Conversion of Catalytically Inert 2D Bismuth Oxide Nanosheets for Effective Electrochemical Hydrogen Evolution...

Oxygen vacancies (V_o) in electrocatalysts are closely correlated with the hydrogen evolution reaction (HER) activity. The role of vacancy defects and the effect of their concentration, however, yet remains unclear. Herein, Bi₂O₃, an unfavorable electrocatalyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy (ΔG_H*), is utilized as a perfect model to explore the function of V_o on HER performance. Through a facile plasma irradiation strategy, Bi₂O₃ nanosheets with different V_o concentrations are fabricated to evaluate the influence of defects on the HER process. Unexpectedly, while the generated oxygen vacancies contribute to the enhanced HER performance, higher V_o concentrations beyond a saturation value result in a significant drop in HER activity. By tunning the V_o concentration in the Bi₂O₃ nanosheets via adjusting the treatment time, the Bi₂O₃ catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52 × 10²⁴ cm^-3 demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm^-2, a Tafel slope of 80 mV dec^-1, and an exchange current density of 316 mA cm^-2 in an alkaline solution, which approaches the top-tier activity among Bi-based HER electrocatalysts. Density-functional theory calculations confirm the preferred adsorption of H* onto Bi₂O₃ as a function of oxygen chemical potential (∆μ_O) and oxygen partial potential (P_O2) and reveal that high V_o concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity. This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.