Molecular Insights into Photochemical Hydrogen Evolution Dual Catalysis within the Shell of Polymer Micelle-Based Nanoreactors

Polymer micelles are promising candidates for facilitating efficient catalysis within their distinguished nanospaces. However, the design of polymer micelle-based nanoreactors for dual photocatalysis, where a photocatalyst and another catalyst are involved in a single catalysis, remains limited in scope due to the lack of molecular insight into the bimolecular process within polymer micelles. Here, we investigated the cooperativity of a photocatalyst and a hydrogen evolution catalyst immobilized within the shell of polymer micelle-based nanoreactors. The results of several photochemical experiments suggested the existence of two types of catalyst pairs, the fluctuated and contacted pairs of the photocatalyst and hydrogen evolution catalyst within the nanoreactors. Moreover, the reaction rates of the photochemical hydrogen evolution were strongly affected by molecular crowding within the shell. Our study paves the way for developing polymer micelle-based nanoreactors for efficient dual photocatalysis.