Co-electrodepositional synthesis of PdCu alloy nanocatalysts for boosting the electrocatalytic semi-hydrogenation of alkynols

Electrocatalytic selective hydrogenation represents a green and atom-efficient synthetic route, yet it remains fundamentally challenging to simultaneously achieve high activity and exceptional selectivity while suppressing competing side reactions, primarily hydrogen evolution and over-hydrogenation. To address this, we fabricate atomically Pd 1 Cu 1 alloy nanoparticles on carbon cloth (Pd 1 Cu 1 /CC) via a facile co-electrodeposition method. The catalyst enables highly efficient and selective electrocatalytic hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) in an aqueous alkaline electrolyte, delivering an MBE production rate of 0.88 mol h −1 g Cat. −1 with 96% selectivity and 92% Faradaic efficiency—performance superior to its monometallic counterparts. The catalyst also demonstrates excellent stability, broad substrate applicability, and promising potential for industrial application. Combined experimental and theoretical results reveal that the Pd 1 Cu 1 /CC catalyst exhibits a lowered activation energy (40.89 kJ mol −1 ), which not only facilitates active *H generation via water dissociation but also weakens the adsorption of MBE due to Cu-induced electronic modulation. This dual mechanism ensures efficient *H supply and prompts product desorption, thereby synergistically boosting selectivity while suppressing both over-hydrogenation and the hydrogen evolution reaction. This work provides insights into the design of advanced electrocatalysts for selective hydrogenation from the perspective of alloy catalyst, contributing to sustainable organic synthesis strategies.