Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover

Abstract Electrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low production efficiency or high energy consumption. Here, we describe a tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, is partnered with component (ii), which can readily release hydrogen for hydrogenation, to enable efficient generation of active hydrogen on component (i) at low overpotentials and timely (i)‐to‐(ii) hydrogen spillover and facile desorptive hydrogenation on component (ii). We examine this concept over bicomponent palladium‐copper catalysts for the production of representative 2‐methyl‐3‐butene‐2‐ol (MBE) from 2‐methyl‐3‐butyne‐2‐ol (MBY) and achieve a record high MBE production rate of 1.44 mmol h −1 cm −2 and a Faraday efficiency of ~88.8 % at a low energy consumption of 1.26 kWh kg MBE −1 . With these catalysts, we further achieve 60 h continuous production of MBE with record high profit space.