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Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst

Kornienko, Nikolay, Resasco, Joaquin, Becknell, Nigel, Jiang, Chang-Ming, Liu, Yi-Sheng, Nie, Kaiqi, Sun, Xuhui, Guo, Jinghua, Leone, Stephen R., Yang, Peidong·2015·Journal of the American Chemical Society
DOI 10.1021/jacs.5b03545
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Abstract

The generation of chemical fuel in the form of molecular H2 via the electrolysis of water is regarded to be a promising approach to convert incident solar power into an energy storage medium. Highly efficient and cost-effective catalysts are required to make such an approach practical on a large scale. Recently, a number of amorphous hydrogen evolution reaction (HER) catalysts have emerged that show promise in terms of scalability and reactivity, yet remain poorly understood. In this work, we utilize Raman spectroscopy and X-ray absorption spectroscopy (XAS) as a tool to elucidate the structure and function of an amorphous cobalt sulfide (CoSx) catalyst. Ex situ measurements reveal that the as-deposited CoSx catalyst is composed of small clusters in which the cobalt is surrounded by both sulfur and oxygen. Operando experiments, performed while the CoSx is catalyzing the HER, yield a molecular model in which cobalt is in an octahedral CoS2-like state where the cobalt center is predominantly surrounded by a first shell of sulfur atoms, which, in turn, are preferentially exposed to electrolyte relative to bulk CoS2. We surmise that these CoS2-like clusters form under cathodic polarization and expose a high density of catalytically active sulfur sites for the HER.

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Metadata

Authors
Kornienko, N., Resasco, J., Becknell, N., Jiang, C.-M., Liu, Y.-S., Nie, K., Sun, X., Guo, J., Leone, S. R., & Yang, P.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2015-06-08
Volume
137
Issue
23
Pages
7448-7455
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.5b03545
OpenAlex
W2290983583
Cited by
396
References
9
FWCI
12.41
Type
journal article
Language
en
Open access
closed
Funders
  • Division of Graduate Education (DGE-0802270)
  • Basic Energy Sciences (DE-AC02-05CH11231)

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CoChat. (2026). Citation check: Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst. https://app.cochat.ai/papers/10.1021/jacs.5b03545
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Kornienko, N., Resasco, J., Becknell, N., Jiang, C.-M., Liu, Y.-S., Nie, K., Sun, X., Guo, J., Leone, S. R., & Yang, P. (2015). Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.5b03545

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