Enhancing Photocatalytic-Transfer Semi-Hydrogenation of Alkynes Over Pd/C3 N4 Through Dual Regulation of Nitrogen Defects and the Mott-Schottky Effect.

Abstract

The selective hydrogenation of alkynes is an important reaction; however, the catalytic activity and selectivity in this reaction are generally conflicting. In this study, ultrafine Pd nanoparticles (NPs) loaded on a graphite-like C3 N4 structure with nitrogen defects (Pd/DCN) are synthesized. The resulting Pd/DCN exhibits excellent photocatalytic performance in the transfer hydrogenation of alkynes with ammonia borane. The reaction rate and selectivity of Pd/DCN are superior to those of Pd/BCN (bulk C3 N4 without nitrogen defects) under visible-light irradiation. The characterization results and density functional theory calculations show that the Mott-Schottky effect in Pd/DCN can change the electronic density of the Pd NPs, and thus enhances the hydrogenation selectivity toward phenylacetylene. After 1h, the hydrogenation selectivity of Pd/DCN reaches 95%, surpassing that of Pd/BCN (83%). Meanwhile, nitrogen defects in the supports improve the visible-light response and accelerate the transfer and separation of photogenerated charges to enhance the catalytic activity of Pd/DCN. Therefore, Pd/DCN exhibits higher efficiency under visible light, with a turnover frequency (TOF) of 2002 min-1 . This TOF is five times that of Pd/DCN under dark conditions and 1.5 times that of Pd/BCN. This study provides new insights into the rational design of high-performance photocatalytic transfer hydrogenation catalysts.