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.