Synergistic enhancement of charge and mass transport in three-dimensional donor-acceptor COFs for efficient contaminant degradation via peroxymonosulfate activation

Cobalt-modulated D-A 3D-COF for superior photocatalytic PMS activation. • Efficient exciton dissociation and enhanced charge separation. • Outstanding pollutant removal and reduced ecological toxicity. The practical application of covalent organic frameworks (COFs) in photocatalytic peroxymonosulfate (PMS) activation is often constrained by sluggish charge kinetics and limited mass transfer. Herein, we construct a series of three-dimensional (3D) donor-acceptor (D-A) COFs to concurrently address these dual challenges. The unique 3D architecture features interconnected porous channels that provide accessible pathways for reactant transport, while metalloporphyrin based D-A engineering significantly enhances charge separation and migration. As a result, the optimized 3D Co COF combines an accessible hierarchical pore network with accelerated charge kinetics, achieving 95.25% SMX removal within 100 min under visible light. Combined experimental and theoretical analyses confirm that the 3D D-A structure with cobalt incorporation fine-tunes the electronic configuration, reduces the exciton binding energy, and facilitates the generation of reactive oxygen species. Moreover, the system exhibits robust continuous-flow performance under visible-light irradiation and effective SMX degradation under natural sunlight, together with favorable detoxification and antibacterial activity. This work highlights the great promise of 3D COFs in overcoming intrinsic kinetic and transport limitations for advanced oxidation processes. Download: Download high-res image (314KB) Download: Download full-size image