Intermolecular cascaded π-conjugation channels for electron delivery powering CO2 photoreduction

Photoreduction of CO 2 to fuels offers a promising strategy for managing the global carbon balance using renewable solar energy. But the decisive process of oriented photogenerated electron delivery presents a considerable challenge. Here, we report the construction of intermolecular cascaded π-conjugation channels for powering CO 2 photoreduction by modifying both intramolecular and intermolecular conjugation of conjugated polymers (CPs). This coordination of dual conjugation is firstly proved by theoretical calculations and transient spectroscopies, showcasing alkynyl-removed CPs blocking the delocalization of electrons and in turn delivering the localized electrons through the intermolecular cascaded channels to active sites. Therefore, the optimized CPs (N-CP-D) exhibiting CO evolution activity of 2247 μmol g −1 h −1 and revealing a remarkable enhancement of 138-times compared to unmodified CPs (N-CP-A). While conversion of CO 2 to fuels may offer a bio-inspired means to renewably utilize fossil fuel emission, most materials demonstrate poor activities for CO 2 reduction. Here, authors construct conjugated polymers that modulate photo-induced electron transfer to CO 2 reduction catalysts.