Photocatalytic Acceptorless Dehydrogenation of Amines for Hydrogen and Imine Production Using Hollow MoS2‐ZnIn2S4/CeO2 Featuring Spatially Separated Redox Active Sites

Abstract Photocatalytic acceptorless dehydrogenation (PAD) of amines represents an innovative method for the production of hydrogen (H 2 ) and imines. Nonetheless, the efficiency of this reaction is often compromised by the formation of undesirable by‐products, such as dibenzylamine resulting from imine hydrogenation and 1,2‐diphenyl ethylenediamine due to C─C coupling. In this study, a novel hollow core/shell photocatalyst, MoS 2 ‐ZnIn 2 S 4 /CeO 2 (M‐ZIS/C), is designed and developed with spatially separated redox active sites to mitigate these challenges. The optimized M 3% ‐ZIS/C 45% catalyst demonstrates remarkable performance, achieving a 27.5‐fold increase in the production rate of H 2 and an 18.7‐fold in increase in the yield of N‐benzylidenebenzylamine (N‐BBA) during the benzylamine PAD reaction compared to pure ZnIn 2 S 4 . Notably, the selectivity for N‐BBA improved significantly from 15.6 to 97.4% upon the modification with MoS 2 . Isotopic tracing experiments further confirmed that H 2 is generated from amines, with trace amounts of water acting as a proton‐transfer mediator to accelerate the reaction kinetics. Additionally, in situ infrared spectroscopy revealed the reaction pathway of N─H bond cleavage to generate aldehyde imine intermediates, which subsequently undergo condensation with amines to yield imine products. This approach represents a significant advancement in energy‐chemical coupled photocatalytic systems for improving efficiency and versatility in H 2 production and imine synthesis.