Photocatalytic C─N Coupling From Alcohols and Ammonia to Amides Mediated by Synergistic Vacancies and Exposed Zn Sites

ABSTRACT The photocatalytic conversion of abundant carbon‐ and nitrogen‐containing small molecules into high‐value organonitrogen compounds presents a promising route to reduce reliance on fossil resources. In this study, a visible‐light‐responsive ZnCdS solid solution with engineered sulfur vacancies (ZCS v ) is developed for the efficient synthesis of amides from alcohols and NH 3 . The optimized ZCS v ‐5 catalyst achieves a high formamide yield rate of ∼4.27 mmol g cat −1 h −1 with 87.4% selectivity from CH 3 OH and NH 3 . Projected density of states (PDOS) analysis and in situ X‐ray photoelectron spectroscopy (XPS) provide direct evidence that S v creates a polarized surface environment and Zn sites serve as hole reservoirs, which synergistically facilitate charge separation. In situ Fourier transform infrared spectroscopy (FTIR), combined with theoretical simulations, reveal that the exposed Zn sites strengthen reactant adsorption and enable selective activation of C─H and N─H bonds for C─N coupling. This work establishes a feasible strategy for sustainable formamide production via photocatalytic C─N coupling and demonstrates its potential applicability to the synthesis of other amide derivatives, such as acetamide and benzamide.