Study on the mechanism of NO adsorption by CaO coupled nitrogen-doped biochar
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摘要: 本研究采用密度泛函理论，探究了不同含氮生物质炭以及CaO耦合掺氮生物质炭对NO吸附性能的影响。理论计算结果表明，掺氮生物质炭在N-down吸附方式下对NO吸附效果更好，且掺杂N-5生物质炭（CN-5）较其含氮基团生物质炭对NO的吸附能更高，其吸附能为−41.22 kJ/mol。CaO显著提升了生物炭对NO的吸附能力，且CaO耦合含N-5生物质炭(CaO/CN-5)的基底作为电子供体为NO提供更多电荷，其吸附能比CN-5高出216.862 kJ/mol，CaO和N-5基团耦合作用下显著提高生物炭的吸附性能。生物炭表面NO的吸附量会随着温度的升高而减少，增加含N-5生物质炭的数量对NO的吸附更有利，而CaO的耦合进一步提高了CN-5表面NO的吸附量，在273 K时，CaO/CN-5体系的吸附量可以达2.846 mmol/g。Abstract: In this study, density functional theory was used to explore the effects of different nitrogenous biochars and CaO-coupled nitrogen-doped biochar on the adsorption performance of NO. The theoretical calculation results showed that nitrogen-doped biomass char had a better adsorption effect on NO under N-down adsorption mode, and the adsorption energy of N-5 biomass char (CN-5) was higher than that of nitrogen-containing biochar, and its adsorption energy was −41.22 kJ/mol. CaO significantly improved the adsorption capacity of biochar to NO, and CaO coupled with the substrate containing N-5 biochar (CaO/CN-5) as an electron donor provides more charge for NO, and its adsorption energy was 216.862 kJ/mol higher than that of CN-5, and the adsorption performance of biochar was significantly improved under the coupling of CaO and N-5 groups. The adsorption capacity of NO on the surface of biochar decreased with the increase of temperature, and increasing the amount of biochar containing N-5 was more conducive to the adsorption of NO, while the coupling of CaO further increased the adsorption capacity of NO-5 surface NO, and the adsorption capacity of CaO/CN-5 system reached 2.846 mmol/g at 273 K.
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Key words:
- biochar /
- nitrogenous groups /
- CaO /
- NO /
- N-5
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图 2 NO在生物炭及掺氮生物炭表面不同的吸附构型
Figure 2 Different adsorption configurations of NO on the surface of biochar and nitrogen-doped biochar
图 3 NO以N-down吸附方式下CN-5的PDOS谱图
Figure 3 PDOS diagram of CN-5 under NO-down adsorption mode
图 5 NO及作用在CaO/BC和CaO/CN-5表面的相关原子编号
Figure 5 NO and the associated atomic numbers acting on the surface of CaO/BC and CaO/CN-5
图 6 掺氮生物质炭与CaO耦合掺氮生物质炭表面NO的吸附量
Figure 6 Adsorption capacity of nitrogen-doped biochar and CaO-coupled nitrogen-doped biochar NO
(a): Nitrogen-doped biochar; (b): CaO coupled nitrogen-doped biochar
表 1 吸附体系中各种基元数量
Table 1 Number of various primitives in the adsorption system
Number of
primitivesAdsorption system CHN CN-5 CN-6 CG-N CN-X BC 9 0 0 0 0 N-5 9 18 9 9 9 N-6 9 9 18 9 9 G-N 9 9 9 18 9 N-X 9 9 9 9 18 
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表 2 NO在生物炭及掺氮生物炭表面的吸附能
Table 2 Adsorption energy of NO on the surface of biochar and nitrogen-doped biochar
Adsorption
structureSide-on Eads /
(kJ·mol−1)N-down Eads /
(kJ·mol−1)BC −15.13 93.94 CN-6 136.59 −32.04 CN-5 −18.79 −41.22 CG-N −5.49 −5.49 CN-X 180.11 −37.62
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表 3 CaO耦合BC与耦合掺CN-5表面NO的吸附能
Table 3 Adsorption energy of CaO-coupled BC and coupled CN-5 surface NO
Adsorption structure Eads /(kJ·mol−1) CaO/BC −248.627 CaO/CN-5 −258.082
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表 4 CaO/BC相关原子Mulliken电荷
Table 4 CaO/BC related atom Mulliken charge changes
Atom s p d Total Charge /e N2 1.66 3.34 0.00 5.00 0.00 O76 1.84 4.58 0.00 6.42 −0.42 O27 1.86 4.82 0.00 6.68 −0.68 Ca29 2.19 6.00 0.70 8.88 1.12 Ca41 2.19 6.00 0.69 8.84 1.16
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表 5 CaO/CN-5相关原子Mulliken电荷
Table 5 CaO/CN-5 related atom Mulliken charge changes
Atom s p d Total Charge /e N2 1.68 3.40 0.00 5.09 −0.09 O76 1.85 4.67 0.00 6.52 −0.52 O27 1.86 4.83 0.00 6.69 −0.69 Ca29 2.19 6.00 0.68 8.86 1.14 Ca41 2.19 6.00 0.69 8.84 1.16
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