Porous ionic polymers as a photocatalyst: Self-assembly of donor-acceptor by regulating the valence state of photo-responsive groups

Abstract

The world is on high alert against trace but extremely hazardous pollution of heavy metals and organic dyes in wastewater. Among various treatments, porous photocatalyst with dual functions of adsorptive enrichment and photodegradation are highly desirable yet challenging. Herein, we demonstrate a robust donor-acceptor (D-A) self-assembly by regulating the valence state of photo-responsive groups to construct porous ionic. The density function theory calculations reveal that the excitons induced on the neutral pyridine group (D) can be attracted by its neighboring cationic pyridinium one (A), thus the distinct charges separation and transfer enhancement can be realized in one PIP-based photocatalyst. Guided by this, a partially ionized pyridine-pyridinium (PB-PIPs) photocatalysts are fabricated, which show excellent adsorption capacity for the heavy metal Cr(VI) anion on pyridinium cations and rhodamine B (RhB) on the pyridine rings. Significantly, the target-adsorptions promote the accurate deliveries of excitons, that the simultaneous photocatalytic reduction of Cr(VI) and oxidation of RhB are achieved. The photodegradation performance of PB-PIPs under visible-light irradiation is superior to the state-of-the-art organic photocatalysts. Therefore, this convenient strategy of the valence state regulation provides a promising solution to the focus of synergistically visible-light harvesting, charges separating and transferring, and target-delivering in photocatalysis.