Engineering Atomic Sites and Proton Transfer Microenvironments for Bioinspired Photocatalytic Alcohol‐Amine Coupling

Abstract Achieving a precise understanding and accurate design of heterogeneous catalysts based on bioinspired principles is challenging yet crucial to digging out optimal materials for artificial catalysis. Here, an ADH‐mimicking dual‐site photocatalyst (YCuCdS) is developed, and demonstrates the powerful effects of atomic site configuration and proton transfer environments on alcohol‐amine coupling. Mechanism studies reveal that the alcohol substrate is effectively dehydrogenated at the Y sites, forming the carbonyl intermediates that rapidly experience condensation with the amine. Meanwhile, the released hydrogen species (H _ads ) migrate from adjacent Cu sites to active S atoms, promoting H ₂ production and hindering the over‐hydrogenation of imine. As a result, a high imine yield of 92% is achieved, along with an H ₂ production rate of 7400 µmol g ⁻¹ h ⁻¹ . This work showcases an effective strategy for the design of heterogeneous catalysts with bioinspiration.