Role of Oxidized Mo Species on the Active Surface of Ni–Mo Electrocatalysts for Hydrogen Evolution under Alkaline Conditions

Jeremy Bau; Sergey Kozlov; Luis Azofra Mesa; Samy Ould-Chikh; Abdul-Hamid M. Emwas; Hicham Idriss; Luigi Cavallo; Kazuhiro Takanabe

doi:10.1021/acscatal.0c02743

Role of Oxidized Mo Species on the Active Surface of Ni–Mo Electrocatalysts for Hydrogen Evolution under Alkaline Conditions

Jeremy Bau, Sergey Kozlov, Luis Azofra Mesa, Samy Ould-Chikh, Abdul-Hamid M. Emwas, Hicham Idriss, Luigi Cavallo, Kazuhiro Takanabe

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Abstract

A Ni–Mo composite functions as a promising non-noble metal electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water. Despite its industrial relevance, the kinetic origin of the high catalytic activity remains under debate. The present report discusses a reaction mechanism of HER on Ni–Mo catalysts by combining experimental and theoretical studies. In contrast to a Ni catalyst, a Ni–Mo catalyst is insensitive to CO gas introduced during HER. In situ spectroscopic measurements including Raman spectroscopy and electron paramagnetic resonance (EPR) show that Mo3+ prevails during HER catalysis. Density functional theory (DFT) simulations corroborate the thermodynamic stability and HER activity of Mo3+-containing centers on Ni(111) at HER potentials. Notably, Ni is demonstrated to play no direct role as a catalytic site but to effectively disperse and activate the oxidized catalytic Mo species. The results illustrate how to improve the electrocatalytic activity for alkaline HER.

Original language	English (US)
Pages (from-to)	12858-12866
Number of pages	9
Journal	ACS Catalysis
DOIs	https://doi.org/10.1021/acscatal.0c02743
State	Published - Oct 20 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-10-23
Acknowledgements: The research reported in this study was supported by the King Abdullah University of Science and Technology. The authors acknowledge the support of SABIC in funding this research. Computational resources were provided primarily by the KAUST Supercomputing Laboratory and the Shaheen II supercomputer. Computational work was also partially performed using resources of the National Supercomputing Centre, Singapore (https://www.nscc.sg).

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@article{fa612c66297142a78c7b07ccfefed13a,

title = "Role of Oxidized Mo Species on the Active Surface of Ni–Mo Electrocatalysts for Hydrogen Evolution under Alkaline Conditions",

abstract = "A Ni–Mo composite functions as a promising non-noble metal electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water. Despite its industrial relevance, the kinetic origin of the high catalytic activity remains under debate. The present report discusses a reaction mechanism of HER on Ni–Mo catalysts by combining experimental and theoretical studies. In contrast to a Ni catalyst, a Ni–Mo catalyst is insensitive to CO gas introduced during HER. In situ spectroscopic measurements including Raman spectroscopy and electron paramagnetic resonance (EPR) show that Mo3+ prevails during HER catalysis. Density functional theory (DFT) simulations corroborate the thermodynamic stability and HER activity of Mo3+-containing centers on Ni(111) at HER potentials. Notably, Ni is demonstrated to play no direct role as a catalytic site but to effectively disperse and activate the oxidized catalytic Mo species. The results illustrate how to improve the electrocatalytic activity for alkaline HER.",

author = "Jeremy Bau and Sergey Kozlov and {Azofra Mesa}, Luis and Samy Ould-Chikh and Emwas, {Abdul-Hamid M.} and Hicham Idriss and Luigi Cavallo and Kazuhiro Takanabe",

note = "KAUST Repository Item: Exported on 2020-10-23 Acknowledgements: The research reported in this study was supported by the King Abdullah University of Science and Technology. The authors acknowledge the support of SABIC in funding this research. Computational resources were provided primarily by the KAUST Supercomputing Laboratory and the Shaheen II supercomputer. Computational work was also partially performed using resources of the National Supercomputing Centre, Singapore (https://www.nscc.sg).",

year = "2020",

month = oct,

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doi = "10.1021/acscatal.0c02743",

language = "English (US)",

pages = "12858--12866",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

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T1 - Role of Oxidized Mo Species on the Active Surface of Ni–Mo Electrocatalysts for Hydrogen Evolution under Alkaline Conditions

AU - Bau, Jeremy

AU - Kozlov, Sergey

AU - Azofra Mesa, Luis

AU - Ould-Chikh, Samy

AU - Emwas, Abdul-Hamid M.

AU - Idriss, Hicham

AU - Cavallo, Luigi

AU - Takanabe, Kazuhiro

N1 - KAUST Repository Item: Exported on 2020-10-23 Acknowledgements: The research reported in this study was supported by the King Abdullah University of Science and Technology. The authors acknowledge the support of SABIC in funding this research. Computational resources were provided primarily by the KAUST Supercomputing Laboratory and the Shaheen II supercomputer. Computational work was also partially performed using resources of the National Supercomputing Centre, Singapore (https://www.nscc.sg).

PY - 2020/10/20

Y1 - 2020/10/20

N2 - A Ni–Mo composite functions as a promising non-noble metal electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water. Despite its industrial relevance, the kinetic origin of the high catalytic activity remains under debate. The present report discusses a reaction mechanism of HER on Ni–Mo catalysts by combining experimental and theoretical studies. In contrast to a Ni catalyst, a Ni–Mo catalyst is insensitive to CO gas introduced during HER. In situ spectroscopic measurements including Raman spectroscopy and electron paramagnetic resonance (EPR) show that Mo3+ prevails during HER catalysis. Density functional theory (DFT) simulations corroborate the thermodynamic stability and HER activity of Mo3+-containing centers on Ni(111) at HER potentials. Notably, Ni is demonstrated to play no direct role as a catalytic site but to effectively disperse and activate the oxidized catalytic Mo species. The results illustrate how to improve the electrocatalytic activity for alkaline HER.

AB - A Ni–Mo composite functions as a promising non-noble metal electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water. Despite its industrial relevance, the kinetic origin of the high catalytic activity remains under debate. The present report discusses a reaction mechanism of HER on Ni–Mo catalysts by combining experimental and theoretical studies. In contrast to a Ni catalyst, a Ni–Mo catalyst is insensitive to CO gas introduced during HER. In situ spectroscopic measurements including Raman spectroscopy and electron paramagnetic resonance (EPR) show that Mo3+ prevails during HER catalysis. Density functional theory (DFT) simulations corroborate the thermodynamic stability and HER activity of Mo3+-containing centers on Ni(111) at HER potentials. Notably, Ni is demonstrated to play no direct role as a catalytic site but to effectively disperse and activate the oxidized catalytic Mo species. The results illustrate how to improve the electrocatalytic activity for alkaline HER.

UR - http://hdl.handle.net/10754/665658

UR - https://pubs.acs.org/doi/10.1021/acscatal.0c02743

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DO - 10.1021/acscatal.0c02743

M3 - Article

SN - 2155-5435

SP - 12858

EP - 12866

JO - ACS Catalysis

JF - ACS Catalysis

ER -

Role of Oxidized Mo Species on the Active Surface of Ni–Mo Electrocatalysts for Hydrogen Evolution under Alkaline Conditions

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