Solar‐Driven Carbon–Nitrogen Coupling Between Biomass‐Derived Alcohol and Ammonia for High‐Value Amine Synthesis

ABSTRACT Photocatalytic carbon–nitrogen (C–N) coupling of biomass‐derived alcohols and inorganic nitrogen sources provides a sustainable route to high‐value amines but is often limited by inefficient C–H activation and uncontrollable nitrogen conversion kinetics. Herein, we report a synergistic redox pathway integrating anaerobic alcohol dehydrogenation and imine hydrogenation, enabled by an atomically dispersed Au species coordinated with three foreign phosphorus atoms on CdS nanorods (AuP 3 ‐CdS). In situ spectroscopy and theoretical calculations elucidate that Au–P 3 sites boost charge separation and enable both alcohol dehydrogenation and imine hydrogenation with optimal reaction energies compared to the conventional Au species coordinated with three intrinsic sulfur atoms on CdS nanorods (AuS 3 ‐CdS). These characteristics enable AuP 3 ‐CdS to achieve a furfurylamine production rate of 41.48 mmol g −1 h −1 with a selectivity of 99.1% from biomass‐derived furfuryl alcohol and ammonia, which is 63 times higher than that of conventional AuS 3 ‐CdS, and notably surpasses other P‐coordinated metal‐loaded CdS catalysts. Moreover, AuP 3 ‐CdS is also applicable to various other alcohols for diverse amine synthesis. Furthermore, this catalyst demonstrates a production rate of 14.24 mmol g −1 h −1 with a selectivity of 97.1% under concentrated natural sunlight (3773 mW cm −2 ) in a scalable reactor, providing a promising strategy for the photosynthetic synthesis of amines from diverse biomass‐derived alcohols and ammonia.