CO hydrogenation on stepped Cu and CuZn alloy surfaces: Competition between methanol synthesis and methanation pathways |
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| Institution: | 1. School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China;2. Research Institute of Applied Chemistry, Jiangxi Academy of Sciences, Nanchang 330096, China;1. Herbert Gleiter Institute for Nanoscience, School of Materials Science and Engineering, Nanjing University of Science & Technology, Nanjing 210094, China;2. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China;3. School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China;1. Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;2. Shunde Graduate School of University of Science and Technology Beijing, Foshan 528399, China;3. State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China;1. Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China;2. School of Materials Science and Energy Engineering, Foshan University, Foshan 528000, China |
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| Abstract: | Comprehensive fundamental understanding of CO hydrogenation reactions over Cu and ZnCu alloy surfaces is of great importance. Herein, we report a comparative DFT calculation study of elementary surface reaction network of CO hydrogenation reactions on stepped Cu(211), Cu(611), ZnCu(211) and ZnCu(611) surfaces. On ZnCu(211) and ZnCu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → H2CO* → H3CO* → CH3OH* → CH3OH with H3CO* hydrogenation as the rate-limiting step and proceeds more facilely on ZnCu(611) surface than on ZnCu(211) surface. On Cu(211) and Cu(611) surfaces, the energetic favorable reaction path of CO hydrogenation reaction follows CO* → HCO* → HCOH* → H2COH* → H3COH* → CH3* → CH4* → CH4 with H2COH* hydrogenation as the rate-limiting step and proceeds more facilely on Cu(611) than on Cu(211). The key difference of CO hydrogenation reaction on ZnCu alloy surface and Cu is that the resulting CH3OH* species desorbs to produce CH3OH on ZnCu alloy but undergoes H*-assisted decomposition to CH3* and eventually to CH4 on Cu surface. These results successfully unveil elementary surface reaction networks and structure sensitivity of Cu and ZnCu alloy-catalyzed CO hydrogenation reactions. |
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