Mechanism of methanol synthesis from CO2 hydrogenation over Rh16/In2O3 catalysts: A combined study on density functional theory and microkinetic modeling

Q3 Energy

燃料化学学报 Pub Date : 2024-10-01 DOI:10.1016/S1872-5813(24)60460-3

WANG Yuning , GONG Jiesong , ZHOU Jiabin , CHEN Zhiyuan , TIAN Dong , NA Wei , GAO Wengui

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引用次数: 0

Abstract

In this study, the hydrogenation of carbon dioxide (CO₂) to methanol (CH₃OH) over Rh₁₆/In₂O₃ catalyst was studied through Density Functional Theory (DFT) and microdynamics modeling. The spontaneous dissociation mechanisms of H₂ and CO₂ adsorption at the Rh₁₆/In₂O₃ interface were investigated. The oxygen vacancies in In₂O₃ enhanced the adsorption process. Bader charge analysis revealed a marginal positive charge on Rh₁₆, elucidating the critical insights into the electronic characteristics and catalytic activity. The study established the RWGS+CO-Hydro pathway as the predominant mechanism for methanol synthesis, characterized by a sequential transformation of intermediates: CO₂*→COOH*→CO*+OH*→HCO*→CH₂O*→CH₂OH*→CH₃OH*. Furthermore, Degree of Reaction Rate Control (DRC) analysis conducted in the range of 373–873 K and 10^–2 to 10³ bar identified two principal kinetic phenomena: at lower temperature and higher pressure, the conversion of CO* + H* to HCO* significantly impacted the overall reaction rate. Conversely, at higher temperature, the step from CH₂O* + H* to CH₃O* was dominate.

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Rh16/In2O3 催化剂氢化 CO2 合成甲醇的机理：密度泛函理论与微动力学模型的结合研究

本研究通过密度泛函理论（DFT）和微动力学建模研究了二氧化碳（CO2）在 Rh16/In2O3 催化剂上加氢转化为甲醇（CH3OH）的过程。研究了 Rh16/In2O3 界面吸附 H2 和 CO2 的自发解离机制。In2O3 中的氧空位增强了吸附过程。Bader 电荷分析揭示了 Rh16 上的边际正电荷，阐明了其电子特性和催化活性的重要见解。研究确定了 RWGS+CO-Hydro 途径是甲醇合成的主要机制，其特点是中间产物的顺序转化：CO2*→COOH*→CO*+OH*→HCO*→CH2O*→CH2OH*→CH3OH*.此外，在 373-873 K 和 10-2-103 bar 范围内进行的反应速率控制度（DRC）分析确定了两种主要的动力学现象：在较低温度和较高压力下，CO* + H* 向 HCO* 的转化对整体反应速率有显著影响。相反，在较高温度下，从 CH2O* + H* 到 CH3O* 的步骤占主导地位。

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来源期刊

燃料化学学报 Chemical Engineering-Chemical Engineering (all)

CiteScore

2.80

自引率

0.00%

发文量

5825

期刊介绍： Journal of Fuel Chemistry and Technology (Ranliao Huaxue Xuebao) is a Chinese Academy of Sciences(CAS) journal started in 1956, sponsored by the Chinese Chemical Society and the Institute of Coal Chemistry, Chinese Academy of Sciences(CAS). The journal is published bimonthly by Science Press in China and widely distributed in about 20 countries. Journal of Fuel Chemistry and Technology publishes reports of both basic and applied research in the chemistry and chemical engineering of many energy sources, including that involved in the nature, processing and utilization of coal, petroleum, oil shale, natural gas, biomass and synfuels, as well as related subjects of increasing interest such as C1 chemistry, pollutions control and new catalytic materials. Types of publications include original research articles, short communications, research notes and reviews. Both domestic and international contributors are welcome. Manuscripts written in Chinese or English will be accepted. Additional English titles, abstracts and key words should be included in Chinese manuscripts. All manuscripts are subject to critical review by the editorial committee, which is composed of about 10 foreign and 50 Chinese experts in fuel science. Journal of Fuel Chemistry and Technology has been a source of primary research work in fuel chemistry as a Chinese core scientific periodical.