Theoretical and experimental investigations of vanadium pentoxide–based electrocatalysts for the hydrogen evolution reaction in alkaline media

A key approach towards better realization of intermittent renewable energy resources, namely, solar and wind, is green electrochemical hydrogen production from water electrolysis. In recent years, there have been increasing efforts aimed at developing noble metal-free electrocatalysts that are earth-abundant and electroactive towards hydrogen evolution reaction (HER) in alkaline electrolytes, wherein an initial water dissociation step is followed by a two-electron transfer cathodic reaction. Although relatively earth-abundant, vanadium-based electrocatalysts have been sparsely reported due to subpar electroactivity and kinetics towards water electrolysis in general and alkaline electrolysis in specific. Herein, we investigate the fine-tuning of orthorhombic V₂O₅-based electrocatalysts as candidates for HER through a scalable two-step sol–gel calcination procedure. Briefly, surface-induced anionic oxygen deficiencies and cationic dopants are synergistically studied experimentally and theoretically. To that end, first-principle facet-dependent density function theory (DFT) calculations were conducted and revealed that the coupling of certain dopants on V₂O₅ and co-induction of oxygen vacancies can enhance the catalytic HER performance by the creation of new electronic states near the Fermi level (E_F), enhancing conductivity, and modulating surface binding of adsorbed protons, respectively. This was reflected experimentally through kinetically non-ideal alkaline electrochemical HER using Zn_0.4V_1.6O₅ whereby − 194 mV of overpotential was required to attain − 10 mA/cm² of current density, as opposed to pristine V₂O₅ which required 32% higher overpotential requirement at the same conditions. The disclosed work can be extended to other intrinsically sluggish transition metal (TM)–based oxides via the presented systematic tuning of surface and bulk microenvironment modulation. Graphical Abstract: (Figure presented.)