailored hierarchical meso-/micro-porous activated carbon for CO2
adsorption. Environ Technol 2019:1–10.
[11] Sun F, Liu J, Chen H, Zhang Z, Qiao W, Long D, et al. Nitrogen-rich mesoporous
Carbons: Highly efficient, regenerable metal-free catalysts for low-temperature
oxidation of H2S. ACS Catal 2013;3(5):862–70.
8
Fuel 289 (2021) 119932
[12] Lillo-Rodenas MA, Juan-Juan J, Cazorla-Amoros D, Linares-Solano A. About
reactions occurring during chemical activation with hydroxides. Carbon 2004;42
(7):1371–5.
[13] Ahmad Z, Yao L, Wang J, Gang D, Islam F, Lian Q, et al. Neodymium embedded
ordered mesoporous carbon (OMC) for enhanced adsorption of sunset yellow:
Characterizations, adsorption study and adsorption mechanism. Chem Eng J 2019;
359:814–26.
[14] Hao G, Li W, Qian D, Lu A. Rapid synthesis of nitrogen-doped porous carbon
monolith for CO2 capture. Adv Mater 2010;22(7):853–7.
[15] Shen W, Fan W. Nitrogen-containing porous carbons: Synthesis and application.
J Mater Chem A 2013;1(4):999–1013.
[16] Arenillas A, Drage TC, Smith K, Snape CE. CO2 removal potential of carbons
prepared by co-pyrolysis of sugar and nitrogen containing compounds. J Anal Appl
Pyrol 2005;74(1–2):298–306.
[17] Przepiórski J, Skrodzewicz M, Morawski A. High temperature ammonia treatment
of activated carbon for enhancement of CO2 adsorption. Appl Surf Sci 2004;225
(1–4):235–42.
[18] Yu Z, Wang X, Song X, Liu Y, Qiu J. Molten salt synthesis of nitrogen-doped porous
carbons for hydrogen sulfide adsorptive removal. Carbon 2015;95:852–60.
[19] Zhou Q, Jiang X, Li X, Jia C, Jiang W. Preparation of high-yield N-doped biochar
from nitrogen-containing phosphate and its effective adsorption for toluene. RSC
Adv 2018;8(53):30171–9.
[20] Liu H, Zhang J, Bao N, Cheng C, Ren L, Zhang C. Textural properties and surface
chemistry of lotus stalk-derived activated carbons prepared using different
phosphorus oxyacids: Adsorption of trimethoprim. J Hazard Mater 2012;235–236:
367–75.
[21] Nahil M, Williams P. Pore characteristics of activated carbons from the phosphoric
acid chemical activation of cotton stalks. Biomass Bioenergy 2012;37:142–9.
[22] Hulicova-Jurcakova D, Kodama M, Shiraishi S, Hatori H, Zhu Z, Lu G. Nitrogen-
enriched nonporous carbon electrodes with extraordinary supercapacitance. Adv
Funct Mater 2009;19(11):1800–9.
[23] Reeves W, Perkins R, Piccolo B, Drake G. Some chemical and physical factors
influencing flame retardancy. Text Res J 1970;40:223–31.
[24] Jin Z, Wang B, Ma L, Fu P, Xie L, Jiang X, et al. Air pre-oxidation induced high yield
N-doped porous biochar for improving toluene adsorption. Chem Eng J 2020;385..
[25] Deng Q, Liu L, Lin X, Du G, Liu Y, Yuan Z. Synthesis and CO2 capture properties of
mesoporous carbon nitride materials. Chem Eng J 2012;203:63–70.
[26] Scheirs J, Camino G, Tumiatti W. Overview of water evolution during the thermal
degradation of cellulose. Eur Polym J 2001;37(5):933–42.
[27] Liu Q, Wang S, Zheng Y, Luo Z, Cen K. Mechanism study of wood lignin pyrolysis
by using TG–FTIR analysis. J Anal Appl Pyrolysis 2008;82(1):170–7.
[28] Fang M, Shen D, Li Y, Yu C, Luo Z, Cen K. Kinetic study on pyrolysis and
combustion of wood under different oxygen concentrations by using TG-FTIR
analysis. J Anal Appl Pyrolysis 2006;77(1):22–7.
[29] Wang S, Ru B, Dai G, Sun W, Qiu K, Zhou J. Pyrolysis mechanism study of
minimally damaged hemicellulose polymers isolated from agricultural waste straw
samples. Bioresour Technol 2015;190:211–8.
[30] El-Sayed Y, Bandosz T. Acetaldehyde adsorption on nitrogen-containing activated
carbons. Langmuir 2002;18(8):3213–8.
[31] Montané D, Torné-Fernández V, Fierro V. Activated carbons from lignin: kinetic
modeling of the pyrolysis of kraft lignin activated with phosphoric acid. Chem Eng
J 2005;106(1):1–12.
[32] Keun-Young P, Ji-Hoon J, Jeung-Eun H, Young-Uk K. Mesoporous thin films of
nitrogen-doped carbon with electrocatalytic properties. J Phys Chem C 2012;116
(32):16848–53.
[33] Sevilla M, Valle-Vigon P, Fuertes AB. N-doped polypyrrole-based porous carbons
for CO2 capture. Adv Funct Mater 2011;21(14):2781–7.
[34] Zeleňák V, Badaničová M, Halamová D, Čejka J, Zukal A, Murafa N, et al. Amine-
modified ordered mesoporous silica: Effect of pore size on carbon dioxide capture.
Chem Eng J 2008;144(2):336–42.
[35] Xing W, Liu C, Zhou Z, Zhang L, Zhou J, Zhuo S, et al. Superior CO2 uptake of N-
doped activated carbon through hydrogen-bonding interaction. Energy Environ Sci
2012;5:7323–7.
[36] Wang L, Yang R. Significantly increased CO2 adsorption performance of
nanostructured templated carbon by tuning surface area and nitrogen doping.
J Phys Chem C 2011;116(1):1099–106.
[37] Zhao Y, Zhao L, Yao K, Yang Y, Zhang Q, Han Y. Novel porous carbon materials
with ultrahigh nitrogen contents for selective CO2 capture. J Mater Chem 2012;22
(37):19726–31.
[38] Hao G, Li W, Qian D, Wang G, Zhang W, Zhang T, et al. Structurally designed
synthesis of mechanically stable poly (benzoxazine-co-resol)-based porous carbon
monoliths and their application as high-performance CO2 capture sorbents. J Am
Chem Soc 2011;133(29):11378–88.
[39] Yuan B, Wu X, Chen Y, Huang J, Luo H, Deng S. Adsorption of CO2, CH4, and N2 on
ordered mesoporous carbon: Approach for greenhouse gases capture and biogas
upgrading. Environ Sci Technol 2013;47(10):5474–80.
[40] Li Y, Zou B, Hu C, Cao M. Nitrogen-doped porous carbon nanofiber webs for
efficient CO2 capture and conversion. Carbon 2016;99:79–89.
[41] Bamdad H, Hawboldt K, MacQuarrie S. A review on common adsorbents for acid
gases removal: Focus on biochar. Renewable Sustainable Energy Rev 2018;81:
1705–20.
[42] Seredych M, Bandosz T. Role of microporosity and nitrogen functionality on the
surface of activated carbon in the process of desulfurization of digester gas. J Phys
Chem C 2008;112(12):4704–11.
Q. Ma et al.
[43] Sun F, Gao J, Liu X, Yang Y, Wu S. Controllable nitrogen introduction into porous
carbon with porosity retaining for investigating nitrogen doping effect on SO2
adsorption. Chem Eng J 2016;290:116–24.
[44] Fang H, Zhao J, Fang Y, Huang J, Wang Y. Selective oxidation of hydrogen sulfide
to sulfur over activated carbon-supported metal oxides. Fuel 2013;108:143–8.
[45] Adib F, Bagreev A, Bandosz T. Effect of pH and surface chemistry on the
mechanism of H2S removal by activated carbons. J Colloid Interface Sci 1999;216
(2):360–9.
[46] Kazmierczak-Razna J, Pietrzak R. The use of microwave radiation for obtaining
carbonaceous adsorbents from biomass and their use in elimination of inorganic
pollutants. Adsorption 2016;22(4):473–80.
Fuel 289 (2021) 119932
[47] Seredych M, Bandosz T. Desulfurization of digester gas on wood-based activated
carbons modified with nitrogen: Importance of surface chemistry. Energy Fuels
2008;22(2):850–9.
[48] Geng Z, Xiao Q, Lv H, Li B, Wu H, Lu Y, et al. One-step synthesis of microporous
carbon monoliths derived from biomass with high nitrogen doping content for
highly selective CO2 capture. Sci Rep 2016;6:30049.
[49] Boujibar O, Souikny A, Ghamouss F, Achak O, Dahbi M, Chafik T. CO2 capture
using N-containing nanoporous activated carbon obtained from argan fruit shells.
J Environ Chem Eng 2018;6(2):1995–2002.