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

Liu, Yuanqi; Gao, Qiang; Shi, Lei; Kearney, Joseph; Han, Xue; Xie, Zhenhua; Wang, Maoyu; Zhou, Hua; Zhu, Huiyuan

doi:10.1039/d5nh00302d

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

Journal Article · Thu Jun 19 00:00:00 UTC 2025 · Nanoscale Horizons

DOI: https://doi.org/10.1039/d5nh00302d · OSTI ID:2573762

^[1]; Gao, Qiang ^[1]; Shi, Lei ^[1]; Kearney, Joseph ^[1];

^[2]; Xie, Zhenhua ^[3]; Wang, Maoyu ^[4]; Zhou, Hua ^[4];

^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2573762

Report Number(s):: BNL--228469-2025-JAAM

Journal Information:: Nanoscale Horizons, Journal Name: Nanoscale Horizons Journal Issue: 9 Vol. 10; ISSN 2055-6764; ISSN 2055-6756

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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