Tailoring the structural design of covalent organic frameworks for enhanced photocatalytic carbon dioxide reduction: a review

Abstract

Covalent organic frameworks (COFs) exhibit distinct advantages such as extensive specific surface areas, chemical versatility, and sustainability, render them superb candidates for applications in the field of photocatalytic CO₂ reduction. In recent years, numerous COFs with remarkable photocatalytic CO₂ reduction activity have been reported, and extensive studies have been conducted to understand the mechanisms underlying the enhancement of their photocatalytic activity. This review delves into three pivotal areas: COF design, post-synthetic modifications, and composite photocatalyst construction. It uniquely examines the intricate structure-performance relationship at the molecular level, emphasizing topology, donor-acceptor interactions, crystallinity, functional groups, and heteroatom doping, thereby refining the design framework for COF-based photocatalysts. Moreover, the review offers a profound mechanistic analysis of CO₂ reduction, encompassing charge transfer, reaction intermediates, and surface kinetics, providing fresh insights into the efficient development of COF-based photocatalysts.