Linking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO2 reduction with H2O

Jie Zhou; Jie Li; Liang Kan; Lei Zhang; Qing Huang; Yong Yan; Yifa Chen; Jiang Liu; Shun-Li Li; Ya-Qian Lan

doi:10.1038/s41467-022-32449-z

Linking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO₂ reduction with H₂O

Nat Commun. 2022 Aug 10;13(1):4681. doi: 10.1038/s41467-022-32449-z.

Authors

Jie Zhou^#¹, Jie Li^#¹, Liang Kan¹, Lei Zhang¹, Qing Huang¹, Yong Yan², Yifa Chen¹, Jiang Liu¹, Shun-Li Li¹, Ya-Qian Lan³

Affiliations

¹ School of Chemistry, South China Normal University, Guangzhou, 510006, P.R. China.
² School of Chemistry, South China Normal University, Guangzhou, 510006, P.R. China. Yong.Yan@m.scnu.edu.cn.
³ School of Chemistry, South China Normal University, Guangzhou, 510006, P.R. China. yqlan@m.scnu.edu.cn.

^# Contributed equally.

Abstract

Mimicking natural photosynthesis to convert CO₂ with H₂O into value-added fuels achieving overall reaction is a promising way to reduce the atmospheric CO₂ level. Casting the catalyst of two or more catalytic sites with rapid electron transfer and interaction may be an effective strategy for coupling photocatalytic CO₂ reduction and H₂O oxidation. Herein, based on the MOF ∪ COF collaboration, we have carefully designed and synthesized a crystalline hetero-metallic cluster catalyst denoted MCOF-Ti₆Cu₃ with spatial separation and functional cooperation between oxidative and reductive clusters. It utilizes dynamic covalent bonds between clusters to promote photo-induced charge separation and transfer efficiency, to drive both the photocatalytic oxidative and reductive reactions. MCOF-Ti₆Cu₃ exhibits fine activity in the conversion of CO₂ with water into HCOOH (169.8 μmol g^-1h^-1). Remarkably, experiments and theoretical calculations reveal that photo-excited electrons are transferred from Ti to Cu, indicating that the Cu cluster is the catalytic reduction center.