Ni–Co–S–Se Alloy Nanocrystals: Influence of the Composition on Their in Situ Transformation and Electrocatalytic Activity for the Oxygen Evolution Reaction

Cite this: ACS Appl. Nano Mater. 2018, 1, 10, 5753–5762
Publication Date (Web):September 27, 2018
Copyright © 2018 American Chemical Society
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The electrocatalytic oxygen evolution reaction (OER) is an important half reaction in various technologies, such as metal air batteries and electrochemical water splitting. Transition metal chalcogenides, especially those based on Co and Ni, are emerging as promising OER catalysts, thanks to their high activity and low cost. However, it is still being debated whether they act as actual catalysts or as catalyst precursors, undergoing structural and morphological changes under OER conditions. To gain a better comprehension of this topic, we have developed a simple colloidal synthesis method for alloy nanocrystals (NCs) based on Ni, Co, S, and Se with a tunable composition, and we studied their structural and morphological evolution during OER. We found that binary CoSe, ternary Ni–Co–Se and quaternary Ni–Co–S–Se NCs, with the exception of NiSe, each undergo structural and morphological changes under OER conditions, forming the corresponding metal oxides/hydroxides, which act as the actual active catalysts. Interestingly, we discovered that the composition of the starting metal chalcogenide NCs plays a major role in dictating the crystallinity, conductivity and activity of such oxide/hydroxide materials. This compositional tuning, that is going from CoSe to Ni0.25Co0.65S0.4Se0.6 NCs, resulted in a ∼7 fold improvement in the OER activity in terms of turnover frequency. Our results suggest that the compositional engineering of metal chalcogenide materials could potentially be used to control their inevitable transformation into the corresponding oxide/hydroxide counterparts, eventually improving their OER activity.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsanm.8b01418.

  • SAED patterns of Ni0.3Co0.74Se NCs before and after OER, XRD patterns of Ni0.42Co0.38S0.68Se0.32NCs, the stability test of Ni0.25Co0.65S0.4Se0.6 NCs, CVs of ternary and quaternary NCs with various compositions, SAED patterns of Ni0.25Co0.65S0.4Se0.6NCs before and after OER, additional HRTEM images of Ni0.25Co0.65S0.4Se0.6 NCs before and after OER, XRD pattern of Ni0.25Co0.65S0.4Se0.6 NCs on an FTO substrate after OER, STEM-EDS spectra of Ni0.3Co0.74Se and Ni0.25Co0.65S0.4Se0.6 NCs after OER, and XPS spectra of Ni0.3Co0.74Se and Ni0.25Co0.65S0.4Se0.6 NCs before and after OER (PDF)

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