Influence of Oxygen Dopants on the HER Catalytic Activity of Electrodeposited MoOxSyElectrocatalysts

Lee Kendall; Amir Chamaani; Zachary Piontkowski; Thomas E. Beechem; Mackenzie Ridley; Elizabeth J. Opila; Giovanni Zangari; Stephen J. McDonnell

doi:10.1021/acsaem.1c02234

Influence of Oxygen Dopants on the HER Catalytic Activity of Electrodeposited MoO_xS_yElectrocatalysts

Lee Kendall, Amir Chamaani, Zachary Piontkowski, Thomas E. Beechem, Mackenzie Ridley, Elizabeth J. Opila, Giovanni Zangari, Stephen J. McDonnell

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

6 Scopus citations

Abstract

Amorphous, polymeric molybdenum sulfide has attracted significant attention as a non-platinum group electrocatalyst for the hydrogen evolution reaction (HER). To elucidate the influence of oxygen incorporation on molybdenum sulfide catalysts, MoOxSy electrocatalysts were synthesized via a potentiostatic electrodeposition method. The presence of oxygen and the associated molybdenum oxidation state were modified by postsynthesis treatments of air exposure, annealing in an inert atmosphere, and annealing in a sulfur flux. The as deposited sample exhibited the best performance, requiring only 171 mV to reach a cathodic current density of 10 mA/cm2. While the modified films exhibited worse HER performance compared to the as deposited sample, by utilizing extensive X-ray photoelectron spectroscopy studies, we highlighted the importance of the Mo5+ oxidation state while identifying a previously unreported state within MoOxSy catalysts between Mo4+ and Mo5+.

Original language	English
Pages (from-to)	13676-13683
Number of pages	8
Journal	ACS Applied Energy Materials
Volume	4
Issue number	12
DOIs	https://doi.org/10.1021/acsaem.1c02234
State	Published - Dec 27 2021
Externally published	Yes

Funding

This work was supported by the University of Virginia’s Nanoscale Materials Characterization Facility and was partially funded by the Virginia Space Grant Consortium Graduate Research STEM Fellowship. Raman interpretation was aided by the Center for Integrated Nanotechnologies at Sandia National Laboratory. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. DOE’s National Nuclear Security Administration under contract DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government.

Funders	Funder number
U.S. Department of Energy
Virginia Space Grant Consortium
National Nuclear Security Administration	DE-NA-0003525
University of Virginia

Keywords

MoS
Raman spectroscopy
X-ray photoelectron spectroscopy
catalysis
electrodeposition
water splitting

UN SDGs

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

Access to Document

10.1021/acsaem.1c02234

Cite this

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title = "Influence of Oxygen Dopants on the HER Catalytic Activity of Electrodeposited MoOxSyElectrocatalysts",

abstract = "Amorphous, polymeric molybdenum sulfide has attracted significant attention as a non-platinum group electrocatalyst for the hydrogen evolution reaction (HER). To elucidate the influence of oxygen incorporation on molybdenum sulfide catalysts, MoOxSy electrocatalysts were synthesized via a potentiostatic electrodeposition method. The presence of oxygen and the associated molybdenum oxidation state were modified by postsynthesis treatments of air exposure, annealing in an inert atmosphere, and annealing in a sulfur flux. The as deposited sample exhibited the best performance, requiring only 171 mV to reach a cathodic current density of 10 mA/cm2. While the modified films exhibited worse HER performance compared to the as deposited sample, by utilizing extensive X-ray photoelectron spectroscopy studies, we highlighted the importance of the Mo5+ oxidation state while identifying a previously unreported state within MoOxSy catalysts between Mo4+ and Mo5+.",

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author = "Lee Kendall and Amir Chamaani and Zachary Piontkowski and Beechem, {Thomas E.} and Mackenzie Ridley and Opila, {Elizabeth J.} and Giovanni Zangari and McDonnell, {Stephen J.}",

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AU - Kendall, Lee

AU - Chamaani, Amir

AU - Piontkowski, Zachary

AU - Beechem, Thomas E.

AU - Ridley, Mackenzie

AU - Opila, Elizabeth J.

AU - Zangari, Giovanni

AU - McDonnell, Stephen J.

PY - 2021/12/27

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N2 - Amorphous, polymeric molybdenum sulfide has attracted significant attention as a non-platinum group electrocatalyst for the hydrogen evolution reaction (HER). To elucidate the influence of oxygen incorporation on molybdenum sulfide catalysts, MoOxSy electrocatalysts were synthesized via a potentiostatic electrodeposition method. The presence of oxygen and the associated molybdenum oxidation state were modified by postsynthesis treatments of air exposure, annealing in an inert atmosphere, and annealing in a sulfur flux. The as deposited sample exhibited the best performance, requiring only 171 mV to reach a cathodic current density of 10 mA/cm2. While the modified films exhibited worse HER performance compared to the as deposited sample, by utilizing extensive X-ray photoelectron spectroscopy studies, we highlighted the importance of the Mo5+ oxidation state while identifying a previously unreported state within MoOxSy catalysts between Mo4+ and Mo5+.

AB - Amorphous, polymeric molybdenum sulfide has attracted significant attention as a non-platinum group electrocatalyst for the hydrogen evolution reaction (HER). To elucidate the influence of oxygen incorporation on molybdenum sulfide catalysts, MoOxSy electrocatalysts were synthesized via a potentiostatic electrodeposition method. The presence of oxygen and the associated molybdenum oxidation state were modified by postsynthesis treatments of air exposure, annealing in an inert atmosphere, and annealing in a sulfur flux. The as deposited sample exhibited the best performance, requiring only 171 mV to reach a cathodic current density of 10 mA/cm2. While the modified films exhibited worse HER performance compared to the as deposited sample, by utilizing extensive X-ray photoelectron spectroscopy studies, we highlighted the importance of the Mo5+ oxidation state while identifying a previously unreported state within MoOxSy catalysts between Mo4+ and Mo5+.

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