Rational modulation of covalent organic frameworks heterogeneous catalyst: Structural cationization effect on accelerating photocatalytic oxidation process

Abstract

Photocatalytic technology has been playing a key role in energy conversion and environmental remediation. It is critical and challenging that understanding and modulating the local structure effect on accelerating each rate-dependent step during the photocatalytic process. Herein, we utilize the highly ordered and structurally tunable COFs as a favorable platform for integrating multiple modulations of photochemical properties, including light capture, exciton dissociation, charge separation, and mass transfer by structural cationization strategy. Moreover, it is found that the cationized COF has a strong enrichment ability on the sulfide substrates, exhibiting an extremely fast selective oxidation rate of sulfides even in air. The calculation results indicate that the structural cationization successfully aggregates reaction substrates and increases the molecular collision probability, generating a reaction environment to promote the photocatalytic performances. This study will be expected to facilitate the new insights for the exploration of highly active COFs heterogeneous photocatalysts.