Unraveling the catalytically active phase of carbon dioxide hydrogenation to methanol on Zn/Cu alloy: Single atom versus small cluster

Wu, Xiao-Kuan1,2,3; Yan, Hui-Min1,2; Zhang, Wei1,2; Zhang, Jie3; Xia, Guang-Jie1,2; Wang, Yang-Gang1,2

2021-10-01

10.1016/j.jechem.2021.02.016

Journal of Energy Chemistry   影响因子和分区

2095-4956

Methanol synthesis from CO2 hydrogenation catalyzed by Zn/Cu alloy has been widely studied, but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process. What is more, as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster, how Zn surface distribution affects catalytic activity is still not clear. In this work, we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface, where the surface oxidation was shown to play the critical role. Before surface oxidation, the Zn single atom/Cu is more active than the Zn small cluster/Cu, but its surface oxidation is difficult to take place. Instead, after the easy surface oxidation by CO2 decomposition, the oxidized Zn small cluster/Cu becomes much more active, which even exceeds the hardly oxidized Zn single atom/Cu to become the active phase. Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors: i) The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster. That makes the O intermediates bind at the Zn/Cu interface, preventing their too tight binding for further hydrogenation; ii) The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates. This work provided one more example that under certain condition, the metal cluster can be more active than the single atom in heterogeneous catalysis. (C) 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

CO2 hydrogenation Surface oxidation Zn/Cu alloy Catalytically active phase

SCI ; EI

英语

第一 ; 通讯

NSFC, China[22022504] ; Guangdong "Pearl River" Talent Plan, China[2019QN01L353] ; Higher Education Innovation Strong School Project of Guangdong Province of China, China[2020KTSCX122] ; Guangdong Provincial Key Laboratory of Catalysis, China[2020B121201002] ; National Key Research and Development Program of China, China[2017YFC0210905]

Chemistry ; Energy & Fuels ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Energy & Fuels ; Engineering, Chemical

WOS:000655125900003

ELSEVIER

20211710240640

Atoms ; Binding sites ; Catalysis ; Catalyst activity ; Hydrogenation ; Methanol ; Oxidation ; Reaction intermediates ; Zinc alloys

Zinc and Alloys:546.3 ; Biochemistry:801.2 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalyt Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Beijing Univ Chem Technol, State Key Lab Chem Resource Engn, Beijing 100029, Peoples R China

Wu, Xiao-Kuan,Yan, Hui-Min,Zhang, Wei,et al. Unraveling the catalytically active phase of carbon dioxide hydrogenation to methanol on Zn/Cu alloy: Single atom versus small cluster[J]. Journal of Energy Chemistry,2021,61:582-593.

Wu, Xiao-Kuan,Yan, Hui-Min,Zhang, Wei,Zhang, Jie,Xia, Guang-Jie,&Wang, Yang-Gang.(2021).Unraveling the catalytically active phase of carbon dioxide hydrogenation to methanol on Zn/Cu alloy: Single atom versus small cluster.Journal of Energy Chemistry,61,582-593.

Wu, Xiao-Kuan,et al."Unraveling the catalytically active phase of carbon dioxide hydrogenation to methanol on Zn/Cu alloy: Single atom versus small cluster".Journal of Energy Chemistry 61(2021):582-593.