Single-atom molybdenum doping induces nickel oxide-to-hydroxide transformation for enhanced alkaline hydrogen evolution

Abstract

NiMoO_x compounds are widely regarded as among the most efficient non-noble metal catalysts for the hydrogen evolution reaction (HER). Nevertheless, understanding the structural evolution under in situ conditions and further enhancing their performance remain key challenges. Herein, we report that single-atom Mo doping in NiO significantly enhances its HER activity, reducing the overpotential to 131 mV at 10 mA cm⁻² compared to undoped NiO. In situ X-ray absorption spectroscopy and Raman spectroscopy reveal that under catalytic conditions, Mo single atoms remain structurally stable, while Ni²⁺ species in NiO are converted to Ni(OH)₂ in alkaline media under the applied working potential for HER. Notably, this transformation is absent in undoped NiO, indicating that Mo doping promotes the formation of active Ni(OH)₂ sites, which, in turn, accelerate the rate-limiting water dissociation step. These findings provide critical mechanistic insights into the structural evolution of NiMoO_x during alkaline HER and highlight the importance of in situ studies in the development of highly efficient catalysts.