Mo掺杂石墨烯催化CO2加氢制甲醇的机理研究

doi:10.12096/j.2096-4528.pgt.23159

发电技术 ›› 2025, Vol. 46 ›› Issue (5): 923-929.DOI: 10.12096/j.2096-4528.pgt.23159

Mo掺杂石墨烯催化CO₂加氢制甲醇的机理研究

杨龙¹, 郝黎明¹, 寻志伟¹, 顾永正², 于芳³, 邓博文³, 高腾飞³

^1.国能锦界能源有限责任公司，陕西省神木市 719319
^2.国电电力发展股份有限公司，辽宁省大连市 116699
^3.国家能源集团新能源技术研究院有限公司，北京市昌平区 102209

收稿日期:2024-06-22 修回日期:2024-08-29 出版日期:2025-10-31 发布日期:2025-10-23
作者简介:杨龙(1988)，男，工程师，研究方向为CCUS与氢能技术，16143176@ceic.com；
高腾飞(1988)，男，博士，工程师，研究方向为CCUS与氢能技术，本文通信作者，20039663@chnenergy.com.cn。
基金资助:
国家重点研发计划氢能专项(2024YFB4006600)

Study on Mechanism of CO₂ Hydrogenation to Methanol Catalyzed by Mo-Doped Graphene

Long YANG¹, Liming HAO¹, Zhiwei XUN¹, Yongzheng GU², Fang YU³, Bowen DENG³, Tengfei GAO³

^1.CHN Energy Jinjie Energy Co. , Ltd. , Shenmu 719319, Shaanxi Province, China
^2.Guodian Power Development Company, Dalian 116699, Liaoning Province, China
^3.New Energy Technology Research Institute, CHN Energy, Changping District, Beijing 102209, China

Received:2024-06-22 Revised:2024-08-29 Published:2025-10-31 Online:2025-10-23
Supported by:
National Key R&D Hydrogen Energy Program(2024YFB4006600)

摘要/Abstract

摘要：

目的 CO₂催化加氢制甲醇是减少CO₂排放的有效途径之一，金属掺杂石墨烯是潜在的CO₂加氢催化剂，为了辅助催化剂设计开发，探究了Mo掺杂石墨烯(Mo-石墨烯)催化CO₂加氢的作用机理。方法利用密度泛函理论(density functional theory，DFT)计算和电子结构分析方法研究了Mo-石墨烯的催化活性、CO₂的吸附和加氢制甲醇反应路径。结果 Mo的掺杂提高了石墨烯催化剂的催化活性；CO₂在催化剂上的最佳吸附构型为碳氧共吸附，吸附的CO₂最初倾向于C和H成键生成关键中间体HCOO，HCOOH形成是CO₂还原的决速步，对应反应路径为CO₂→HCOO→HCOOH→HCO→H₂CO→H₃CO→CH₃OH。结论 Mo的掺杂可以提高石墨烯催化剂催化CO₂加氢路径的选择性，有利于提高甲醇选择性。

关键词: 碳捕集, 碳排放, 石墨烯, Mo掺杂, CO₂加氢, 甲醇

Abstract:

Objectives The catalytic hydrogenation of CO₂ to methanol is one of the effective approaches for CO₂ emission reduction. Metal-doped graphene is a potential catalyst for CO₂ hydrogenation. To support the design and development of catalysts, the mechanism of CO₂ hydrogenation catalyzed by Mo-doped graphene (Mo-graphene) is investigated. Methods Density functional theory (DFT) calculations and electronic structure analysis methods are used to study the catalytic activity of Mo-graphene, CO₂ adsorption, and the reaction pathway for methanol production methanol production via hydrogenation. Results Mo doping improves the catalytic activity of the graphene-based catalyst. The optimal adsorption configuration of CO₂ on the catalyst is co-adsorption of carbon and oxygen. The adsorbed CO₂ initially tends to bond with C and H, generating the key intermediate HCOO. The formation of HCOOH is identified as the rate-determining step in CO₂ reduction. The corresponding reaction pathway is: CO₂→_{HCOO→_{HCOOH→_{HCO→_{H₂CO→_{H₃CO→_{CH₃OH. Conclusions Mo doping can improve the selectivity of the CO₂ hydrogenation pathway on graphene-based catalysts, which is conducive to enhancing the selectivity of methanol.}}}}}}

Key words: carbon capture, carbon emission, graphene, Mo doping, CO₂ hydrogenation, methanol

中图分类号:

TK 01

杨龙, 郝黎明, 寻志伟, 顾永正, 于芳, 邓博文, 高腾飞. Mo掺杂石墨烯催化CO₂加氢制甲醇的机理研究[J]. 发电技术, 2025, 46(5): 923-929.

Long YANG, Liming HAO, Zhiwei XUN, Yongzheng GU, Fang YU, Bowen DENG, Tengfei GAO. Study on Mechanism of CO₂ Hydrogenation to Methanol Catalyzed by Mo-Doped Graphene[J]. Power Generation Technology, 2025, 46(5): 923-929.

图/表 8

图1 石墨烯和Mo-石墨烯模型的优化构型

Fig. 1 Optimized configurations of graphene and Mo-doped graphene models

图2 石墨烯和Mo-石墨烯表面的电子密度差图

Fig. 2 Electron density difference of graphene and Mo-doped graphene surfaces

图3 C1、C2和Mo的s、p和d轨道PDOS图

Fig. 3 PDOS map of s, p, and d orbitals for C1, C2, and Mo

图4 H2在Mo-石墨烯催化剂表面的吸附解离

Fig. 4 Adsorption and dissociation of H2 on Mo-doped graphene catalyst surface

图5 CO2在Mo-石墨烯催化剂表面的吸附构型

Fig. 5 Adsorption configurations of CO2 on Mo-doped graphene catalyst surface

图6 CO2加氢生成甲醇反应路径

Fig. 6 Reaction pathways for CO₂ hydrogenation to methanol

图7 Mo-石墨烯表面二氧化碳氢化生成甲醇涉及中间体COOH的构型和能量曲线

Fig. 7 Configuration and energy curve of COOH intermediate in CO₂ hydrogenation to methanol on Mo-doped graphene surface

图8 Mo-石墨烯表面二氧化碳氢化生成甲醇涉及中间体HCOO的构型和能量曲线

Fig. 8 Configuration and energy curve of HCOO intermediate in CO2 hydrogenation to methanol on Mo-doped graphene surface

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Mo掺杂石墨烯催化CO₂加氢制甲醇的机理研究

Study on Mechanism of CO₂ Hydrogenation to Methanol Catalyzed by Mo-Doped Graphene

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