Dipole moment regulation for enhancing internal electric field in covalent organic frameworks photocatalysts

Abstract

Covalent organic frameworks (COFs) have recently emerged as a kind of promising photocatalytic platform in addressing the growing threat of trace pollutants in aquatic environments. Along this, we propose a strategy of constructing internal electric field (IEF) in COFs through the dipole moment regulation, which intrinsically facilitates the separation and transfer of photogenerated excitons. Two COFs of BTT-TZ-COF and BTT-TB-COF are developed by linking the electron-donor of benzotrithiophene (BTT) block and the electron-acceptor of triazine (TZ) or tribenzene (TB) block, respectively. DFT calculations demonstrate TZ block with larger dipole moment can achieve more efficient IEF due to the stronger electron-attractive force and hence narrower bandgap. Moreover, featuring the highly-order crystalline structure for accelerating photo-excitons transfer and rich porosity for facilitating the adsorption, BTT-TZ-COF exhibited an excellent universal performance of photocatalytic degradations of various dyes. Specifically, a superior photodegradation efficiency of 99% Rhodamine B (RhB) is achieved within 20 min under the simulated sunlight. Therefore, this convenient construction approach of enhanced IEF in COFs through rational regulation of the dipole moment can be a promising way to realize high photocatalytic activity.