镍钴双原子团簇催化甲烷干重整反应机理及其动力学研究

张建辉; 何启容; 慕红梅; 刘佳; 李文雅; 冷艳丽

doi:10.19906/j.cnki.JFCT.2023055

镍钴双原子团簇催化甲烷干重整反应机理及其动力学研究

doi: 10.19906/j.cnki.JFCT.2023055

张建辉^{1, 2,},
何启容^1,,
慕红梅^2,,
刘佳^2,,
李文雅^2,,
冷艳丽^1, ,

1.
贵州民族大学化学工程学院, 贵州贵阳 550025
2.
兰州资源环境职业技术大学黄河流域生态环境产教融合研究院, 甘肃兰州 730021

基金项目: 贵州民族大学自然科学基金一般项目(GZMUZK[2021]YB11)，兰州资源环境职业技术大学黄河流域生态环境产教融合研发基金项目(HHYF2023-08)资助

详细信息

通讯作者:
E-mail: gslengyl@126.com

中图分类号: O643.32
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出版历程
- 录用日期: 2023-07-25
- 网络出版日期: 2023-09-01

Theoretical and Kinetic Studies on the Reaction of Dry Reforming of Methane Catalyzed by Ni-Co Diatomic Clusters

ZHANG Jianhui^{1, 2
,},
HE Qirong^1
,,
MU Hongmei^2
,,
LIU Jia^2
,,
LI Wenya^2
,,
LENG Yanli^{1
, ,}

1.
School of Chemical Engineering, Guizhou Minzu Unversity, Guiyang 550025 Guizhou, China
2.
Yellow River Basin Ecotope Integration of Industry and Education Research Institute, Lanzhou Resources & Environment Voc-Tech University, Lanzhou 730021 Gansu, China

Funds: The project was supported by the Scientific Research Foundation of Guizhou Minzu University (GZMUZK[2021] YB11), Lanzhou Resources & Environment Voc-Tech University, Yellow River Basin Ecotope Integration of Industry and Education R&D Fund (HHYF2023-08)

摘要

摘要: 本研究采用密度泛函理论方法对NiCo双原子团簇催化甲烷干法重整反应的体系进行了计算研究。通过计算结果得出甲烷脱氢、二氧化碳活化、C*和CH*的氧化、H₂和H₂O的生成四个反应过程可能的反应路径。最后，运用能量跨度模型分析循环反应的动力学信息，发现298K时甲烷脱氢过程中不易生成C*。913K时甲烷脱氢过程决速中间体由IM1-1变成了IM6-1、决速过渡态由TS78-1变成了TS56-1；虽然可以生成C*，但能量跨度的减小加快了C*和CH*的消去。本工作可以了解NiCo双原子团簇催化甲烷干法重整的作用机理，为实验研究提供理论基础。
- 甲烷干重整 /
- 镍钴双原子团簇 /
- 反应机理 /
- 能量跨度模型
Abstract: In this work, the reaction mechanism of DRM catalyzed by NiCo diatomic cluster was studied by density functional theory. Based on our studied that the minimum energy reaction path was found for four steps: CH₄ dissociation, CO₂ dissociation, oxidation of intermediates C* and CH*, and generation of H₂ and H₂O. Finally, the energetic span model is applied in the cycle reaction to obtain some kinetic information. At 298K, it is hard to generate C* during the methane dehydrogenation process. At 913K, the determining intermediate changed from IM1-1 to IM6-1, and the determining transition state changed from TS78-1 to TS56-1 of dehydrogenation of methane, because of the reduction of energy spans, the elimination of C* and CH* are accelerated. This work can understand the mechanism of DRM catalyzed by NiCo diatomic clusters, which can provide theoretical reference for the experimental development.
- dry reforming of methane /
- ni-co diatomic cluster /
- reaction mechanism /
- energetic span model

HTML全文

图 1 甲烷干法重整反应可能的反应路径

Figure 1 The possible reaction path of methane dry reforming

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图 2 甲烷脱氢中各物质的几何构型（键长Å，键角°）

Figure 2 Geometries of the methane dehydrogenation process, bond length in angstrom and bond angle in degree

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图 3 甲烷脱氢反应能量路径示意图

Figure 3 Energy change for the methane dehydrogenation process

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图 4 二氧化碳活化中各物质的稳定几何构型（键长Å，键角°）

Figure 4 Geometries of the activation process for CO₂, bond length in angstroms and bond angle in degree

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图 5 二氧化碳活化反应能量路径示意图

Figure 5 Energy change for the reactions of path the activation process for CO₂

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图 6 C*和CH*的氧化反应各物质的稳定几何构型（键长Å，键角°）

Figure 6 Geometries of the reactions of oxidation process of C* and CH* species，bond length in angstroms and bond angle in degree

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图 7 C*和CH*的氧化反应中能量路径示意图

Figure 7 Energy change for the oxidation process of C* and CH* species: A. C* with O; B. C* with OH; C. CH* with O; D. CH* with OH

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图 8 氢气和水的生成中各物质的稳定几何构型（键长Å，键角°）

Figure 8 Energy changes during the formation of H₂ and H₂O: bond length in angstroms and bond angle in degree

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图 9 H₂和H₂O的生成反应能量路径示意图

Figure 9 Energy change for the generate H₂ and H₂O process

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图 10 NiCo催化甲烷干法重整的反应路径（黑色箭头为可能的反应路径，红色箭头为主要反应路径）

Figure 10 Reaction path of DRM process on catalyst NiCo (Black arrows are possible reaction paths; Red arrows is the main reaction path)

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