Atomic high-spin cobalt(II) center for highly selective electrochemical CO reduction to CH3OH

Jie Ding; Zhiming Wei; Fuhua Li; Jincheng Zhang; Qiao Zhang; Jing Zhou; Weijue Wang; Yuhang Liu; Zhen Zhang; Xiaozhi Su; Runze Yang; Wei Liu; Chenliang Su; Hong Bin Yang; Yanqiang Huang; Yueming Zhai; Bin Liu

doi:10.1038/s41467-023-42307-1

Atomic high-spin cobalt(II) center for highly selective electrochemical CO reduction to CH₃OH

Nat Commun. 2023 Oct 17;14(1):6550. doi: 10.1038/s41467-023-42307-1.

Authors

Jie Ding^#^{1

2}, Zhiming Wei^#¹, Fuhua Li^#², Jincheng Zhang², Qiao Zhang¹, Jing Zhou³, Weijue Wang⁴, Yuhang Liu⁵, Zhen Zhang⁶, Xiaozhi Su⁷, Runze Yang⁶, Wei Liu⁴, Chenliang Su⁸, Hong Bin Yang⁹, Yanqiang Huang⁴, Yueming Zhai¹⁰, Bin Liu¹¹

Affiliations

¹ The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, China.
² Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, SAR 999077, China.
³ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China. zhoujing@sinap.ac.cn.
⁴ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
⁵ School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China.
⁶ China Astronaut Research and Training Center, Beijing, 100094, China.
⁷ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China.
⁸ International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Engineering Technology Research Center for 2D Materials Information Functional Devices and Systems of Guangdong Province, Institute of Microscale Optoeletronics, Shenzhen University, Shenzhen, 518060, China. chmsuc@szu.edu.cn.
⁹ School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China. yanghb@usts.edu.cn.
¹⁰ The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, China. yueming@whu.edu.cn.
¹¹ Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, SAR 999077, China. bliu48@cityu.edu.hk.

^# Contributed equally.

Abstract

In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co²⁺ can enhance the electron backdonation via the d_xz/d_yz-2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.