Identification of origin of insulating polymer maneuvered photoredox catalysis

Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalized π electrons along the molecular chain framework. Up to date, origin of insulating polymer regulated charge transfer has not yet been uncovered. In this work, we unleash the root origin of charge transport capability of insulating polymer in photocatalysis. We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides (TMCs), which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics, triggering the generation of defect over TMCs for prolonging carrier lifetime, and acting as hole-trapping mediator for retarding charge recombination. These synergistic roles contribute to the charge transfer of insulating polymer. Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.