Electron Bridge Effect Induced by Oxygen‐Bridged Ga on PdMo Bimetallene Nanoribbons for Boosting Electrocatalytic Alkynol Semihydrogenation

Abstract The utilization of green hydrogen sources in H₂O for alkynols electrocatalytic semihydrogenation reaction (ESHR) at ambient temperature provides a promising pathway toward the sustainable conversion of alkynols. However, it is still a great challenge to construct specific interfacial structure to adjust the electronic structure of Pd for the purpose of altering the strong adsorption of Pd with active hydrogen to enhance the production of alkenols. Here, the atomically dispersed GaO_x‐PdMo bimetallene nanoribbons (GaO_x‐PdMo BNRs) via oxygen bridging Ga atoms is designed to the surface of PdMo BNRs for 2‐methyl‐3‐butyn‐2‐ol (MBY) ESHR to the synthesis of 2‐methyl‐3‐buten‐2‐ol (MBE). The GaO_x‐PdMo BNRs achieve the excellent MBE selectivity (≈97.4%), Faraday efficiency (≈96.1%), and maintain long‐term stability. Density functional theory demonstrates that the top electron‐enriched Ga atoms and the bottom electron‐deficient Pd atoms construct a “pyramidal” interface via the oxygen bridge. The unique surface can effectively activate H₂O and weaken interaction between catalyst and MBE, thus promoting MBE generation. Moreover, the electron bridge effect between Ga‐O‐PdMo can induce p‐d orbital hybridization to achieve lower the d‐band center of surface Pd thus modulating the reactants adsorption. This work provides a strategy to improve ESHR performance by electron bridge effect to modulate interfacial electron distribution.