金属氧化物耦合含吡咯氮生物质炭吸附CO<sub>2</sub>的机理研究

汪辉春; 顾明言; 陈萍; 王莹; 葛振凌; 汪一

doi:10.19906/j.cnki.JFCT.2023026

金属氧化物耦合含吡咯氮生物质炭吸附CO₂的机理研究

doi: 10.19906/j.cnki.JFCT.2023026

汪辉春^1,,
顾明言^1,,
陈萍^1, ,,
王莹^1,,
葛振凌^1,,
汪一^2,

1.
安徽工业大学能源与环境学院, 安徽马鞍山 243002
2.
华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

基金项目: 国家自然科学基金青年项目（52206129），安徽省自然科学基金青年项目（2208085QE158），煤燃烧国家重点实验室开放基金（FSKLCCA2206）和2022年安徽工业大学“大学生创新创业训练计划”（S202210360403）资助

详细信息

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Tel:18395581520, E-mail: chp0109@126.com

中图分类号: TK6
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出版历程
- 收稿日期: 2023-01-10
- 修回日期: 2023-03-08
- 录用日期: 2023-03-24
- 网络出版日期: 2023-04-06
- 刊出日期: 2023-08-01

Study on the mechanism of CO₂ adsorption by metal oxide coupled with pyrrole nitrogen biochar

WANG Hui-chun^1
,,
GU Ming-yan^1
,,
CHEN Ping^{1
, ,},
WANG Ying^1
,,
GE Zhen-ling^1
,,
WANG Yi^2
,

1.
School of Energy and Environment, Anhui University of Technology, Ma'anshan, 243002, China
2.
State Key Laboratory of Energy Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

Funds: The project was supported by the National Natural Science Foundation of China Youth Program (52206129), Natural Science Foundation of Anhui Province (2208085QE158), State Key Laboratory of Coal Combustion Open Fund (FSKLCCA2206) and 2022 Anhui University of Technology “Innovation and Entrepreneurship Training Program for College Students” (S202210360403)

摘要

摘要: 本研究采用密度泛函理论，研究含吡咯氮生物质炭(CN5)及其耦合不同金属氧化物(ZnO、CaO、Na₂O)对CO₂吸附特性的影响机理。计算CO₂在不同金属氧化物耦合含吡咯氮生物质炭(CN5@MO_x∶CN5@ZnO、CaO、Na₂O)上的吸附量，并结合吸附热对吸附量差异进行分析，发现CO₂在CN5@Na₂O表面发生多层吸附，相较于CN5@ZnO及CN5@CaO，CO₂在CN5@Na₂O上吸附热与吸附量均较高，100 kPa、20 ℃时达到6.11 mmol/g，相互作用更强，更有利于吸附。进一步考察了CN5@MO_x吸附能，计算结果表明，CN5@Na₂O对CO₂吸附能高于CN5@CaO和CN5@ZnO，与吸附量一致。然后对其开展电荷差分密度及态密度分析，电荷差分密度表明CN5@Na₂O吸附能高是由于Na₂O中Na参与吸附，与CO₂中O之间发生电荷转移，态密度分析结果表明CO₂在CN5@Na₂O表面吸附更稳定。
- 生物质炭 /
- 含吡咯氮基团 /
- 金属氧化物 /
- CO₂ /
- 吸附特性
Abstract: In this study, density functional theory was used to study the influence mechanism of pyrroleaze-containing biochar (CN5) and its coupling of different metal oxides (ZnO, CaO, Na₂O) on the adsorption characteristics of CO₂. Calculating the adsorption capacity of CO₂ on different metal oxides coupled with pyrrole nitrogen-containing biochar (CN5@MO_x∶CN5@ZnO, CN5@CaO, CN5@Na₂O), and analyzing the difference in adsorption capacity combined with adsorption heat, it was found that CO₂ multi-layer adsorption occurred on the CN5@Na₂O surface, compared with CN5@ZnO and CN5@CaO, CO₂ adsorption heat and adsorption capacity on CN5@Na₂O were higher, reaching 6.11 mmol/g at 100 kPa and 20 ℃, with stronger interaction and more utilization of adsorption. The CN5@MO_x adsorption energy was further investigated, and the calculation results showed that the CN5@Na₂O adsorption energy for CO₂ was higher than that of CN5@CaO and CN5@ZnO, which was consistent with the adsorption capacity. The charge differential density and state density analysis were carried out, and the charge differential density showed that due to the participation of Na in Na₂O in adsorption, charge transfer occurred between O in CO₂, and the state density analysis showed that CO₂ was more stable adsorption on the CN5@Na₂O surface.
- biochar /
- pyrrole-containing groups /
- metal oxides /
- CO₂ /
- adsorption characteristics

HTML全文

FIG. 2584. FIG. 2584.

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图 1 C−H、C−N5片段

Figure 1 C−H, C−N5 fragments

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图 2 不同生物质炭优化后的构型

Figure 2 Optimized configuration of different biochars

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图 3 CH、CN5构型孔径分布

Figure 3 Pore size distribution of CH and CN5 configuration

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图 4 CN5与ZnO在不同位点耦合构型

Figure 4 (a), (b) and (c) are coupling configurations of CN5 and ZnO at Top, Bridge and Hollow sites, respectively

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图 5 CN5与ZnO不同耦合位点吸附CO₂

Figure 5 CN5 adsorbs CO₂ at different coupling sites with ZnO

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图 6 不同金属氧化物Top位点耦合含吡咯氮生物质炭优化构型

Figure 6 Optimized configuration of pyrroleaze-containing biochar coupled with different metal oxides

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图 7 吸附量随温度的变化

Figure 7 Adsorption capacity varies with temperature

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图 8 20 ℃下CO₂在各生物质炭上吸附量

Figure 8 Amount of CO₂ adsorbed on each biomass char at 20 ℃

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图 9 20 ℃时生物质炭表面CO₂的等温吸附曲线

Figure 9 Isothermal adsorption curve of CO₂ on biochar surface at 20 ℃

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图 10 CO₂在各生物质炭上吸附热

Figure 10 CO₂ adsorbs heat on each biochar

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图 11 CO₂在不同金属氧化物耦合含吡咯氮生物质炭表面的吸附构型

Figure 11 Adsorption configuration of CO₂ coupled with pyrrole nitronitrogen-containing biochar in different metal oxides

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图 12 (a)、(c)、(e)分别为CO₂在不同生物质炭上吸附电荷差分密度图(蓝色、黄色区域分别为得到和失去电子);(b)、(d)、(f)分别为其剖面图(蓝色、红色区域分别为得到和失去电子)

Figure 12 (a), (c) and (e) were the differential density maps of CO₂ adsorption charges on different biochars (the blue and yellow regions gained and lost electrons, respectively); (b), (d), (f) are their profiles (blue and red areas gain and loss of electrons, respectively)

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图 13 CO₂在CN5@MO_x表面的PDOS谱图

Figure 13 PDOS of CO₂ on CN5@MO_x

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表 1 CH、CN5构型比表面积和孔容

Table 1 CH, CN5 configuration specific surface area and pore volume

Sample	BET surface area/(m²·g⁻¹)	Total pore volume/(cm³·g⁻¹)
CH	1556.34	0.69
CN5	1803.37	0.70

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表 2 CN5与ZnO不同耦合位点优化平衡能量

Table 2 CN5 and ZnO have different coupling sites to optimize the balance energy

Coupling site	Balance energy /eV
Top	−74207.0723
Bridge	−74207.1353
Hollow	−74207.2676

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表 3 CN5与ZnO不同耦合位点对CO₂吸附能

Table 3 CN5 and ZnO have different coupling sites for CO₂ adsorption energy

Coupling site	Adsorption energy /eV	Adsorption energy / (kJ·mol⁻¹)
Top	−1.23	−119.05
Bridge	−1.20	−116.19
Hollow	−1.15	−111.05

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表 4 100 kPa时不同温度下CO₂在生物质炭上吸附量

Table 4 At 100 kPa, the amount of CO₂ adsorbed on biochar at different temperature strips

Structure	Uptake /(mmol·g⁻¹)
Structure	0 ℃	20 ℃	50 ℃
CH	4.41	2.73	1.46
CN5	4.45	2.69	1.42
CH@ZnO	4.95	3.05	1.62
CN5@ZnO	5.30	3.51	1.88
CH@CaO	6.17	4.19	2.64
CN5@CaO	6.61	4.51	2.82
CH@Na₂O	7.68	5.45	3.62
CN5@Na₂O	8.86	6.11	4.10

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表 5 20 ℃下各吸附模型拟合常数

Table 5 Fitting constants for each adsorption model at 20 ℃

Structure	Langmuir			Freundlich
Structure	Q_m	A_L	R²	A_F	n	R²
CH	12.877	0.003	0.999	0.050	1.148	0.999
CN5	15.709	0.002	0.999	0.043	1.116	0.999
CH@ZnO	11.132	0.004	0.999	0.070	1.211	0.999
CN5@ZnO	9.713	0.005	0.998	0.099	1.293	0.999
CH@CaO	6.057	0.020	0.962	0.381	1.928	0.993
CN5@CaO	6.345	0.020	0.963	0.414	1.947	0.994
CH@Na₂O	6.429	0.037	0.876	0.870	2.557	0.966
CN5@Na₂O	7.252	0.036	0.889	0.956	2.524	0.972

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表 6 吸附能计算

Table 6 Result of the adsorption energy calculation

Structure	E_pro /eV	E_slab /eV	E_adsorbate /eV	E_ads /eV	E_ads /(kJ·mol⁻¹)
CN5@ZnO	−74207.29	−75241.52	−1032.98	−1.25	−120.88
CN5@CaO	−55031.81	−56066.17	−1032.98	−1.38	−133.04
CN5@Na₂O	−75948.70	−76983.19	−1032.98	−1.51	−145.86

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