Selective photocatalytic semihydrogenation of alkynols to alkenols on Pd–C3N4 nanosheets under ambient conditions

Abstract

Selective hydrogenation of alkynols to alkenols is an essential process for producing fine and intermediate chemicals. Currently, thermocatalytic alkynol hydrogenation faces several challenges, e.g., the safety of high-pressure hydrogen (H2) gas and the need for elevated temperature, and unavoidable side reactions, e.g., overhydrogenation. Here, a novel photocatalytic strategy is proposed for selectively reducing alkynols to alkenols with water as a hydrogen source under ambient temperature and pressure. Under the irradiation of simulated solar light, carbon nitride (C3N4) nanosheets with palladium (Pd) nanoparticles as cocatalysts (Pd–C3N4 NSs) exhibit a 2-methyl-3-butyn-2-ol (MBY) conversion of 98% and 2-methyl-3-buten-2-ol (MBE) selectivity of 95%, outperforming state-of-the-art thermocatalysts and electrocatalysts. After natural-sunlight irradiation (average light intensity of 25.13 mW cm−2) for 36 h, a MBY conversion of 98% and MBE selectivity of 92% was achieved in a large-scale photocatalytic system (2500 cm2). Experimental and theoretical investigations reveal that Pd cocatalysts on C3N4 facilitate the adsorption and hydrogenation of MBY as well as the formation of active hydrogen species, which promote the selective semihydrogenation of alkynols. Moreover, the proposed strategy is applicable to various water-soluble alkynols. This work paves the way for photocatalytic strategies to replace thermocatalytic hydrogenation processes using pressurized hydrogen.