Enhanced CO2 Electroreduction on Neighboring Zn/Co Monomers by Electronic Effect

Wenjin Zhu; Lei Zhang; Sihang Liu; Ang Li; Xintong Yuan; Congling Hu; Gong Zhang; Wanyu Deng; Ketao Zang; Jun Luo; Yuanmin Zhu; Meng Gu; Zhi-Jian Zhao; Jinlong Gong

doi:10.1002/anie.201916218

Enhanced CO₂ Electroreduction on Neighboring Zn/Co Monomers by Electronic Effect

Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12664-12668. doi: 10.1002/anie.201916218. Epub 2020 Apr 28.

Authors

Wenjin Zhu¹, Lei Zhang¹, Sihang Liu¹, Ang Li¹, Xintong Yuan¹, Congling Hu¹, Gong Zhang¹, Wanyu Deng¹, Ketao Zang², Jun Luo², Yuanmin Zhu³, Meng Gu^{3

4}, Zhi-Jian Zhao¹, Jinlong Gong^{1

5}

Affiliations

¹ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Weijin Road 92, Tianjin, 300072, China.
² Center for Electron Microscopy, TUT-FEI Joint Laboratory, Tianjin Key laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China.
³ USTech Academy for Advanced Interdisciplinary studies, Southern University of Science and Technology of China, China.
⁴ Department of Materials Science and Engineering, Southern University of Science and Technology China, China.
⁵ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China.

PMID: 32227608
DOI: 10.1002/anie.201916218

Abstract

It is of great significance to reveal the detailed mechanism of neighboring effects between monomers, as they could not only affect the intermediate bonding but also change the reaction pathway. This paper describes the electronic effect between neighboring Zn/Co monomers effectively promoting CO₂ electroreduction to CO. Zn and Co atoms coordinated on N doped carbon (ZnCoNC) show a CO faradaic efficiency of 93.2 % at -0.5 V versus RHE during a 30-hours test. Extended X-ray absorption fine structure measurements (EXAFS) indicated no direct metal-metal bonding and X-ray absorption near-edge structure (XANES) showed the electronic effect between Zn/Co monomers. In situ attenuated total reflection-infrared spectroscopy (ATR-IR) and density functional theory (DFT) calculations further revealed that the electronic effect between Zn/Co enhanced the *COOH intermediate bonding on Zn sites and thus promoted CO production. This work could act as a promising way to reveal the mechanism of neighboring monomers and to influence catalysis.

Keywords: CO2 electrochemical reduction; cobalt; electronic effects; single atoms; zinc.

Grants and funding

21525626/National Natural Science Foundation of China