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Significance of surface formate coverage on the reaction kinetics of methanol synthesis from CO2hydrogenation over Cu
Wu, Panpan1,2,3; Yang, Bo1,2,4
2017
发表期刊ACS Catalysis
卷号7期号:10页码:7187-7195
摘要The hydrogenation of CO2to methanol over copper-based catalysts has attracted considerable attention recently. Among all the proposed reaction mechanisms, a large number of experimental and theoretical studies have focused on the one that includes a HCOO intermediate due to the fact that high coverages of formate over catalyst surfaces were observed experimentally. To systematically understand the influence of formate species coverage on the reaction kinetics of methanol synthesis, the energetics of the CO2hydrogenation pathway over clean and one- or two-formate preadsorbed Cu(211) are obtained using density functional theory calculations, and these energetics are further employed for microkinetic modeling. We find that the adsorption energies of the intermediates and transition states involved in the reaction pathway are changed in the presence of spectating formate species, and consequently, the potential energy diagrams are varied. Microkinetic analysis shows that the turnover frequencies (TOFs) over different formate preadsorbed surfaces vary under the same reaction condition. In particular, the reaction rates obtained over clean Cu(211) are generally the lowest, while those over one- or two-formate preadsorbed surfaces depend on the reaction temperatures and pressures. Meanwhile, we find that only when the formate coverage effect is considered, some of the TOFs obtained from microkinetic modeling are in fair agreement with previous experimental results under similar conditions. After the degree of rate control analysis, it is found that the combination of HCOO and HCOOH hydrogenation steps can be treated as the "effective rate-determining step", which can be written as HCOO∗ + 2H∗ → H2COOH∗ + 2∗. Therefore, the formation of methanol is mainly controlled by the surface coverage of formate and hydrogen at the steady state, as well as the free energy barriers of the effective rate-determining step, i.e., effective free energy barriers. © 2017 American Chemical Society.
DOI10.1021/acscatal.7b01910
EI入藏号20174504368826
EI主题词Surface reactions
EI分类号641.1 Thermodynamics - 801.4 Physical Chemistry - 802.2 Chemical Reactions - 804 Chemical Products Generally - 922.1 Probability Theory
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被引频次:5[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sic.ac.cn/handle/331005/25696
专题中国科学院上海硅酸盐研究所
作者单位1.School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Shanghai; 201210, China;
2.Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai; 200050, China;
3.University of Chinese Academy of Sciences, Beijing; 101407, China;
4.Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai; 201210, China
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Wu, Panpan,Yang, Bo. Significance of surface formate coverage on the reaction kinetics of methanol synthesis from CO2hydrogenation over Cu[J]. ACS Catalysis,2017,7(10):7187-7195.
APA Wu, Panpan,&Yang, Bo.(2017).Significance of surface formate coverage on the reaction kinetics of methanol synthesis from CO2hydrogenation over Cu.ACS Catalysis,7(10),7187-7195.
MLA Wu, Panpan,et al."Significance of surface formate coverage on the reaction kinetics of methanol synthesis from CO2hydrogenation over Cu".ACS Catalysis 7.10(2017):7187-7195.
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