Hydrogen-coverage-dependent Ni active sites govern activity and selectivity in large-current methanol oxidation reaction

Jiawei Shi; Huawei He; Weiwei Cai; Jing Li; Anantharaj Sengeni; Ligang Feng

doi:10.1016/j.jechem.2026.01.038

Hydrogen-coverage-dependent Ni active sites govern activity and selectivity in large-current methanol oxidation reaction

Jiawei Shi
, Huawei He
, Weiwei Cai
, Jing Li^*
, Anantharaj Sengeni
, Ligang Feng^*

^*Corresponding author for this work

Kunming University of Science and Technology
China University of Geosciences, Wuhan
Indian Institute of Technology Kanpur

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The unclear decisive factors make it tricky to realize high activity and selectivity for the methanol oxidation reaction (MOR) at an industrial-level current. Using Ni-based hydroxides as model catalysts, we reveal that Ni sites undergo a progressive dehydrogenation from NiO₂H₂ to low-hydrogen-coverage NiO₂H₁₋_x species, which serve as the active centers under high current densities. This transformation shifts the rate-determining step from catalyst dehydrogenation (NOR mechanism) to *CH₃O dehydrogenation, while the adsorption behavior of *HCOO dictates product selectivity. Guided by these insights, a Fe-NiCo ternary hydroxide catalyst was rationally designed to modulate intermediate adsorption energetics. The optimized Fe-NiCo-TH catalyst delivers industrially relevant MOR performance, achieving >500 mA cm−2 at 1.47 V, >90% formate selectivity, and excellent long-term durability. This study establishes hydrogen-coverage-dependent active sites as a decisive factor in MOR and provides a mechanistic foundation for designing Ni-based electrocatalysts for coupled hydrogen production.

Original language	English
Pages (from-to)	625-630
Number of pages	6
Journal	Journal of Energy Chemistry
Volume	116
DOIs	https://doi.org/10.1016/j.jechem.2026.01.038
State	Published - May 2026
Externally published	Yes

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This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Hydrogen coverage
Industrial current density
Mechanistic study
Methanol oxidation reaction
Ni-based hydroxide

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10.1016/j.jechem.2026.01.038

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title = "Hydrogen-coverage-dependent Ni active sites govern activity and selectivity in large-current methanol oxidation reaction",

abstract = "The unclear decisive factors make it tricky to realize high activity and selectivity for the methanol oxidation reaction (MOR) at an industrial-level current. Using Ni-based hydroxides as model catalysts, we reveal that Ni sites undergo a progressive dehydrogenation from NiO2H2 to low-hydrogen-coverage NiO2H1−x species, which serve as the active centers under high current densities. This transformation shifts the rate-determining step from catalyst dehydrogenation (NOR mechanism) to *CH3O dehydrogenation, while the adsorption behavior of *HCOO dictates product selectivity. Guided by these insights, a Fe-NiCo ternary hydroxide catalyst was rationally designed to modulate intermediate adsorption energetics. The optimized Fe-NiCo-TH catalyst delivers industrially relevant MOR performance, achieving >500 mA cm−2 at 1.47 V, >90\% formate selectivity, and excellent long-term durability. This study establishes hydrogen-coverage-dependent active sites as a decisive factor in MOR and provides a mechanistic foundation for designing Ni-based electrocatalysts for coupled hydrogen production.",

keywords = "Hydrogen coverage, Industrial current density, Mechanistic study, Methanol oxidation reaction, Ni-based hydroxide",

author = "Jiawei Shi and Huawei He and Weiwei Cai and Jing Li and Anantharaj Sengeni and Ligang Feng",

note = "Publisher Copyright: {\textcopyright} 2026 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.",

year = "2026",

month = may,

doi = "10.1016/j.jechem.2026.01.038",

language = "英语",

volume = "116",

pages = "625--630",

journal = "Journal of Energy Chemistry",

issn = "2095-4956",

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TY - JOUR

T1 - Hydrogen-coverage-dependent Ni active sites govern activity and selectivity in large-current methanol oxidation reaction

AU - Shi, Jiawei

AU - He, Huawei

AU - Cai, Weiwei

AU - Li, Jing

AU - Sengeni, Anantharaj

AU - Feng, Ligang

N1 - Publisher Copyright: © 2026 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

PY - 2026/5

Y1 - 2026/5

N2 - The unclear decisive factors make it tricky to realize high activity and selectivity for the methanol oxidation reaction (MOR) at an industrial-level current. Using Ni-based hydroxides as model catalysts, we reveal that Ni sites undergo a progressive dehydrogenation from NiO2H2 to low-hydrogen-coverage NiO2H1−x species, which serve as the active centers under high current densities. This transformation shifts the rate-determining step from catalyst dehydrogenation (NOR mechanism) to *CH3O dehydrogenation, while the adsorption behavior of *HCOO dictates product selectivity. Guided by these insights, a Fe-NiCo ternary hydroxide catalyst was rationally designed to modulate intermediate adsorption energetics. The optimized Fe-NiCo-TH catalyst delivers industrially relevant MOR performance, achieving >500 mA cm−2 at 1.47 V, >90% formate selectivity, and excellent long-term durability. This study establishes hydrogen-coverage-dependent active sites as a decisive factor in MOR and provides a mechanistic foundation for designing Ni-based electrocatalysts for coupled hydrogen production.

AB - The unclear decisive factors make it tricky to realize high activity and selectivity for the methanol oxidation reaction (MOR) at an industrial-level current. Using Ni-based hydroxides as model catalysts, we reveal that Ni sites undergo a progressive dehydrogenation from NiO2H2 to low-hydrogen-coverage NiO2H1−x species, which serve as the active centers under high current densities. This transformation shifts the rate-determining step from catalyst dehydrogenation (NOR mechanism) to *CH3O dehydrogenation, while the adsorption behavior of *HCOO dictates product selectivity. Guided by these insights, a Fe-NiCo ternary hydroxide catalyst was rationally designed to modulate intermediate adsorption energetics. The optimized Fe-NiCo-TH catalyst delivers industrially relevant MOR performance, achieving >500 mA cm−2 at 1.47 V, >90% formate selectivity, and excellent long-term durability. This study establishes hydrogen-coverage-dependent active sites as a decisive factor in MOR and provides a mechanistic foundation for designing Ni-based electrocatalysts for coupled hydrogen production.

KW - Hydrogen coverage

KW - Industrial current density

KW - Mechanistic study

KW - Methanol oxidation reaction

KW - Ni-based hydroxide

UR - https://www.scopus.com/pages/publications/105034504807

U2 - 10.1016/j.jechem.2026.01.038

DO - 10.1016/j.jechem.2026.01.038

M3 - 文章

AN - SCOPUS:105034504807

SN - 2095-4956

VL - 116

SP - 625

EP - 630

JO - Journal of Energy Chemistry

JF - Journal of Energy Chemistry

ER -

Hydrogen-coverage-dependent Ni active sites govern activity and selectivity in large-current methanol oxidation reaction

Abstract

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Keywords

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