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

Photoreduction of CO2 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 pi-conjugation channels for powering CO2 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 mu mol g(-1) h(-1) and revealing a remarkable enhancement of 138-times compared to unmodified CPs (N-CP-A). While conversion of CO2 to fuels may offer a bio-inspired means to renewably utilize fossil fuel emission, most materials demonstrate poor activities for CO2 reduction. Here, authors construct conjugated polymers that modulate photo-induced electron transfer to CO2 reduction catalysts.