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 H₂ production and hindering the over-hydrogenation of imine. As a result, a high imine yield of 92% is achieved, along with an H₂ production rate of 7400 µmol g⁻¹ h⁻¹. This work showcases an effective strategy for the design of heterogeneous catalysts with bioinspiration.