Polyampholytic Graft Copolymers as Matrix for TiO2/Eosin Y/[Mo3S13]2− Hybrid Materials and Light‐Driven Catalysis

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic‐inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO2 core functionalized with a polyampholytic (poly(dehydroalanine)‐graft‐(n‐propyl phosphonic acid acrylamide) shell (PDha‐g‐PAA@TiO2). The PDha‐g‐PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO2 core. This resulted in high visible‐light‐driven H2 generation. The enhanced light‐driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha‐g‐PAA@TiO2 was possible by introducing [Mo3S13]2− cluster anions as hydrogen‐evolution cocatalyst. This novel design approach is an example for a multi‐component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species. A tailor‐made polyampholyte matrix enables effective interaction of different components in light‐driven hydrogen evolution reaction, in our case TiO2 nanoparticles, thiomolybdate [Mo3S13]2− clusters, and Eosin Y as photosensitizer. Altogether, high photocatalytic activity for H2 generation under visible‐light irradiation was observed for well‐defined hybrid materials.