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 () and Bin Liu ()
Additional contact information
Jie Ding: Wuhan University
Zhiming Wei: Wuhan University
Fuhua Li: City University of Hong Kong
Jincheng Zhang: City University of Hong Kong
Qiao Zhang: Wuhan University
Jing Zhou: Chinese Academy of Sciences
Weijue Wang: Chinese Academy of Sciences
Yuhang Liu: Suzhou University of Science and Technology
Zhen Zhang: China Astronaut Research and Training Center
Xiaozhi Su: Chinese Academy of Sciences
Runze Yang: China Astronaut Research and Training Center
Wei Liu: Chinese Academy of Sciences
Chenliang Su: Shenzhen University
Hong Bin Yang: Suzhou University of Science and Technology
Yanqiang Huang: Chinese Academy of Sciences
Yueming Zhai: Wuhan University
Bin Liu: City University of Hong Kong

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: 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 dxz/dyz−2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.

Date: 2023
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DOI: 10.1038/s41467-023-42307-1

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