Abstract
Photochemical dehydrogenation of N-heterocyclic amines to corresponding N-heteroaromatics paired with hydrogen (H2) production represents a promising route for the green and sustainable organic synthesis and clean fuel generation. Herein, metal-organic frameworks (MOFs)-supported CdS nanoparticles are gingerly fabricated for the visible light-initiated acceptorless dehydrogenation of diverse N-heterocycles at ambient conditions. With further nickel cocatalysts modification via a simple photodeposition method, the optimized MIL-101 @CdS-Ni composite exhibits remarkably enhanced activities, which are 8 folds higher than that of binary MIL-101 @CdS and 2.8 times higher than that of MOF-removed CdS-Ni counterparts, along with high selectivity and good stability. Mechanism studies reveal that active nickel species plays a key role in accelerating the separation of photogenerated charge carries and the cleavage of C-H and N-H bonds in the scaffold of N-heterocycles on the catalyst surface. This work is expected to guide the rational catalysts design of MOF-based multifunctional materials for photochemical coupling of concurrent organic synthesis with H2 production.
NSTL