钠对焦炭非均相还原NO的微观作用机理

张秀霞; 吕晓雪; 伍慧喜; 谢苗; 林日亿; 周志军

钠对焦炭非均相还原NO的微观作用机理

1.
中国石油大学(华东)新能源学院, 山东青岛 266580
2.
浙江大学能源清洁利用国家重点实验室, 浙江杭州 310027

基金项目:

中央高校基本科研业务费专项资金 18CX02073A

国家自然科学基金面上项目 51874333

详细信息

中图分类号: TK16;X511
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- 被引次数: 0
出版历程
- 收稿日期: 2020-05-06
- 修回日期: 2020-06-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-06-10

Microscopic mechanism for effect of sodium on NO heterogeneous reduction by char

1.
College of New Energy, China University of Petroleum(East China), Qingdao 266580, China
2.
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Funds:

the Fundamental Research Funds for the Central Universities 18CX02073A

National Natural Science Foundation of China 51874333

More Information

Corresponding author: ZHANG Xiu-xia.E-mail: zhangxx@upc.edu.cn

摘要

摘要: 基于密度泛函理论研究了钠对焦炭非均相还原NO的微观作用机理。计算结果表明，Na原子可以在焦炭边缘游离，最倾向于吸附在焦炭边缘穴位，释放出174.2 kJ/mol的能量。波函数分析显示，Na原子以强静电吸引的方式与边缘碳原子结合，电子由Na转移到焦炭上。NO以O临近Na原子的方式吸附在焦炭边缘最稳定。Na促进第一个NO分子的吸附，但对第二个NO分子的吸附影响不大。内禀反应坐标计算与Mayer键级分析表明非均相还原通道中Na与O之间经历"结合-分离"，通过"氧化-还原"的方式影响反应的进行。N₂分子的化学解吸附步是非均相还原的速控步。采用正则变分过渡态理论进行动力学分析，发现Na对速控步的活化能影响不大，但会增加焦炭上活性位点的数量，加快反应的进行。
- 焦炭 /
- 一氧化氮 /
- 非均相还原 /
- 钠 /
- 密度泛函理论
Abstract: A thorough theoretical exploration of microscopic mechanism for effect of sodium (Na) on nitric oxide (NO) heterogeneous reduction by char was performed based on density functional theory with consideration of London dispersion interaction. Calculation results show that the Na atom could migrate at edge of char and prefers to be incorporated into a five-atom ring forming a pentagon with 174.2 kJ/mol released. A strong electrostatic attraction between the Na atom and carbon atoms at the edge is found by reduced density gradient analysis. Electrons transfer from the Na atom to char, resulting in electron rearrangement on char. It is the most stable mode for adsorption of the first NO molecule when O atom in NO molecule is adjacent to the Na atom. The doping of Na could promote adsorption of the first NO molecule, but has little effect on that of the second NO molecule. The intrinsic reaction coordinate calculations and Mayer bond order analyses suggest that the Na atom affects heterogeneous reduction through "oxidized-reduced" cycle via "combination-separation" with the O atom. Desorption of N₂ molecule is the rate-determining step in the whole reaction channel. The canonical variational theory was used for kinetic analyses, considering the tunneling effect along the reaction coordinate with Wigner method. It is found that the reaction is accelerated by doping Na atom. Although the addition of Na would not significantly reduce activation energy of the rate-determining step, but would increase activation sites at the edge of char.
- char /
- nitric oxide /
- heterogeneous reduction /
- sodium /
- density functional theory

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图 1 Armchair结构焦炭模型(Am)

Figure 1 Char model with armchair configuration (Am)

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图 2 Na在焦炭边缘的吸附结构(键长单位：nm)

Figure 2 Adsorption configurations of Na at the edge of char (bond length: nm)

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图 3 Na在焦炭边缘吸附的反应势能面

Figure 3 Potential energy surface for adsorption of Na at the edge of char

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图 4 Am-H电子结构分析

Figure 4 Electronic structure analysis of Am-H

(a): electron density difference plots; (b): iso-surface of RDG (isovalue 0.5); (c): scatter graph of RDG vs sign(λ₂)ρ; (d): color-mapped ELF; (e): distribution of Hirshfeld atomic charge; (f): ESP mapped vdW surface

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图 5 NO吸附产物几何结构(键长单位：nm)

Figure 5 Optimized adsorption configurations of the NO molecule (bond length: nm)

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图 6 AmNaNO-A电子结构分析

Figure 6 Electronic structure analysis of AmNaNO-A

(a): electron density difference plots; (b): ESP mapped vdW surface

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图 7 N₂在Am边缘释放步中间体与过渡态的几何构型(键长单位：nm)

Figure 7 Geometrical parameters for stable species and the transition states for N₂ desorption from Am (bond length: nm)

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图 8 NO在Na修饰焦炭边缘非均相还原反应通道中的中间体与过渡态的几何构型(键长单位：nm)

Figure 8 Geometrical parameters for stable species and transition states in the pathway of NO heterogeneous reduction at the edge of Na-decorated char (bond length: nm)

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图 9 NO非均相还原反应势能面

Figure 9 Potential energy surface of NO heterogeneous reduction on char

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图 10 过渡态IRC路径上的键级变化

Figure 10 Mayer bond orders along IRC of transition states

(a): AmNa-TS1; (b): AmNa-TS2; (c): AmNa-TS3; (d): AmNa-TS4

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图 11 正则变分理论得到的反应速率常数

Figure 11 Rate constant k calculated by CVT

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表 1 拟合所得反应动力学参数

Table 1 Fitted kinetic parameters of Arrhenius expressions

Reaction	A/s^-1	E_a /(kJ·mol^-1)
C()+2NO→N₂+C(O)	2.37×10¹³	148.5
C(Na)+2NO→N₂+C(Na)+C(O)	7.04×10¹⁴	139.5

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