Designing covalent organic frameworks with Co-O4 atomic sites for efficient CO2 photoreduction

Abstract

Cobalt coordinated covalent organic frameworks have attracted increasing interest in the field of CO₂ photoreduction to CO, owing to their high electron affinity and predesigned structures. However, achieving high conversion efficiency is challenging since most Co related coordination environments facilitate fast recombination of photogenerated electron-hole pairs. Here, we design two kinds of Co-COF catalysts with oxygen coordinated Co atoms and find that after tuning of coordination environment, the reported Co framework catalyst with Co-O₄ sites exhibits a high CO production rate of 18000 µmol g⁻¹ h⁻¹ with selectivity as high as 95.7% under visible light irradiation. From in/ex-situ spectral characterizations and theoretical calculations, it is revealed that the predesigned Co-O₄ sites significantly facilitate the carrier migration in framework matrixes and inhibit the recombination of photogenerated electron-hole pairs in the photocatalytic process. This work opens a way for the design of high-performance catalysts for CO₂ photoreduction.

A class of inexpensive aminoanthraquinone organic dyes are shown to facilitate visible-light-driven CO₂ reduction. Overall reaction efficiencies were found to be optimal when both electron donating and accepting groups were on a single dye molecule.