Modulated Connection Modes of Redox Units in Molecular Junction Covalent Organic Frameworks for Artificial Photosynthetic Overall Reaction

Qi Li; Jia-Nan Chang; Zengmei Wang; Meng Lu; Can Guo; Mi Zhang; Tao-Yuan Yu; Yifa Chen; Shun-Li Li; Ya-Qian Lan

doi:10.1021/jacs.3c07471

Modulated Connection Modes of Redox Units in Molecular Junction Covalent Organic Frameworks for Artificial Photosynthetic Overall Reaction

J Am Chem Soc. 2023 Oct 25;145(42):23167-23175. doi: 10.1021/jacs.3c07471. Epub 2023 Oct 11.

Authors

Qi Li¹, Jia-Nan Chang², Zengmei Wang¹, Meng Lu², Can Guo², Mi Zhang², Tao-Yuan Yu³, Yifa Chen², Shun-Li Li², Ya-Qian Lan²

Affiliations

¹ Jiangsu Key Laboratory of Construction Materials, College of Materials Science and Engineering, Southeast University, Nanjing 211189, P.R. China.
² School of Chemistry, South China Normal University Guangzhou, Guangzhou 510006, P.R. China.
³ Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P.R. China.

PMID: 37820308
DOI: 10.1021/jacs.3c07471

Abstract

The precise tuning of components, spatial orientations, or connection modes for redox units is vital for gaining deep insight into efficient artificial photosynthetic overall reaction, yet it is still hard achieve for heterojunction photocatalysts. Here, we have developed a series of redox molecular junction covalent organic frameworks (COFs) (M-TTCOF-Zn, M = Bi, Tri, and Tetra) for artificial photosynthetic overall reaction. The covalent connection between TAPP-Zn and multidentate TTF endows various connection modes between water photo-oxidation (multidentate TTF) and CO₂ photoreduction (TAPP-Zn) centers that can serve as desired platforms to study the possible interactions between redox centers. Notably, Bi-TTCOF-Zn exhibits a high CO production rate of 11.56 μmol g^-1 h^-1 (selectivity, ∼100%), which is more than 2 and 6 times higher than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn, respectively. As revealed by theoretical calculations, Bi-TTCOF-Zn facilitates a more uniform distribution of energy-level orbitals, faster charge transfer, and stronger *OH adsorption/stabilization ability than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn.