Density Functional Theory Study of CO2 Hydrogenation on Transition-Metal-Doped Cu(211) Surfaces

Yushan Wang; Mengting Yu; Xinyi Zhang; Yujie Gao; Jia Liu; Ximing Zhang; Chunxiao Gong; Xiaoyong Cao; Zhaoyang Ju; Yongwu Peng

doi:10.3390/molecules28062852

Density Functional Theory Study of CO₂ Hydrogenation on Transition-Metal-Doped Cu(211) Surfaces

Molecules. 2023 Mar 22;28(6):2852. doi: 10.3390/molecules28062852.

Authors

Yushan Wang¹, Mengting Yu¹, Xinyi Zhang¹, Yujie Gao¹, Jia Liu¹, Ximing Zhang², Chunxiao Gong², Xiaoyong Cao³, Zhaoyang Ju^{1

2}, Yongwu Peng⁴

Affiliations

¹ College of Chemical & Material Engineering, Quzhou University, Quzhou 324000, China.
² College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou 310058, China.
³ Institute of Zhejiang University-Quzhou, Quzhou 324000, China.
⁴ College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China.

Abstract

The massive emission of CO₂ has caused a series of environmental problems, including global warming, which exacerbates natural disasters and human health. Cu-based catalysts have shown great activity in the reduction of CO₂, but the mechanism of CO₂ activation remains ambiguous. In this work, we performed density functional theory (DFT) calculations to investigate the hydrogenation of CO₂ on Cu(211)-Rh, Cu(211)-Ni, Cu(211)-Co, and Cu(211)-Ru surfaces. The doping of Rh, Ni, Co, and Ru was found to enhance CO₂ hydrogenation to produce COOH. For CO₂ hydrogenation to produce HCOO, Ru plays a positive role in promoting CO dissociation, while Rh, Ni, and Co increase the barriers. These results indicate that Ru is the most effective additive for CO₂ reduction in Cu-based catalysts. In addition, the doping of Rh, Ni, Co, and Ru alters the electronic properties of Cu, and the activity of Cu-based catalysts was subsequently affected according to differential charge analysis. The analysis of Bader charge shows good predictions for CO₂ reduction over Cu-based catalysts. This study provides some fundamental aids for the rational design of efficient and stable CO₂-reducing agents to mitigate CO₂ emission.

Keywords: Bader charge; CO2 hydrogenation; Cu-based catalyst; DFT.

Abstract

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