Fuel 332 (2023) 126243

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

Full Length Article

Functional molecular engineering hierarchical pore-interface based on

thermodynamic-kinetic synergy strategy for efficient CO2 capture
and separation
Xuefei An , Jiahan Yang , Guanxiao Qi , Tongxin Li , Kun Zhao, Dong Fu *
Hebei Key Lab of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding
071003, PR China

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

Keywords:
CO2 absorption properties
3d-hierarchical porous structure
Functional molecular modification
Regeneration energy consumption
Thermodynamic-kinetic synergistic effect
Simulated industrial flue gas
The concern of traditional CO2 adsorbents on business cost and low CO2 adsorption/separation performance have
motivated the production of efficient porous carbons adsorbents from green cheap materials. Combining the
tailoring process of pore structure of materials with microscopic surface functionalization engineering, and
constructing the relationship between kinetics/thermodynamics and adsorption selectivity at the molecular
level, are the key issues to reveal the competition mechanism of adsorption and separation of CO2/N2 mixtures in
science-engineer field. In this work, the nitrogen-groups modified porous carbon microspheres materials
(MNPCS) were fabricated from cheap glucose via a creative ethanol-assisted hydrothermal technology. The
reasonable design of pore effect and functionalized molecular configuration guaranteed the maximization of
thermodynamic-kinetic synergistic effect, and enhanced the adsorption performance and stability in the sepa­
ration of CO2 from flue gas. Impressively, MNPCS exhibits superior CO2 properties (4.77 mmol/g) and high
efficiency separation (the selectivity of CO2/N2 (vol15%: vol85%) reached 56.9) at 313 K. More importantly,
MNPCS balances CO2 adsorption performance and regeneration heat via selection of functional groups config­
uration and 3d-hierarchical porous structure design, which guarantees high CO2 adsorption properties and low
regenerative heat. Comprehensively, the excellent CO2 adsorption performance, water resistance, stability and
low energy consumption of MNPCS make it have great prospects in industrial application.

1. Introduction limitations of strong corrosive, high regenerative energy consumption,

A large number of CO2 emissions led to the continuous rise of the
earth’s surface temperature [1]. CO2 has a certain capacity of heat ab­
sorption, its amount in the atmosphere is very large and its residence
time is very long, so CO2 contributes greatly to global warming [2]. In
order to cope with global warming, more and more countries have made
a commitment to achieve zero net CO2 emissions or carbon neutrality.
Carbon capture, storage and utilization (CCUS) technology can separate
CO2 from industrial tail gas, direct use or permanent emission reduction,
which is an important part of the technology portfolio to achieve carbon
neutralization goal [3]. Efficient and highly selective carbon capture is
the key to promote the popularization and application of CCUS tech­
nology. Currently, amine scrubbing is the only engineering demonstra­
tion project that has received extensive interests from both academic
and industrial communities. However, it suffers from some intrinsic
and high transportation and storage cost of the amine solution. There­
fore, solid adsorption materials by virtue of stability and efficiency have
been suggested as alternative candidates for CO2 separation in industrial
applications [4].
Recently, porous carbon materials attracted researchers’ attention
because of its high specific surface area, abundant pore structure and
modifiable surface functional characteristics [5–7]. Under the back­
ground of low-carbon requirements and carbon emission reduction,
many studies on the application of porous carbon in CO2 capture were
reported every year [8–11]. Traditionally, in order to reduce the overall
cost, waste precursors are generally preliminary purified by alkali liquid
cleaning and activated by physical or chemical activation agents to
fabricate porous carbon materials [12], however, they still suffered
several disadvantages, such as cumbersome preparation process, un-
uniform material structure, low adsorption selectivity and poor

* Corresponding author.
E-mail address: fudong@tsinghua.org.cn (D. Fu).

https://doi.org/10.1016/j.fuel.2022.126243
Received 7 June 2022; Received in revised form 5 September 2022; Accepted 5 October 2022
Available online 12 October 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
X. An et al.
stability [13]. These disadvantages of porous carbon limited its practical
application in the industrial flue gas (CO2: N2 = 15: 85, 313 K-343 K and
high humidity). Besides, previous investigations have indicated that
traditional porous carbon generally lacks specific CO2 affinity sites, and
the CO2 adsorption performance strongly depends on the molecular
sieving ability of the pore structure, which makes selectivity and
adsorption capacity of traditional porous carbon adsorbent relatively
poor [14]. Because of those disadvantages of traditional porous carbon,
it is urgent to design a new porous carbon material to overcome the
limitations of traditional biomass porous carbon in practical application.
Interestingly, according to the mechanism of CO2 adsorption and sepa­
ration, in addition to molecular sieving, the thermodynamics and ki­
netics effects of CO2 in the adsorbent molecular interface are important
factors affecting the mixture gas separation efficiency [15–17]. Specif­
ically, thermodynamic effect realizes the preferential adsorption of
specific components through specific intermolecular interaction. Kinetic
separation is based on the difference of diffusion behavior of gas mol­
ecules in confined space to achieve the separation of different compo­
nents [18]. Therefore, based on the characteristics of porous carbon
adsorbent and CO2 adsorption and separation mechanism, the efficient
separation of CO2/N2 can be achieved by the synergistic effect of ther­
modynamics and kinetics [19]. Therefore, we skillfully combined the
engineering of microscope surface functionalization with the thermo­
dynamic/kinetic effects [20], and flexibly controlled the diffusion and
adsorption behavior of CO2 and N2 in adsorbent by tailoring the func­
tional molecular engineering hierarchical pore-interface structure, so as
to effectively adsorb and separate CO2 from industrial flue gas [21].
Recently, many researches focused on optimizing carbon materials
through heteroatom doping methods to improve the CO2 adsorption
performance [22–25]. The introduction of nitrogen can enhance the
electronegativity of the carbon framework and increase the number of
alkaline functional groups, thereby improving CO2 adsorption and
selectivity [26]. Therefore, in this work, we fabricated a series of rich
nitrogen doped porous carbons and in-depth investigated the relation­
ship of ‘hierarchical pore structure-microscope surface functionalization
–thermodynamics /kinetics effects-adsorption capacity/selectivity’
from the molecular level [27].
Herein, the porous carbon microspheres were fabricated via ethanol
assisted hydrothermal method with glucose as carbon source and nickel
acetate as activator [28]. And we used nitrogen-doped methods to
functionalize the microscope surface of porous carbon spheres [29].
Physical activation endows carbon materials with inter-connected hi­
erarchical pore structure properties and enhances diffusion and
adsorption performance of CO2 in the pore [30]. In addition to physical
activation, carbon surface functionalization can increases the chemical
adsorption sites on the microscope surface and enhances the surface
molecular polarity of the materials, so as to significantly improve the
adsorption force and adsorption rate between the material molecular
interface and CO2 [31]. More importantly, the reasonable design of pore
effect and functionalized molecular configuration guarantees the
maximization of synergistic effect, and enhances the adsorption per­
formance and stability in the separation of CO2 from simulated flue gas.
On this basis, we systematically analyzed and evaluated the key pa­
rameters of adsorption and separation thermodynamics, adsorption and
desorption kinetics, thermal stability, cycle stability and water resis­
tance for the design of CO2 adsorption and separation process.
In a word, we have successfully constructed the relationship between
the microstructure and chemical properties of adsorbent materials at the
molecular level. More importantly, the pore structure and microscopic
surface functionalization of the adsorbent materials designed by us are
controllable, which overcomes the defects of traditional carbon mate­
rials, solves the shortcoming of uncontrollable shape and size of tradi­
tional carbon materials, and further optimizes the preparation process.
Adsorption and desorption results showed that MNPCS possesses
excellent performance and stability under the assessment of industrial
application standards. It can be expected that MNPCS will paves a
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Fuel 332 (2023) 126243
creative way for designing of CO2 adsorption material and possess great
engineering significance in the practical application of separating CO2
from ultra-low emission industrial flue gas.
2. Experimental section
2.1. Materials
Glucose (C6H12O6) and nickel acetate (Ni(CH3COO)2) were pur­
chased from Shanghai Cartesi Biotechnology Co. Ltd., Melamine
(C3H6N6) was obtained by tianjin Hengxing Chemical Reagent
Manufacturing Co. Ltd., Ethanol (C2H6O, 99.9 %) and Methanol
(CH3OH, 99.9 %) were supplied by Tianjin Mikeou Sci-Tech Co. Ltd.,
Hydrochloric acid (HCl) and Urea (CO(NH2)2) were provided by Aladdin
Biophysiochemical technology (shanghai) Co. Ltd., CO2, N2, and Ar
gases of ultra-high purity (99.999 %) were provided by Baoding Jinglian
Co. Ltd.
2.2. Preparation of samples
To obtain the porous carbon spheres, glucose was used as carbon
source and nickel acetate was used as an activator. One step hydro­
thermal method was adopted, after which the product under goes an
activation process at high temperature. Subsequently, porous carbon
spheres were subjected to microscopic surface functionalization and
some functional groups were introduced to get final samples. The pro­
cess is shown in Fig. 1. The modified porous carbon spheres were syn­
thesized with three-steps process, the specific details are as follows:
(1) 4.5 g of glucose and 0.35 g of nickel acetate (Cobalt acetate/zinc
acetate/ manganese acetate) were dissolved in the mixed solution of
water / ethanol (vol90%: vol10%); the solution was transferred to a 100
ml autoclave after dissolved ultrasound. The autoclave was reacted in a
160℃ for 8 h to obtain the sample, and the nano-carbon spheres pre­
cursor was obtained after multiple filtrations and washing.
(2) The nano-carbon spheres predictor was heat treated at 600℃ for
1 h (heating rate of 10 K/min, N2 atmosphere), and the PCS (PCS-Ni,
PCS-Mn, PCS-Co, PCS-Zn) with hierarchical pore-interface structure was
obtained.
(3) Typically, 0.5 g of nano-carbon spheres predictor was dispersed
into 50 ml methanol solution containing melamine (the mass fraction of
melamine was 2 wt%). The mixture was stirred at room temperature for
48 h. Then, the solid product obtained by centrifugation was activated at
600℃ in a tubular furnace (heating rate of 10 K/min, N2 atmosphere) to
obtain MNPCS. Under the same experimental conditions, replacing the
impregnated fluid to 2 wt% of the urea water solution will get nitrogen
doped porous carbon microsphere materials (NPCS).
The samples obtained at activation temperatures of 450℃ and 750℃
were referred to as MNPCS-450 and MNPCS-700, respectively.
2.3. Material performance test
2.3.1. Static adsorption performance test
The adsorption capacity of samples was tested by using a Micro­
meritics JW-BK122W volumetric adsorption analyzer. The specific
operation is as follows: (1). Weigh a certain amount of adsorbent, load it
into the sample tube and dry it in vacuo 120℃ for 8 h. (2). Charge a
quantity of gas into the sample tube to measure the gas adsorption ca­
pacity under different balance pressure.
2.3.2. Dynamic adsorption performance test
The gas dynamic penetration curve was measured by using a self-
made gas dynamic separation device. MNPCS was degassed and dried
in a vacuum environment at 120 ◦ C for 5 h. Filling a certain amount of
sample into the inner column of the fixed bed, and controlling the intake
gas temperature at 313 k and the intake gas rate at 30 ml / min, and then
the outlet gas volume was recorded by the gas flow meter and the CO2
X. An et al. Fuel 332 (2023) 126243

Fig. 1. Schematic representation of MNPCS fabrication process.

Fig. 2. SEM images of PCS (a) and MNPCS (b, c); TEM images of MNPCS (d); N2 adsorption–desorption isotherms (e) and pore size distributions(f) of CS, PCS and
MNPCS. The EDS-SEM mapping of MNPCS(g);

3
X. An et al.
content was recorded through the CO2 analyzer (on-line gas analyzer,
UE55-ST-CO2).
Cycle experiment: After CO2 adsorption is balanced, heat the fixed
bed temperature to 105 ◦ C and purge with N2 for 30 min for desorption,
and then repeat the above adsorption experimental steps for cyclic
experimental measurement. The outlet gas volume was recorded by the
gas flow meter and the CO2 content was recorded through the CO2
analyzer. Besides, Water vapor adsorption was determined by Multi-
Component Adsorption Breakthrough Curve Analyzer.
2.4. Adsorbent′ s characterizations
Scanning electron microscopy (SEM, JSM-7800F instrument) and
Transmission electron microscope (TEM, FEI-Tecnai G2 F20) were
employed to characterize the morphology and structure. The chemical
functional groups of the material Fourier were investigated by means of
transform infrared spectrometer (FTIR, Theromo Fisher, America). X-ray
photoelectron spectroscopy (XPS) of various samples was conducted on
a photoelectron spectrometer (Thermo Fisher Scientific). The specific
surface and pore analyzer were identified by Brunauer-Emmett-Teller
(BET, Micromeritics ASAP 2020 adsorption analyzer). Thermal stabil­
ities were assessed via the thermogravimetric analysis method (TGA,
STA 409 PC, Netzsch, Germany) in an inert nitrogen atmosphere.
3. Result and discussion
3.1. Characterization
SEM micrographs of the PCS with different amounts of activators
(Fig. 2(a)) and MNPCS (Fig. 2(b, c)) are respectively illustrated. It can be
clearly observed that the material mainly presents a spherical structure
with a uniform morphology. The spherical structure has high particle
fluidity and excellent mechanical strength, which are helpful to main­
tain the stability of the adsorption performance. As can be observed from
the Fig. 2(a), the addition of activator (nickel acetate) has obvious
impact on the pore morphology. With the addition of activator, the
molecular interface structure of the material is constantly etched and
then become a porous structure [32]. Moreover, the composition and
porous structure of PCS activated at different amounts of activators also
have dramatic difference, and the molecular interface is etched more
seriously at higher addition of activators. Meanwhile, the internal
composition and uniformly dispersed spherical structure of MNPCS are
showed with TEM images (d). In addition, the N2 adsorption–desorption
isotherms and pore size distribution (PSD) of samples are illustrated in
Fig. 2(e, f), high microporosity of MNPCS presents since the isotherms of
MNPCS exhibit type Ia and the microporous structure is further
confirmed in the PSD of MNPCS. As can be seen from the Fig. 2(f), the
PSD of MNPCS from micro- to meso-to macropore structure (the mac­
ropore structure of MNPCS is also clearly observed in the Fig. 2(b)),
which indicates MNCPS has a 3d- hierarchical porous structure. Due to
capillary condensation, a large number of micropores and small-
mesopores play a decisive role in CO2 adsorption, and mesopores and
macropores promote CO2 transfer. Therefore, the 3d- hierarchical
porous structure is conducive to CO2 adsorption. It is well known that in
industrial applications, the problem of great pressure drop in fixed bed
adsorption can affect the performance of porous carbon materials
[33,34]. And the physical properties of adsorbent particles, such as
particle size, shape, surface roughness, etc., can affect the pressure drop
of the fixed bed. The morphology of MNPCS is a spherical structure with
connected pores, and the spherical particles have high particle fluidity
and excellent mass transfer performance. Therefore, compared with
other powdered porous carbon, it can reduce the mechanical energy loss
of gas flowing in the bed and reduce the influence of pressure drop to a
certain extent. In addition, compared with PCS, MNPC shows a higher
specific surface area and pore volume (see in Table S1), suggesting that
the introduction of nitrogen into carbon framework at high temperature
4
Fuel 332 (2023) 126243
increases the molecular etching in carbon materials. Furthermore, the
EDS-SEM mapping of MNPCS can be used to further understand the N-
elemental distribution. Uniformly distributed N elements in Fig. 2(g)
illustrates that the N element is successful and uniformly doped into the
porous carbon.
To explore the graphitic degree of carbon in the material after N-
doping, the Raman spectra of PCS and MNPCS (Fig. 3(b)) provides direct
evidence to reflect the difference. The D band indicates structural de­
fects, indicating that there is an amorphous carbon structure in material.
This kind of defect structure makes the porous carbon spheres possess
more active adsorption sites. the G band represents the regular structure,
indicating that the carbon material itself has a regular sp2 structure
similar to graphene. The existence of such a regular structure in the
porous carbon is beneficial to reduce the resistance to the adsorption
and transfer of ions or gas molecules. Considering that the intensity ratio
of the G and D bands (IG/ID) can be used to reflect the graphitic degree of
carbon, and the IG/ID ratio of PCS (1.1) is larger than that of MNPCS
(0.94). The introduction of N-groups into carbon framework increases
the levels of defects and disorder in MNPCS, indicating that a large
amount of adsorption active site is added to the surface of the MNPCS
molecule. To deeply investigate the existence and form of N-functional
groups in MNPCS, the FTIR spectroscopy (Fig. 3(a)) and XPS spectrum
(Fig. 3(c-e)) of the samples were measured. It can be observed from
Fig. 3(a) that the surfaces of CS and PCs mainly contain oxygen-
containing functional groups such as –OH and C– – O. After the intro­
duction of N-functional groups, the stretching vibration peaks of C–N
(1030 cm− 1) and R’–NH-R (1380 and 1670 cm− 1) are observed in the
infrared spectra of MNPCS. To understand the relationship between the
preparation conditions and N-functional groups of the carbons, the total
nitrogen content and the amount of various nitrogen-containing func­
tional groups were investigated by XPS. As shown in Fig. 3(c-e), the N1s
spectrum reveals three nitrogen species on the surface of MNPCS,
namely pyridinic N, pyrrollc N and graphitic N. Generally, the pyridinic
N and pyrrolic N are located at the edge of the graphitic carbon layer
which are favorable for the surface adsorption, while the graphitic N is
arranged inside the graphitic carbon layer bonds which could enhance
the electronic conductivity of the carbon networks [35]. More inter­
estingly, the relative percentages of the nitrogen species are influenced
by the activation temperature. The relative percentages of nitrogen
species are calculated from the corresponding peak areas of the decon­
voluted N1s spectra. In addition, the relative contents of N-groups
change obviously with the increase of the temperature. The proportion
of pyridinic-N increases as the carbonization temperature increases,
indicating that under pyrolytic conditions, pyridinic-N is the most stable
N species.
3.2. Adsorption performance test
Adsorption is a surface mass transfer process, the pore size and pore
volume will affect the molecular diffusion and capture. Activator is the
main factor affecting the structure of the adsorbent [36]. PCS with
different pore structures were obtained by adjusting the type and
amount of activator (acetate), and their CO2 adsorption properties were
determined. Through the comparison of the structure and absorption
properties, a suitable way to explore the influence of the type and
amount of activator on the pore structure of the material can be pro­
vided. As shown in Fig. 4 (a), when 0.35 g nickel acetate is added to 4.5 g
glucose as activator, PCS achieves the best adsorption performance
(3.02 mmol/g, 313 K). After high temperature activation, the nickel
element is present in the form of nickel atoms. To explore the effect of
zinc in PCS on the adsorption of CO2, PCS was soaked in dilute hydro­
chloric acid to remove Ni2+, and then its adsorption performance was
measured. As can be seen from Fig. 4b, the CO2 adsorption performance
of PCS and acidified PCS remains almost unchanged, indicating that the
effect of the existence of Ni atoms in PCS on the adsorption of CO2 can be
ignored. Generally, the efficient green N-doping method follows the
X. An et al. Fuel 332 (2023) 126243

Fig. 3. FTIR spectra of CS, PCS and MNPCS (a); Raman spectra of PCS and MNPCS (b); XPS species fitted N1s for MNPCS. 450 ℃(c), 600 ℃(d), and 750 ℃(e).

Fig. 4. The adsorption performance of PCS was prepared under different activator conditions(a); CO2 adsorption isotherms of PCS, acidified PCS(b), NPCS and
MNPCS(c); CO2 adsorption isotherms of MNPCS (unit mass) (d); (unit surface area) (e); The contents of nitrogen functional groups in MNPCS(f).

preparation-line of ‘solution impregnation → High temperature
carbonization’. Through the simple selection of the impregnation solu­
tion of the nitrogen-containing precursor, we found that when melamine
was used as the nitrogen-containing impregnation solution, the obtained
MNPCS had a higher CO2 adsorption capacity, which reached 4.77
mmol/g at 313 K and 1 bar. (Fig. 4 (c)). The results show that the
introduction of a large number of N-functional groups can effectively
improve the CO2 adsorption performance. The carbonization tempera­
ture also affects the degree of N-doping in MNPCS. Fig. 4 (d) shows the
CO2 adsorption isotherms of MNPCS at carbonation temperatures of
450℃, 600℃ and 750℃. The MNPCS-600 has the highest CO2 adsorp­
tion capacity. In order to further explore the relationship between the
surface chemical properties of the material and the CO2 adsorption ca­
pacity, adsorption isotherms based on unit surface area (Fig. 4(e)) were

5
X. An et al.
measured. According to the data presented in Fig. 4(e), MNPCS-750
possesses the lowest adsorption capacity compared with MNPCS-450
and MNPCS-600. Interestingly, MNPCS-750 has higher specific surface
area and pore volume (as shown in Table S1), while the content of ni­
trogen functional groups is the lowest (Fig. 4(f)). The phenomenon in­
dicates that the CO2 adsorption capacity is related to the content of N
functional groups on the material surface. The excellent CO2 adsorption
capacity of MNPCS-600 benefits from the synergistic effect of pore
structure and surface functional groups. Appropriate micropore size,
high specific surface area and rich N-groups are the key factors affecting
CO2 adsorption properties.
To quantitatively explore the influence of N-functional groups on
CO2 adsorption, the ratio of different nitrogen components in the sample
was obtained by calculating the peak area of different nitrogen com­
ponents in XPS. Fig. 4 (f) provides the total nitrogen content and the
nitrogen content of the different nitrogen-containing functional groups
in the three samples. Obviously, the presented CO2 adsorption capacity
has a poor linearly relationship with the total amount of nitrogen
functional groups of the MNPCS. However, there is good trend between
adsorption capacity and the amount of specific nitrogen functional
groups [37]. Therefore, we can regulate the composition of nitrogen
function group in the adsorbent by adjusting the nitrogen source and
activation temperature, which in turn affects the performance of the
adsorbent.
3.3. Thermodynamics and kinetics
The separation of CO2 / N2 based on physical adsorption can be
divided into equilibrium separation, kinetic separation and molecular
sieving, and the former is chosen in this work. The equilibrium sepa­
ration is governed by thermodynamic factors. It realizes the preferential
adsorption of CO2 through specific intermolecular interactions, and
strong interactions are usually conducive to promoting the recognition
effect between molecules. Therefore, the adsorption heat corresponding
to the separation of CO2 and N2 is high, but the high adsorption heat
increases the difficulty of adsorbent regeneration. Impressively, a
Fig. 5. The isosteric heat of CO2 and N2 (a); The isosteric heat of CO2 in three adsorbents(b); CO2 adsorption curves (a); CO2 adsorption rate (d) of PCS and MNPCS;
CO2 adsorption kinetics of PCS and MNPCS (e).
6
Fuel 332 (2023) 126243
number of literatures have reported a method to balance the higher
regeneration energy consumption by synergistic effects of kinetic effects
in the CO2/N2 separation process [38–40]. The so-called synergistic
kinetic effect refers to the separation of different components by con­
structing reasonable spatial modules within the material to selectively
limit the diffusion behavior and adsorption rate of gas molecules at the
porous molecular interface of the material. Therefore, highly efficient
and easily regenerable MNPCS can be designed based on
thermodynamic-kinetic effects. Based on this idea, we investigated the
competition mechanism of adsorption and separation of CO2/N2
mixtures.
The isosteric heat of adsorption can be predicted from the parameters
derived from the isotherm models (The isotherms of MNPCS at different
temperatures are displayed in the Fig. S1) using the Clausius-Clapeyron
equation:
( )
ΔHs ∂lnP
=− (1)
RT 2 ∂T q
In which ΔHs (kJ/mol) is the isosteric heat of adsorption, p (kPa) is
the partial pressure of CO2, R (8.314 J/mol/ K) is the universal gas
constant, and T (K) is the reaction temperature. The equivalent
adsorption heat was calculated, and presented in Fig. 5(a). The result
exhibits the declining heats of CO2 adsorption in the MNPCS with
increasing adsorption capacity, indicating the heterogeneity of the
adsorption sites. The adsorption heat of MNPCS is higher than that of
single physical process (20KJ/mol), but less than 40KJ/mol, which
shows that the adsorption of CO2 on nitrogen-containing porous carbon
materials is mainly physical adsorption, but there is a certain amount of
chemical adsorption at the same time. In addition, the material exhibits
different thermodynamic affinity to CO2/N2. Compared with the
isothermal heat of PCS, MNPCs has higher CO2 isothermal heat (32 kJ /
mol) and lower N2 isothermal heat (11.85 kJ/mol) at low degree of CO2
coverage, which indicates that CO2 has stronger interaction with the
adsorption sites on the molecular surface of MNPCS. And the adsorption
heat difference of MNPCS increased, which represents MNPCS possesses
X. An et al.
better separation selectivity for CO2/N2 gas mixture. Furthermore, it can
be clearly observed in Fig. 5(b) that the adsorption heat of MNPCS-600 is
less than that of MNPCS-450 and greater than that of MNPCS-700.
However, the CO2 adsorption capacity of MNPCS-600 is much higher
than that of the other two samples, which verifies that the high CO2
adsorption capacity of MNPCS-600 benefits from the synergistic effect of
the pore structure and surface heterogeneous active site. Therefore,
MNPCS has higher CO2 adsorption selectivity for CO2/N2 gas mixture.
Compared with some reported nitrogen doped adsorbents (as displayed
in Fig. S2), MNPCS possesses high adsorption performance and low
adsorption heat. The major reason is that the high separation perfor­
mance of MNPCS is not completely contributed by thermodynamic
factors, and the kinetic effect also promotes the separation of CO2/N2.
Therefore, the time-dependent adsorption capacity (Fig. 5 (c)) and
adsorption kinetics (Fig. 5 (e)) of MNPCS and PCS were measured by
static adsorption method, and then the adsorption rate was calculated
(Fig. 5 (d)). The adsorption rate parameters in CO2 adsorption kinetics
were selected to investigate the separation performance of MNPCS.
From Fig. 5(d), we found that MNPCS has a higher CO2 adsorption rate,
which facilitates CO2 to faster occupy the adsorption site on the sur­
face，thereby improve the competitive adsorption of CO2 in the gas
mixture and enhance the separation performance. The data presented in
Fig. 5(e) could be used to more intuitively compare the adsorption ki­
netics of MNPCS and PCS. The CO2 adsorption performance of MNPCS
was preliminarily evaluated according to the CO2/N2 separation
mechanism, MNPCS possesses higher CO2 adsorption capacity and can
reach adsorption equilibrium in a shorter time, which greatly improves
the CO2 adsorption potential and separation performance. More
importantly, MNPCS has high thermodynamically and kinetics dual
priority adsorption characteristics of CO2, and can achieve efficient
separation of CO2/N2 by synergistic effect.
Fig. 6. DSLF fitting of the CO2 and N2 adsorption isotherms of PCS (a) and MNPCS(b). Breakthrough curves of CO2 and N2 (c). The structure–performance rela­
tionship of MNPCS sorbents (d). IAST predicted and experiment measured selectivity on MNPCS (e). Comparison of the selectivity for other nitrogen-doped ad­
sorbents (f).
7
Fuel 332 (2023) 126243
3.4. Separation performance of CO2 from simulated flue gas
The main components of industrial flue gas meeting ultra-low
emission standards are 15 % CO2 and 85 % N2 [2]. Effective CO2 ad­
sorbents are expected to have high selectivity for CO2 over other gases in
industrial flue gas separation application [41]. Therefore, it has great
significance to explore the adsorption selectivity theorem of CO2 and N2
by combining experiments and models for the selection of adsorbents
and the optimization of operating conditions [42]. The selectivity of
adsorption was predicted from the parameters derived from the dual-site
Langmuir-Freundlich (DSLF) model using the ideal adsorbed solution
theory (IAST):
( )( )
x1 y2
S= (2)
x2 y1
where S represents adsorption selectivity; x1, x2 and y1, y2 represent the
mole fractions of CO2 and N2 in the adsorbent and the gas phase,
respectively [43]. The adsorption isotherm data of CO2 and N2 were
fitted by DSFL model (see in Fig. 6(a, b), the values of all parameters in
DSFL model are mentioned in the Table S2 and Table S3.) combined
with IAST theory to calculate the selectivity of PCS(S = 18.9) and
MNPCS (S = 51.7) for CO2/N2 gas mixture(vol:15/85) at 313 K (as
shown in Fig. 6(e)) [44–46]. To verify the accuracy of the IAST pre­
diction and evaluate the dynamic CO2 adsorption capacity and selec­
tivity over N2, dynamic “breakthrough” separation experiments were
conducted at 1.0 bar and 313 K [47]. The experiment was carried out in
the self-made fixed bed, and the experimental device diagram is shown
in Fig. 6(d). And the result is presented in Fig. 6(c), the penetration time
of CO2 and N2 on the adsorbent is quite different, so that MNPCS
adsorbent can effectively separate CO2 and N2 in industrial flue gas that
meets ultra-low emission standards [48]. The dynamic absorption ca­
pacity of MNPCS for CO2 and N2 in CO2 / N2 (vol: 15/85) mixture gas are
1.757 mmol/g and 0.175 mmol/g, respectively. Interestingly, it could be
found from Fig. 6 (e) that the separation coefficient measured by fixed
X. An et al. Fuel 332 (2023) 126243

bed experiment reaches 56.9, which is higher than the value predicted reported in the literature, MNPCS has relatively excellent performance
by IAST theoretical model (s = 51.7). It is inferred that the deviation in and lower cost, so it should have a greater cost advantage in future in­
the N2 adsorption capacity of N2 and CO2 selectivity are caused by the dustrial applications.
crowding-out effect of CO2 on N2. In addition, compared with the
selectivity of PCS, the selectivity of MNPCS is greatly improved, which
3.5. Thermal stability and cycle stability
further emphasizes the greater importance of nitrogen groups in
affecting both the CO2 adsorption capacity and the selectivity [49]. To
In general, for the industrial application of adsorbents, besides
more fully understand the properties of adsorbent, comparison with the
excellent adsorption performance and selectivity, good stability and
performance of other N-doped porous carbon adsorbents reported in the
regeneration performance are also essential [54]. The high stability and
recent literature (the status is observed in Fig. 6 (f)), the adsorption
the high-water resistance can improve the energy utilization rate, and
capacity and selectivity of MNPCS are relatively excellent, and achieving
can keep the continuous stability of the adsorption effect in practical
advanced adsorbent levels in industrial application [50–53]. Further­
application. Therefore, the thermal stability of the sample was deter­
more, compared with these adsorbents, MNPCS prepared by innovative
mined by thermogravimetric analysis, and the weight loss of MNPCS
ethanol auxiliary water thermal method has a uniform spherical struc­
with temperature changes can be observed in Fig. 7 (a). The weight loss
ture, and its adsorption properties and mass transfer properties are more
of MNPCS at 97 ◦ C was about 3. 5 % due to the volatilization of water
stable than traditional powder adsorbents. By controlling nitrogen
and impurity molecules in the sample, but no further mass loss was
doping temperature to adjust the degree of functionalization of the
found at further heating up to 200 ◦ C, indicating that the MNPCS sample
material, the reasonable pore effect and functional molecular configu­
has good thermal stability below 200 ◦ C. between 200 ◦ C and 400 ◦ C,
ration is guaranteed. MNPCS has higher adsorption performance than
MNPCS displays a slight weight loss about 2.72 %, which also reveals its
these biomass carbon adsorbents. Additionly, compared with some
high thermal stability. In addition, one crucial factor to evaluate CO2
traditional activated carbon properties (as see in Table. S5), MPNCS also
adsorbent performance is the regeneration. To provide the required
has better adsorption capacity and selectivity. In addition, the cost of
desorption parameters of the regeneration heat, the adsorp­
MNPCS, PCS and other reported adsorbents were calculated and
tion–desorption experiment of MNPCS was measured (as illustrated in
analyzed (as displayed in Table. S6). Compared with PCS, although the
Fig. 7 (b)). The adsorption experiments were carried out at 313 K and the
cost of MNPCS is slightly increased, its adsorption performance and
adsorbed gas was pure CO2. Desorption experiments were carried out at
selectivity are greatly improved. Compared with other adsorbents
378 K. Significantly, regeneration energy consumption is an important

Fig. 7. The TGA curves (a); CO2 adsorption–desorption profiles (b) of MNPCS; Comparison of regeneration heats (c). recycle runs of MNPCS (d). Adsorption isotherm
of H2O (e) and CO2 after exposure to different humidity(f). The effect of wet CO2 on the adsorption of CO2 by MNPCS(g).

8
X. An et al.
indicator for evaluating material performance, which possesses very
important engineering significance. The required regeneration heat (Qr)
was calculated by the equation S1 (see in the Supplementary Material.
The heat capacity of MNPCS is shown in Fig. S3 and the values of all
parameters are mentioned in the Table S4.). As shown in Fig. 7 (c),
MNPCS has a relatively lower regenerative heat (0.97 MJ/kg) compared
to other reported solid-modified porous materials [55–57]. MNPCS
balances CO2 adsorption performance and regeneration heat via
reasonable selection of functional group configuration and 3d-hierarchi­
cal porous structure design, which guarantees high CO2 adsorption
performance and low regenerative heat. Meanwhile, green synthetic
MNPCS with low regenerative energy consumption and high CO2
adsorption performance have great prospects and engineering signifi­
cance in industrial applications. Moreover, we conducted the consecu­
tive CO2 adsorption/desorption cycles under the above conditions.
Through Fig. 7 (d), it can be seen that the fluctuation of CO2 adsorption
capacity is not large, and the adsorption efficiency can still reach 91 %
after 30 cycles, which indicates that the MNPCS has good long-term
stability.
In addition to CO2 and N2, there is a small amount of water vapor in
the flue gas that meets the ultra-low emission standards. Therefore, it is
necessary to study the effect of water vapor in flue gas on the perfor­
mance of adsorbents. To explore the water resistance of MNPCS, the
water vapor adsorption isotherm was measured (Fig. 7. (e)), indicating
that the adsorption isotherm of MNPCS is S-shaped and the adsorption
force of water vapor is weak when the relative humidity is less than 40
%. In addition, the preservation and application process of the material
is difficult to ensure that the fully dry environment in in the practical
situation, so the CO2 adsorption performance of MNPCS is measured
after the material is exposed to a high humid environment in a period of
time. As we can see from Fig. 7(f), the CO2 adsorption capacity of
MNPCS shows almost no fluctuations after the sample is exposed to
different humidity environments for 36 h, indicating that MNPCS
possess excellent water resistance. More importantly, in order to more
intuitively explore the effect of water vapor, the CO2 adsorption ca­
pacities of MNPCS for the mixture gas containing different content of
water vapor (50 %CO2/ 50 % (water vapor þ N2)) was measured. The
CO2 adsorption capacities of MNPCS for the CO2 mixture with different
content of water vapors are shown in the Fig. 7(g), the CO2 adsorption
capacities of MNPCS decreases slightly in the presence of water. When
the humidity of mixture gas reaches 30 %, the adsorption efficiency of
MNPCS can still reached 92 %, which is sufficient to meet industrial
needs in practical applications.
4. Conclusion
In summary, we successfully developed a convenient strategy for the
fabrication of nitrogen-rich hierarchical porous carbon spheres by
simultaneously carbonization and nitrogen-functional. The resultant
MNPCS possesses well-developed 3D-hierarchical porous structure and
rich nitrogen-functional groups. Compared with the carbon-based ad­
sorbents dominated by physical adsorption reported in recent years,
MNPCS has achieved a CO2 adsorption capacity of 4.77 mmol/g and a
CO2/N2 (15:85) separation coefficient of 56.9 at 313 K and 1 bar,
reaching the level of international excellent adsorbent. Moreover, the
reasonable design of pore effect and functionalized molecular configu­
ration guaranteed the superior CO2 adsorption capacity, excellent
thermal/cycle stability, good water resistance and high selectivity of
MNPCS. Impressively, we also constructed the relationship between the
parameters of kinetic/thermodynamic and separation selectivity from
the molecular-level, which is the significant issue for revealing the CO2/
N2 mixture adsorption separation mechanism in science-engineer field.
At the same time, the effectiveness of thermodynamic-kinetic synergy
strategy to improve the gas adsorption and separation performance of
porous materials is verified. The strategy also has good mobility, which
can provide a new idea for the separation and purification of other gas
9
Fuel 332 (2023) 126243
mixtures. Besides, regulating CO2 adsorption performance and regen­
eration heat via reasonable selection of functional groups configuration
and 3d-hierarchical porous structure design, which guarantees high CO2
adsorption performance and low regenerative heat. Therefore, it can
improve the progress of energy efficiency engineering in industrial
applications.
CRediT authorship contribution statement
Xuefei An: Conceptualization, Methodology, Investigation, Valida­
tion, Writing – original draft, Data curation, Visualization. Jiahan
Yang: Methodology, Validation, Data curation, Visualization, Writing -
review & editing. Guanxiao Qi: Methodology, Formal analysis, Inves­
tigation, Data curation. Tongxin Li: Investigation, Data curation. Kun
Zhao: . Dong Fu: Resources, Writing – review & editing, Supervision,
Project administration, Funding acquisition.
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.
Data availability
The authors are unable or have chosen not to specify which data has
been used.
Acknowledgments
The authors appreciate the financial support from the National
Natural Science Foundation of China (No. 51776072; 42007327 and
41731279).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2022.126243.
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