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From NiMoO 4 to γ-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy

Abstract : Water electrolysis powered by renewable energies is a promising technology to produce sustainable fossil free fuels. The development and evaluation of effective catalysts are here imperative; however, due to the inclusion of elements with different redox properties and reactivity, these materials undergo dynamical changes and phase transformations during the reaction conditions. NiMoO4 is currently investigated among other metal oxides as a promising noble metal free catalyst for the oxygen evolution reaction. Here we show that at applied bias, NiMoO4·H2O transforms into γ-NiOOH. Time resolved operando Raman spectroscopy is utilized to follow the potential dependent phase transformation and is collaborated with elemental analysis of the electrolyte, confirming that molybdenum leaches out from the as-synthesized NiMoO4·H2O. Molybdenum leaching increases the surface coverage of exposed nickel sites, and this in combination with the formation of γ-NiOOH enlarges the amount of active sites of the catalyst, leading to high current densities. Additionally, we discovered different NiMoO4 nanostructures, nanoflowers, and nanorods, for which the relative ratio can be influenced by the heating ramp during the synthesis. With selective molybdenum etching we were able to assign the varying X-ray diffraction (XRD) pattern as well as Raman vibrations unambiguously to the two nanostructures, which were revealed to exhibit different stabilities in alkaline media by time-resolved in situ and operando Raman spectroscopy. We advocate that a similar approach can beneficially be applied to many other catalysts, unveiling their structural integrity, characterize the dynamic surface reformulation, and resolve any ambiguities in interpretations of the active catalyst phase.
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https://hal-cea.archives-ouvertes.fr/cea-03321066
Contributor : Serge Palacin Connect in order to contact the contributor
Submitted on : Tuesday, August 17, 2021 - 7:19:50 AM
Last modification on : Tuesday, August 24, 2021 - 2:18:11 PM

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Robin Dürr, Pierfrancesco Maltoni, Haining Tian, Bruno Jousselme, Leif Hammarström, et al.. From NiMoO 4 to γ-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy. ACS Nano, American Chemical Society, In press, 15 (8), pp.13504-13515. ⟨10.1021/acsnano.1c04126⟩. ⟨cea-03321066⟩

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