石墨炭负载单原子铁催化剂非均相还原 NO 的微观作用机理：DFT研究

赵妍; 李响; 黄金凯; 李先春; 朱亚明; 王焕然

doi:10.1016/S1872-5813(23)60407-4

石墨炭负载单原子铁催化剂非均相还原 NO 的微观作用机理：DFT研究

doi: 10.1016/S1872-5813(23)60407-4

赵妍^1,,
李响^1,,
黄金凯^1,,
李先春^2,,
朱亚明^2,,
王焕然^1, ,

1.
辽宁科技大学辽宁土木工程学院辽宁鞍山 114051
2.
辽宁科技大学辽宁化学工程学院辽宁鞍山 114051

基金项目: 辽宁省教育厅青年项目(JYTQN2023237)资助

详细信息

通讯作者:
Tel: 18341357135, Fax: 0412-5929619, E-mail: 312166@ustl.edu.cn

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2023-11-30
- 修回日期: 2023-12-27
- 录用日期: 2023-12-27
- 网络出版日期: 2024-01-18
- 刊出日期: 2024-05-01

Mechanism of heterogeneous reduction of NO over graphite-supported single-atom Fe catalyst: DFT study

ZHAO Yan^1
,,
LI Xiang^1
,,
HUANG Jinkai^1
,,
LI Xianchun^2
,,
ZHU Yaming^2
,,
WANG Huanran^{1
, ,}

1.
University of Science and Technology Liaoning School of Civil Engineering, Anshan 114051, China
2.
University of Science and Technology Liaoning School of Chemical Engineering, Anshan 114051, China

Funds: The project was supported by Youth Project of Liaoning Department of Education (JYTQN2023237).

摘要

摘要: 基于密度泛函理论和经典过渡态理论，探究了石墨炭负载单原子Fe催化剂（Fe/G）异相还原NO的微观机理，并对催化剂失活原因进行分析。结果表明，基于E-R机理，NO还原反应依次经历了N₂O形成与释放、N₂形成与释放四个阶段。而基于L-H机理，NO还原反应主要经历了N₂形成与释放两个阶段。在E-R机理作用下，NO分子以N,O-down结构吸附在Fe原子上发生的NO还原反应的控速步骤能垒值仅为15.5 kJ/mol，小于其余路径控速步骤能垒值。由能垒角度分析，Fe原子上残留的活性氧被还原的能垒值高于NO还原生成N₂的能垒值。NO分解后残留在Fe原子表面的活性氧抑制了NO的吸附与还原，Fe原子活性位的缺失导致催化剂的失活，单原子Fe的存在促进了NO还原反应的进行。由动力学角度分析，随着反应温度的升高，NO还原速率较活性氧转移速率提升更为显著。
- 单原子铁催化剂 /
- 氮氧化物 /
- 密度泛函理论 /
- 机理 /
- 失活
Abstract: The mechanism of nitrogen oxide (NO) reduction over graphite carbon-supported single-atom iron (Fe) catalyst (Fe/G) was investigated by density functional theory (DFT) and transition state theory (TST). The catalyst deactivation was also analyzed. The results revealed that the NO reduction, based on the Eley-Rideal (E-R) mechanism, underwent four stages including N₂O formation and release as well as N₂ formation and release. However, the NO reduction only involved two stages according to Langmuir-Hinshelwood (L-H) mechanism: N₂ formation and release. Furthermore, for the E-R mechanism, the rate-controlling step was NO reduction, where a NO molecule was adsorbed on an Fe atom with an N, O-down structure with energy barrier of 15.5 kJ/mol, lower than that of other paths. Energy barrier analysis indicated that the energy barrier for the reduction of reactive oxygen species was higher than that for the formation of N₂. Reactive oxygen species remaining on the surface of Fe atoms after NO decomposition inhibited the adsorption and reduction of NO, leading to catalyst deactivation due to the absence of active sites. The single-atom Fe species promoted the NO reduction. Kinetic analysis results suggested that, upon increasing the reaction temperature, the NO reduction rate increased more significantly than the reactive oxygen transfer rate.
- singe-atom Fe catalyst /
- nitrogen oxides /
- density functional theory /
- mechanism /
- deactivation

HTML全文

FIG. 3138. FIG. 3138.

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图 1 Fe/G反应模型示意图

Figure 1 Reaction model of Fe/G

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图 2 基于P1与P2路径下Fe/G还原NO反应中间组分的几何构型

Figure 2 Geometric configurations of intermediates over Fe/G based in P1 and P2 (Bond length: nm)

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图 3 基于P1与P2路径下Fe/G还原NO的势能面

Figure 3 Potential energy surface of NO reduction over Fe/G based in P1 and P2

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图 4 N₂O还原反应中间组分的几何构型

Figure 4 Geometric configurations of intermediates in N₂O reduction (Bond length: nm)

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图 5 N₂O还原反应的势能面

Figure 5 Potential energy surface of N₂O reduction

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图 6 基于P3路径下Fe/G还原NO反应中间组分的几何构型

Figure 6 Geometric configurations of intermediates in NO reduction over Fe/G based in P3 (Bond length: nm)

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图 7 基于P3路径下Fe/G还原NO的势能面

Figure 7 Potential energy surface of NO reduction over Fe/G based in P3

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图 8 O*还原反应中间组分的几何构型

Figure 8 Geometric configurations of intermediates in O* reduction (Bond length: nm)

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图 9 O*还原反应的势能面

Figure 9 Potential energy surface of O* reduction

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图 10 不同温度下的反应速率常数

Figure 10 Reaction rate constants at different temperatures

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表 1 反应动力学参数

Table 1 Reaction kinetic parameters

Course of reaction	Pre-exponential factor A/s⁻¹	Activation energy E_a/(kJ·mol⁻¹)	Arrhenius equation
P1-IM2→P1-IM3	1.32×10¹⁵	19.28	k=1.32×10¹⁵e^−2318.98/T
P2-IM2→P1-IM3	6.68×10¹²	111.99	k=6.68×10¹²e^{−13470.04/T}
P3-IM1→P3-P+CO₂	9.72×10¹⁴	61.36	k=9.72×10¹⁴e^−7380.32/T
CO-IM1→IM0+CO₂	4.36×10¹¹	37.16	k=4.36×10¹¹e^−4469.57/T

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