Spin Manipulation in a Metal–Organic Layer through Mechanical Exfoliation for Highly Selective CO2 Photoreduction

Dayu Wu, Hua Qing Yin, Zeshi Wang, Mingren Zhou, Chengfeng Yu, Jing Wu, Huixian Miao, Takashi Yamamoto, Wenjiang Zhaxi, Zetao Huang, Luying Liu, Wei Huang, Wenhui Zhong, Yasuaki Einaga, Jun Jiang, Zhi Ming Zhang

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center. Due to spin transition of catalytic center, mixed-spin catalyst exhibits a high CO yield of 19.7 mmol g−1 with selectivity of 91.6 %, much superior to that of high-spin bulk counterpart (50 % selectivity). Density functional theory calculations reveal that low-spin 3d-orbital electronic configuration performs a key function in promoting CO2 adsorption and reducing activation barrier. Hence, the spin manipulation highlights a new insight into designing highly efficient biomimetic catalysts via optimizing spin state.

Original languageEnglish
Article numbere202301925
JournalAngewandte Chemie - International Edition
Volume62
Issue number18
DOIs
Publication statusPublished - 2023 Apr 24

Keywords

  • CO Reduction
  • Iron
  • Metal–Organic Layer
  • Photocatalysis
  • Spin Crossover

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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