Electronic regulation of hcp-Ru by d-d orbital coupling for robust electrocatalytic hydrogen oxidation in alkaline electrolytes.

ABSTRACT

Bimetallic alloys hold exceptional promise as candidate materials because they offer a diverse parameter space for optimizing electronic structures and catalytic sites. Herein, we fabricate ruthenium-cobalt alloy nanoparticles uniformly dispersed within hollow mesoporous carbon spheres (hcp-RuCo@C) via impregnation and pyrolysis strategies. The intriguing hollow mesopore structure of hcp-RuCo@C facilitates efficient contact between active sites and reactants, thereby accelerating hydrogen oxidation reaction (HOR) kinetics. As anticipated, the hcp-RuCo@C showcases remarkable exchange current density and mass activity of 3.73 mA cm-2 and 2.8 mA µgRu-1, respectively, surpassing those of commercial Pt/C and documented Ru-based electrocatalysts. Notably, hcp-RuCo@C demonstrates robust resistance to 1000 ppm CO, a trait lacking in Pt/C catalysts. Comprehensive experimental results reveal that the alloying-induced d-d electronic interactions between Ru and Co species significantly optimizes hydrogen binding energy (HBE) and hydroxide binding energy (OHBE). This optimization promotes the vital Volmer step, ameliorating the alkaline HOR properties of hcp-RuCo@C.