Fuel Processing Technology 241 (2023) 107613

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Ultra-microporous biochar-based carbon adsorbents by a facile chemical

activation strategy for high-performance CO2 adsorption
Zhipei Tang a, Jianmin Gao a, *, Yu Zhang a, *, Qian Du a, Dongdong Feng a, Heming Dong a,
Yirui Peng a, Tianhang Zhang a, Min Xie b
a
School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
b
Harbin Electric Science and Technology Co., Ltd., Harbin 150028, China

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

Keywords: The new adsorption-enhanced compressed CO2 energy storage technology uses high-performance adsorbents to
Porous biochar adsorb and store CO2 in low-pressure tanks, reducing vessel costs while significantly increasing energy storage
Ultra-microporous density. In this paper, porous biochar with excellent CO2 adsorption capacity is prepared by carbonization
Microporosity
combined with KOH chemical activation using pine nut shells, which can be used for the energy storage system.
CO2 storage
The influence of pore structure is revealed by changing the activation temperature. The results show that the
Chemical activation
activity of KOH is moderate at 700 ◦ C, which can promote the formation of ultramicropores. The specific surface
area of the obtained porous biochar is 1027 m2⋅g− 1, the distribution center of ultramicropores is about 0.65 nm,
and the microporosity can up to 91.7%, which is very suitable for CO2 adsorption under atmospheric pressure
and room temperature. The CO2 adsorption capacities are 6.05 mmol⋅g− 1 and 3.96 mmol⋅g− 1 at 1 bar, 273 K and
298 K with the pore volume is only 0.56 cm3⋅g− 1. The material also has a low value of isosteric heat of adsorption
about 25 kJ⋅mol− 1. These findings suggest that pine nut shells can be used to design highly porous biochar for the
system of new adsorption-enhanced compressed CO2 energy storage.

1. Introduction dioxide energy storage system was created [6]. By using the intermo­
lecular interaction between the carbon dioxide molecules and the ad­
As industrialization progresses, the energy demand is growing by sorbents at room temperature and pressure, high-density storage of CO2
leaps and bounds, thus bringing about increasingly serious environ­ under atmospheric pressure can be achieved. Meanwhile, the CO2
mental problems. The massive use of fossil fuels, which are the mainstay adsorption performance of the adsorbent materials at room temperature
of the energy system, has led to increasing levels of carbon dioxide in the and pressure is a key factor affecting the energy storage density of the
atmosphere. In 2020, the amount of CO2 in the atmosphere was up to system. Therefore, the preparation of porous materials with excellent
412.5 ppm [1]. It causes sea level rise, global warming, frequent extreme CO2 adsorption performance at room temperature and pressure becomes
natural disasters, etc. [2]. Therefore, different forms of CO2 resource the core issue of this energy storage technology.
utilization, capture and storage technologies such as post-combustion There are many studies on CO2 adsorbents, such as zeolite [7–9],
CO2 capture (PCC) [3] and CO2 capture, utilization and storage MOFs [10–12], metal oxides [13–15], carbon-based materials (activated
(CCUS) [4,5] are receiving more and more attention. The new carbon, biochar, graphene and other carbon isomers) [16–20]. Among
supercritical/trans-critical compressed carbon dioxide storage cycle, a them, the adsorption performance of zeolite is more outstanding, but the
representative technology of CCUS, not only regulates peak and valley expensive preparation cost limits its large-scale application. Biomass-
power but also serves as a buffer regulator for new energy generation based porous activated carbon has excellent CO2 adsorption perfor­
plants by closed-loop carbon dioxide stored underground. However, the mance, which can realize the utilization of waste biomass resources, and
system relies on special geological conditions such as salt caverns, has a good application prospect, so it has gradually become a research
abandoned mines and caves, which affects its wide-scale application. hotspot. Biomass wastes such as rice husk, arundo donax, pine nut shells,
Based on this, a novel adsorption-type trans-critical compressed carbon coconut shells, water caltrop shells, sawdust, etc. [21–26] have become

* Corresponding authors.
E-mail address: [email protected] (J. Gao).

https://doi.org/10.1016/j.fuproc.2022.107613
Received 1 August 2022; Received in revised form 23 November 2022; Accepted 9 December 2022
Available online 22 December 2022
0378-3820/© 2022 Elsevier B.V. All rights reserved.
Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Table 1 microporosity is 87%, while the CO2 uptake could reach 4.06 mmol⋅g− 1
Industrial and elemental analysis of pine nut shells. at 1 bar, 25 ◦ C. Marta et al. [26] used sawdust with the hydrothermal
Industrial analysis (wt%) Elemental analysis (wt%) method and chemical activation to obtain the porous carbon with 88%
percentage of micropores (<1 nm) and CO2 uptake of 4.8 mmol⋅g− 1 at 1
Mad Aad Vad Fc* C H O N S
bar, 25 ◦ C, along with a good CO2-N2 adsorption selectivity. However,
1.21 0.61 78.62 19.56 49.34 5.67 39.53 0.28 0 its microporosity is also lower than 90%, which has a lot of room for
ad: air dry base, *: calculated by difference-subtraction method. improvement.
As a whole, the pore structure and surface functional group distri­
the preferred targets for the development of outstanding performance bution of the adsorbents are the key factors affecting the CO2 adsorption
and low cost CO2 adsorbents. performance of the material. The research hotspots are divided into two
Biomass-based activated carbon generally requires two stages of categories, one is the directional regulation of the pore structure, and the
carbonization and activation to become a high-performance adsorbents other is the surface modification by doping with heteroatoms at different
with a well-developed pore structure [27]. The porosity of the material stages of the activation process. The former aims to optimize the pore
can be further developed by activation operation. Physical activation structure and strengthen the van der Waals force interaction between
and chemical activation are used for activating commonly. The physical pores and adsorbed molecules; the latter through synergistic effect be­
activation method is simpler but the degree of activation is not as good tween chemical interaction and van der Waals force. As for pore struc­
as the chemical method, while the chemical activation can obtain porous ture, it is worth noting that increasing the microporosity, especially the
materials with developed pore structure and the specific surface area can proportion of ultra-microporous, is the key to improve the CO2
up to 3000 m2⋅g− 1. Commonly used activating agents are KOH, NaOH, adsorption performance of materials under atmospheric pressure [34].
K2CO3, H3PO4, ZnCl2, etc. [28–33]. Deng et al. [23] mainly investigated However, for the current regulation of the pore structure of porous
the effect of different working temperature on the optimal adsorption materials, the microporosity is basically 50–90%, and the CO2 adsorp­
pore size of CO2 adsorption under atmospheric pressure, and found that tion capacity under atmospheric pressure and room temperature is
the ultra-microporous pores of 0.33–0.63 nm were the main influencing limited. Therefore, in this paper, we aim to investigate the development
factor at 25 ◦ C under ambient pressure. He et al. [21] prepared a rice of pore structure during the activation process by regulating the acti­
husk-based porous biochar and modified the surface with chitosan as the vation temperature of porous activated carbon materials. Through the
nitrogen source. However, the modification effect was not satisfactory, pre‑carbonization of pine nut shells combined with the activation of
and the CO2 uptake was only 3.68 mmol⋅g− 1 at 1 bar, 25 ◦ C, while it’s KOH directional construction of porous biochar with high microporosity
microporosity is only 56%. Zhao et al. [25] obtained the porous acti­ and concentrated distribution of micropore size, which can achieve high
vated carbon with a nitrogen content of 8.48 wt% and a specific surface performance adsorption of CO2 at room temperature and pressure.
area of 2384 m2 g− 1 by water caltrop shells and melamine. The

Fig. 1. The preparation process and SEM photos of samples. (a) Preparation of biomass-based porous activated carbon; SEM results of samples of (b)PC-500; (c)AC-
700; (d)AC-900.

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Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Fig. 2. Nitrogen adsorption-desorption isotherms and pore size distribution. (a) N2 adsorption-desorption isotherms; (b) Change of pore volume; (c) Pore size
distribution with HK method [30]; (d) Overall distribution of pores with NLDFT method [34].

2. Materials and methods 2.2. Materials characterization

2.1. Materials preparation The surface morphology of the material was investigated by ultra-
high resolution field esmission scanning electron microscopy (HITA­
Pine nut shells were obtained from a farm in Yichun, Heilongjiang CHI UHR FE-SEM SU8010). The specific surface area and pore structure
Province. The industrial analysis and elemental analysis of pine nut parameters of the material were tested by low temperature (− 196 ◦ C) N2
shells are shown in Table 1, with a carbon content of 49.34 wt% and a adsorption-desorption according to a specific surface area and pore size
high content of fixed carbon and volatile fraction [35]. The pine nut microporous analyzer (3H-2000 PM volumetric sorption analyzer,
shells need to be rinsed with deionized water before the experiment and BeiShiDe Instrument Technology Co., Ltd). The samples need to be
dried in a vacuum drying oven. Then, the dried pine nut shells were degassed at 300 ◦ C for 6 h before testing. The specific surface area and
crushed with a crusher and sieved to produce 0.45–0.9 mm particles. pore volume of the material can be acquired from the adsorption-
The next step is the preparation of biochar. A certain amount of the desorption isotherms combined with the BET method. The pore size
sieved pine nut shell pellets were weighed and carbonized at high distribution of the material can be calculated using nonlocalized DFT
temperature in a horizontal tube furnace. Before carbonization, 300 (NLDFT), while the micropores were fitted by the Horvath–Kawazoe
ml⋅min− 1 of pure N2 steam should be introduced to purge the air inside (HK) method. The elemental content of the material surface was tested
the tube. Then the temperature was increased to 500 ◦ C with a ramp rate by XPS (Thermo ESCALAB 250XI) with an operating voltage of 12.5 kV
of 5 ◦ C⋅min− 1 and kept for 90 min. The process was carried out under the and a filament current of 16 mA. Raman spectrometer was used to
N2 (200 ml⋅min− 1) atmosphere, and the carbonization yield was about analyze the degree of material defects (Finder insight pro, Beijing Zhuoli
34%. The prepared biochar was denoted as PC-500. The activation Hanguang Instrument Co., Ltd) with a light source wavelength of 532
process was carried out by the KOH chemical activation method. 1 g of nm and an analysis range of 800–2000 cm− 1. The crystalline phase
biochar was mixed with 2 g of KOH and 20 ml deionized water and composition was acquired by powder X-ray diffraction (XRD) on Rigaku
mechanically stirred at 80 ◦ C until the mixture was dried. And then dried SmartLab diffractometer. Fourier transform infrared(FT-IR) spectros­
at 105 ◦ C overnight. Next, the samples should be activated at copy was used to analyze the surface functionalization by the Thermo
600–900 ◦ C in a pure N2 flow for 90 min (with a ramp rate of IS50.
5 ◦ C⋅min− 1). The activated samples were then washed with 1 M HCl
solution and deionized water until the pH was 7. Finally, we dried the
2.3. CO2 adsorption analysis
samples at 105 ◦ C for 24 h. The resulting samples were labeled as AC-T
(AC denotes activated carbon and T is the corresponding activation
The CO2 adsorption test was performed by H-Sorb 2600 High Pres­
temperature). The preparation process of samples are shown in Fig. 1a.
sure Ads. Analyzer. A sample of 0.2 g was first weighed and placed in a

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Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Table 2 where Qst is the isosteric heat of adsorption, kJ⋅mol− 1; T is the temper­
Specific surface area and pore structure parameters. ature corresponding to adsorption isotherm, K; P is the pressure at which
Sample SBET Smicroa Vtb Vmicc Vmic/ Average a specific equilibrium adsorption amount of CO2 is reached at T, Pa; R is
(m2⋅g− 1) (m2⋅g− 1) (cm3⋅g− 1) (cm3⋅g− 1) Vt pore size the universal gas constant, 8.314 J⋅(K⋅mol)− 1.
(%) D (nm) In addition, the cycle life of the material can be characterized by the
21.2596/ cycle absorption and desorption test. Fixed bed dynamic breakthrough
PC-500 3 0 0.0153 0.0007 4.6
1.2846 experiments were used to evaluate the adsorption kinetic properties of
AC- 2.2346/ the materials. The sample should be degassed at 200 ◦ C for 30 min
800 777 0.4471 0.4038 90.3
600 0.6485
AC- 2.2087/
before the test. The dynamic adsorption capacity of the material can be
1028 999 0.5675 0.5204 91.7 obtained by comparing the difference in sample mass before and after
700 0.6509
AC- 2.1532/ the adsorption test or the integral value of the breakthrough curve. The
1372 1344 0.7386 0.6842 92.6
800 0.7068 slope of the breakthrough curve is the rate of adsorption.
AC- 2.1555/
1850 1806 0.9969 0.8645 86.7
900 0.7141
a
3. Results and discussion
Calculated by the t-plot method.
b
Total pore volume at p/p0 = 0.99.
c 3.1. Porous properties analysis
Micropore volume calculated by H–K method.

Nitrogen adsorption-desorption isotherms were used to determine

test tube, degassed at 300 ◦ C under vacuum for 6 h, and then the CO2
the textural characteristics of AC-X. As we can see from Fig. 2a that a
adsorption isotherms of the samples were tested at 273 K and 298 K with
high amount of nitrogen adsorption at low pressure, indicating that the
the pressure range from 0 to 1 bar, respectively. Meanwhile, the isosteric
internal pore structure is mainly microporous [25]. At the same time, it’s
heat of adsorption can be calculated by the isotherm combined with the
obvious that the saturation capacity of nitrogen sorption increases
Clausius-Clapeyron Eq. [36].
significantly with the increase of activation temperature. But the
( )
P1 T2 − T1 adsorption rate decreases, indicating that the internal pores of activated
ln = Qst × (1) carbon are further developed under high temperature, while part of the
P2 R × T1 × T2
microporous structure is further etched, prompting the pore size to
become larger [37]. Furthermore, the accumulate pore volume is

Fig. 3. XPS of samples. (a) XPS spectrum; (b) C1s peak of AC-700; (c) The distribution of C1s peak; (d) N1s peak of AC-700; (e) The distribution of N1s peak; (f) O1s
peak of AC-700; (g) The distribution of O1s peak.

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Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Fig. 4. Physicochemical properties of samples. (a) Raman spectrum; (b) Ratio of Raman peak area; (c) XRD patterns (d) FT-IR spectra.

increasing sharply when the pore is <0.7 nm in Fig. 2b. As illustrated in appeared excessive etching on the surface, especially the pore entrance,
Fig. 2c, the whole pore size distribution center shifts to right, but the collapse is more obvious, the overall pore diameter gradually become
overall structure is still microporous. Combined with Table 2, the spe­ larger [26].
cific surface area of the biomass-based activated carbon can reach about The elemental composition of the material surface was analyzed by
1850 m2⋅g− 1 and the pore volume can reach 0.99 cm3⋅g− 1, while its XPS. As illustrated in Fig. 3a, the prepared porous activated carbon has
microporosity can up to 92.6%. The pore size distribution in Fig. 2 c- 86.47%–91.42% of carbon atoms, with a high degree of carbonization.
d was obtained by analyzing the adsorption-desorption isotherms at 77 In addition, the more obvious peak on the spectrum is C1s (284 eV)、
K with Horvath–Kawazoe (HK) method and nonlocalized DFT (NLDFT) O1s (525 eV), while the peak of N1s(400 eV) is weak. As we can see from
method [30,34]. The pore size distribution center is basically around Fig. 3b and c, C1s peaks can be fitted by C– – C, C–C, and C–O peaks
0.68 nm at the activation temperature of 600 ◦ C. But, its overall pore with binding energies of 284.7 eV, 285.2 eV, and 287.9 eV [37]. It is
volume is small. The degree of etching was enhanced and the micropore worth noting that materials with different activation temperatures have
volume was improved as the temperature increased to 700 ◦ C. However, similarity distribution of the C1s peaks. Exceptionally, the lower C– –C
when the activation temperature was further increased, the activation content of the activated material indicates an increase in the degree of
degree of KOH was higher. Therefore, most of the ultramicroscopic defects in the sample after etching of activating agent [38]. As illustrated
pores were further etched, resulting in a rightward shift of the center of in Fig. 3d and e, the N1s peaks can be divided into pyridinic-N (N-6),
pore size distribution of activated carbon, while the pore size distribu­ pyridonic-N (N-5), and oxidized nitrogen (N–O) peaks with binding
tion range became wider and the overall pore size became larger. energies of 397.2 eV, 400.8 eV, and 406.6 eV [39]. It is worth noting that
with the increase of activation temperature, the N-5 keeps increasing
3.2. Morphology and surface physicochemical properties along with the decrease of the N-6 ratio, mainly because N-6 promotes
the etching of KOH during the activation process. Therefore, at high
As shown in Fig. 1 b-d, the microscopic morphological changes of temperature, the N-6 is continuously consumed as the degree of etching
biochar before and after activation are characterized respectively. The progress [25]. The O1s peak can then be fitted by four peaks of C– – O, C-
surface of biochar before activation is smoother with a small number of O-C, O H, and O2/H2O with binding energies of 531.5 eV, 532.7 eV,
–
pores as shown in Fig. 1b. The small amount of pores contained may be 533.7 eV, and 536.1 eV, as illustrates in Fig. 3f and g [40,41].
due to volatile fraction removal during high temperature carbonization The extent of defects in the material structure was analyzed by
[22]. Fig. 1c is the activated carbon of AC-700. Due to the high tem­ Raman spectroscopy. The typical disordered structure of carbon (D
perature etching effect of KOH, more folds were produced on the surface peak) and the graphitized structure of carbon (G peak) can be got from
of the material, while the pores were fully developed and distributed Fig. 4a with the distribution ranges of 1324–1330 cm− 1 and 1583–1595
densely [29]. The activity of activating agent is higher, as the temper­ cm− 1, respectively [42,43]. As distributed in Fig. 4b, the ID/IG of PC-500
ature increases to 900 ◦ C. It can be seen from Fig. 1d, pore structure is 0.612, which shows that the material has rich graphitization structure.

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Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Fig. 5. CO2 adsorption of samples at (a) 273 K/1 bar; (b) 298 K/1 bar; (c) Distribution of CO2 adsorption capacity; (d) Isosteric heat of adsorption of samples
calculated from adsorption isotherms obtained at 273 and 298 K.

But, the ID/IG of the material after activation is 0.933–0.991, which 3.3. CO2 adsorption studies
becomes larger as the activation temperature increases. The increasing
number of defect structures in the material indicates the variability in The CO2 adsorption isotherms of the materials at 273 K and 298 K
the degree of etching of the activating agent at different temperatures, under ambient pressure were measured by a gas adsorption analyzer, as
and the more intense etching at a higher temperature, which results in shown in Fig. 5. The observed static adsorption capacity of the materials
the formation of more defect structures [44,45]. was ranged from 4.99 to 6.05 mmol⋅g− 1 for 273 K and 3.04–3.96
As illustrated in Fig. 4c, there is a strong diffraction peak of (002) at mmol⋅g− 1 for 298 K, under ambient pressure. As we can see, AC-700 has
2θ=23◦ -26◦ corresponding to crystal face of carbon, while a weak peak a maximum CO2 uptake 6.05 mmol⋅g− 1 at 273 K under ambient pres­
of (100) at 2θ=43◦ is associated with amorphous carbon [25]. Inter­ sure, while the CO2 uptake decreases to 3.96 mmol⋅g− 1 at 298 K.
estingly, with the increase of activation temperature, the intensity of Obviously, CO2 adsorption capacity of the materials increases with the
peak (002) becomes weaker and peak (100) becomes stronger [40]. The pressure increasing. What’s more, there is a high adsorption rate of CO2
results show that the degree of defects inside the material increases at low pressure, which is attributed to the filling of the ultra-
gradually due to KOH etching at high temperature, coinciding with the microporous [34]. Besides, the adsorption processes is dominated by
Raman data. physical adsorption and is an exothermic process, leading to the CO2
FT-IR spectra of PC-500 and all samples are presented in Fig. 4d. adsorption capacity increase with decreasing temperature [47].
There is a strong absorption peak at 3441 cm− 1, which is corresponding Fig. 5b illustrates the CO2 adsorption isotherm at 298 K. With the
to the O–H stretching vibration in carboxyl and phenol [21]. The weak increase of activation temperature, the static adsorption capacity of CO2
absorption peaks at 2923 cm− 1 and 2852 cm− 1 correspond to the showed a trend of increasing and then decreasing [48]. Among them,
stretching vibration of -CH2- group [30]. The band observed at 1626 AC-700 has a maximum CO2 adsorption capacity up to 3.96 mmol⋅g− 1.
cm− 1 is related to the C– – O stretching vibration in aliphatic ketone or Combined with the Table 2 nitrogen sorption data, the specific surface
C–– C stretching vibration in alkene [28]. The weak absorption peak at area of AC-700 is 1027 m2⋅g− 1 with a small pore volume is 0.5675
1381 cm− 1 represents the C– – O or C–O stretching vibration, and the cm3⋅g− 1, which is smaller than that of AC-800 and AC-900. However,
band observed at 1011 cm− 1 corresponding to C–O stretching vibration combined with the pore size distribution in Fig. 2c, it can be found that
or O–H bending vibration [46]. The bands located at 796 cm− 1 and 545 AC-700 has 91.7% micro-pore volume and its central pore size is about
cm− 1 can be attributed to the out of plane bending vibration of O–H 0.68 nm which is about twice the kinetic diameter of CO2 molecules
[29]. [49]. According to the Quenched-Solid Density Functional Theory
(QSDFT) [21], we can know that its narrower pore size distribution can
result in stronger van der Waals force interaction with CO2 molecules.

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Fig. 6. (a) Adsorption and desorption test; (b) Cyclic absorption and desorption test; (c) Comparison of the CO2 adsorption capacities of nanoporous activated
biochars; (d) The breakthrough curve of CO2 (25 ◦ C).

At the same time, the CO2 adsorption capacity of AC-600 and AC-800 performance of the materials as well as the level of energy consumption
at 298 K demonstrates that the “suitable” pore size distribution plays an for regeneration. Based on the CO2 adsorption isotherms at 273 K and
important role in the CO2 adsorption. Fig. 5b clearly shows that the 298 K under ambient pressure, the number of Qst was calculated using
adsorption curves of AC-600 and AC-800 have a point of intersection at a the Eq. (1) [36]. As shown in Fig. 5d, the number first increases rapidly
pressure of about 0.58 bar, which means that the CO2 adsorption ca­ with the increase of adsorption amount, and gradually reaches the
pacity of AC-600 is higher at lower pressure. Combined with Fig. 2b, it adsorption saturation with further adsorption, so that the heat of
can be seen that AC-600 has more microporous pore volume (<0.68 nm) adsorption gradually tends to be stable [29]. It shows the inhomogeneity
than AC-800. Generally, the ultra-microporous pores are more suitable of adsorption sites on the surface of porous activated carbon [40,50]. In
for CO2 uptake at low pressure. The filling of CO2 molecules in the ultra- particular, it can be seen that the isosteric heat of adsorption of the
microporous pores tends to saturate as the pressure increases further. materials is basically around 12–27 kJ⋅mol− 1, which is in accordance
Therefore the slightly larger micropores become the dominant factor with the characteristics of physical adsorption [51,52], and it is also
affecting the adsorption of CO2 [16]. shown that it requires only a small amount of energy to achieve
Interestingly, as we can see from Fig. 5 that the static adsorption desorption regeneration with lower regeneration energy consumption
capacity of AC-900 at 298 K is not as good as that of AC-600, but it has a and a more economic regeneration cost.
better performance at 273 K. Therefore, much more attention should In order to evaluate the cycle life of the material, we performed the
also be paid to the applied temperature when constructing the excellent adsorption-desorption test and cyclic adsorption performance compar­
porous activated carbon. Because the applied temperature have an ison. It should be noted that the sample was degassed at 300 ◦ C under
important influence in adsorption, which can change the relationship vacuum before each cyclic adsorption test and the whole test was con­
between the molecular thermal movement capacity and the force be­ ducted at 25 ◦ C and 1 bar. As shown in Fig. 6a, the CO2 desorption curve
tween adsorbents [23]. is lower than the adsorption curve. The main reason is that the
Moreover, we summarize the CO2 adsorption capacity for a number desorption test is carried out under the same temperature with adsorp­
of nanoporous activated biocarbons as illustrated in Fig. 6c. The porous tion(25 ◦ C). As we all know, desorption is an endothermic process, but
biochar presented in this study has competitive adsorption properties there is no heat replenishment during the test, so the desorption process
with a high gas storage density, which can be up to 6.05 mmol⋅g− 1 with presents a hysteresis phenomenon [37]. In addition, cyclic adsorption
a small pore volume. Although the value is not the highest, compared to tests have shown promising results. As illustrated in Fig. 6b, the CO2
the others, it has a much higher energy storage density without complex adsorption capacity can up to 97.5% of the original after the 5th cycle,
production step. indicating its excellent cyclic adsorption performance [53].
The thermal effect of the adsorption process can evaluate the The adsorption kinetics of the material was characterized by fixed

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Z. Tang et al. Fuel Processing Technology 241 (2023) 107613

Fig. 7. The mechanism of CO2 adsorption in high ultra-microporous biochar.

bed dynamic breakthrough experiments. Firstly, the N2 flow (255 (3) In addition, porous biochar has excellent adsorption kinetics and
ml⋅min− 1) is inlet into the vertical fixed-bed system to vent the internal cyclic adsorption performance. CO2 can break through the bed at
gases of the system. Following this, the CO2 flow (45 ml⋅min− 1) is ~1 min according to fixed bed dynamic breakthrough experi­
opened, and the gas mixture with a total flow rate of 300 ml⋅min− 1 (15% ments. And after repeated cyclic adsorption-desorption tests, the
CO2) is mixed through the gas mixing device and then passed into the CO2 adsorption capacity of the porous biochar can still up to
fixed-bed system [53]. Dynamic adsorption experiments can visually 97.5% of the original after the 5th cycle, indicating its excellent
compare the dynamic adsorption performance of activated carbon under cyclic adsorption performance.
different activation temperature conditions. The breakthrough curves in
Fig. 6d show that the four samples break through the bed in a short time CRediT authorship contribution statement
and reach adsorption saturation, ~1 min, with good adsorption kinetic
properties [54]. At the same time, AC-700 showed the maximum CO2 Zhipei Tang: Conceptualization, Data curation, Formal analysis,
uptake of 1.105 mmol⋅g− 1, which is closer to the static adsorption test of Writing – original draft, Visualization, Writing – review & editing.
0.15 bar. This measure demonstrates the ability of the material to be Jianmin Gao: Conceptualization, Resources, Funding acquisition. Yu
applied to actual CO2 adsorption. Zhang: Validation, Project administration. Qian Du: Validation, Project
Fig. 7 shows the mechanism of CO2 adsorption in high ultra- administration. Dongdong Feng: Methodology, Validation. Heming
microporous biochar. As we can see, the porous biochar has a rich Dong: Conceptualization, Data curation. Yirui Peng: Investigation,
microporous structure and the surface has a rich microporous structure Writing – review & editing. Tianhang Zhang: Investigation, Writing –
and the surface has some N/O functional groups. The micropores review & editing. Min Xie: Supervision, Validation.
especial ultra-micropores are more attractive to adsorb CO2 molecules.
The Van der Waals forces and electromagnetic interactions play an
important role in CO2 adsorption, indicating the process is physical Declaration of Competing Interest
adsorption [55].
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
4. Conclusions
the work reported in this paper.
The porous biochar with excellent CO2 adsorption performance has
Data availability
been prepared by high temperature carbonization combined with KOH
chemical activation using biomass pine nut shells with 49.34% carbon
No data was used for the research described in the article.
element as raw material. The material can be applied to the system of
new adsorption-enhanced compressed CO2 energy storage which can
significantly drive the development of energy storage technology. The Acknowledgments
specific results are presented as follows:
This work is supported⋅by the 2022⋅Heilongjiang Prov­
(1) The porous biochar has excellent CO2 adsorption properties and ince’s⋅“Emission and carbon neutrality” the open competition mecha­
high energy storage density. The AC-700 has well-developed nism to select the best candidates project (Adsorption-type compression
ultra-microporous distribution with a 91.7% content of micro­ of carbon dioxide energy storage key technology research and demon­
pores, which is more favorable for CO2 adsorption under ambient stration: 2022ZXJ09C01).
pressure conditions, and its CO2 adsorption capacities are 6.05
mmol⋅g− 1 and 3.96 mmol⋅g− 1 at 1 bar, 273 K and 293 K with the References
pore volume is only 0.56 cm3⋅g− 1.
[1] V.F.D. Martins, C.V. Miguel, J.C. Goncalves, A.E. Rodrigues, L.M. Madeira,
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