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

• Published in: Nature communications Vol. 13; no. 1; p. 4681
• Main Authors: Zhou, Jie, Li, Jie, Kan, Liang, Zhang, Lei, Huang, Qing, Yan, Yong, Chen, Yifa, Liu, Jiang, Li, Shun-Li, Lan, Ya-Qian
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group 10.08.2022; Nature Publishing Group UK; Nature Portfolio
• Subjects: Active sites; Carbon dioxide; Catalysts; Charge efficiency; Charge transfer; Chemical reduction; Chemical synthesis; Clusters; Copper; Covalent bonds; Crystal structure; Crystallinity; Electron transfer; Electrons; Oxidation; Photocatalysis; Photosynthesis; Separation; Strategy; Titanium
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-32449-z

Abstract Mimicking natural photosynthesis to convert CO 2 with H 2 O into value-added fuels achieving overall reaction is a promising way to reduce the atmospheric CO 2 level. Casting the catalyst of two or more catalytic sites with rapid electron transfer and interaction may be an effective strategy for coupling photocatalytic CO 2 reduction and H 2 O oxidation. Herein, based on the MOF ∪ COF collaboration, we have carefully designed and synthesized a crystalline hetero-metallic cluster catalyst denoted MCOF-Ti 6 Cu 3 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-Ti 6 Cu 3 exhibits fine activity in the conversion of CO 2 with water into HCOOH (169.8 μmol g −1 h −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.