Nature Communications (Oct 2023)

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
https://doi.org/10.1038/s41467-023-42307-1
Journal volume & issue
Vol. 14, no. 1
pp. 1 – 10

Abstract

Read online

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.