Hollow microtubular chalcogen derived conjugated organic polymers for CO2 photoreduction: Morphology regulation and electron delocalization refining via atom substitution

The design of high-performance organic photocatalysts with special morphologies via subtle engineering at the atomic level is difficult. In this study, a sequence of hollow microtubular chalcogen (O, S, Se, and Te) conjugated organic polymers (COPs) for CO 2 photoreduction was successfully synthesized for the first time. The introduction of chalcogen atoms into molecular skeletons can regulate the flexibility of the building blocks, drive the polymerization of materials to evolve into a hollow tube morphology and significantly modify the energy band. The Se and Te atoms as semimetal elements, introduced in the organic molecules, distinctly boost the delocalization degree of excited electrons and accelerate the charge separation. The Se, Te-COPs show high photocatalytic CO 2 -to-CO conversion activity, namely 233.4, 347.3 μmol·g −1 in 6 h and 0.42 %, 0.67 % apparent quantum yield at 365 nm, respectively. This study presents the possibility of exploiting high-activity organic photocatalysts with special morphologies via a atom substitution strategy.