Boosting Exciton Dissociation and Charge Transfer in Triazole-Based Covalent Organic Frameworks by Increasing the Donor Unit from One to Two for the Efficient Photocatalytic Elimination of Emerging Contaminants

Abstract

As novel photocatalysts, covalent organic frameworks (COFs) have potential for water purification. Insufficient exciton dissociation and low charge mobility in COFs yet restricted their photocatalytic activity. Excitonic dissociation and charge transfer in COFs could be optimized via regulating the donor–acceptor (D–A) interactions through adjusting the number of donor units within COFs, yet relevant research is lacking. By integrating the 1,2,4-triazole or bis-1,2,4-triazole unit with quinone, we fabricated COF-DT (with a single donor unit) and COF-DBT (with double donor units) via a facile sonochemical method and used to decontaminate emerging contaminants. Due to the stronger D–A interactions than COF-DT, the exciton binding energy was lower for COF-DBT, facilitating the intermolecular charge transfer process. The degradation kinetics of tetracycline (model contaminant) by COF-DBT (k = (12.21 ± 1.29) × 10^–2 min^–1) was higher than that by COF-DT (k = (5.11 ± 0.59) × 10^–2 min^–1) under visible-light irradiation. COF-DBT could efficiently photodegrade tetracycline under complex water chemistry conditions and four real water samples. Moreover, six other emerging contaminants, both Gram-negative and Gram-positive strains, could also be effectively eliminated by COF-DBT. High tetracycline degradation performance achieved in a continuous-flow system and in five reused cycles in both laboratory and outdoor experiments with sunlight irradiation showed the stability and the potential for the practical application of COF-DBT.