Morphological and Structural Evolution of Co3O4 Nanoparticles Revealed by in Situ Electrochemical Transmission Electron Microscopy during Electrocatalytic Water Oxidation

  • Nathaly Ortiz Peña
    Nathaly Ortiz Peña
    Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504 CNRS − Université de Strasbourg, 23 rue du Loess, BP 43, Strasbourg Cedex 2, France
  • Dris Ihiawakrim
    Dris Ihiawakrim
    Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504 CNRS − Université de Strasbourg, 23 rue du Loess, BP 43, Strasbourg Cedex 2, France
  • Madeleine Han
    Madeleine Han
    Sorbonne Université, CNRS, Collège de France, Laboratoire Chimie de la Matière Condensée de Paris, 4 Place Jussieu, 75005 Paris, France
    Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91192 Gif sur Yvette, France
  • Benedikt Lassalle-Kaiser
    Benedikt Lassalle-Kaiser
    Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91192 Gif sur Yvette, France
  • Sophie Carenco
    Sophie Carenco
    Sorbonne Université, CNRS, Collège de France, Laboratoire Chimie de la Matière Condensée de Paris, 4 Place Jussieu, 75005 Paris, France
  • Clément Sanchez
    Clément Sanchez
    Sorbonne Université, CNRS, Collège de France, Laboratoire Chimie de la Matière Condensée de Paris, 4 Place Jussieu, 75005 Paris, France
  • Christel Laberty-Robert
    Christel Laberty-Robert
    Sorbonne Université, CNRS, Collège de France, Laboratoire Chimie de la Matière Condensée de Paris, 4 Place Jussieu, 75005 Paris, France
  • David Portehault*
    David Portehault
    Sorbonne Université, CNRS, Collège de France, Laboratoire Chimie de la Matière Condensée de Paris, 4 Place Jussieu, 75005 Paris, France
    *E-mail: [email protected]
  • , and 
  • Ovidiu Ersen*
    Ovidiu Ersen
    Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504 CNRS − Université de Strasbourg, 23 rue du Loess, BP 43, Strasbourg Cedex 2, France
    *E-mail: [email protected]
    More by Ovidiu Ersen
Cite this: ACS Nano 2019, 13, 10, 11372–11381
Publication Date (Web):October 4, 2019
Copyright © 2019 American Chemical Society
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Unveiling the mechanism of electrocatalytic processes is fundamental for the search of more efficient and stable electrode materials for clean energy conversion devices. Although several in situ techniques are now available to track structural changes during electrocatalysis, especially of water oxidation, a direct observation, in real space, of morphological changes of nanostructured electrocatalysts is missing. Herein, we implement an in situ electrochemical Transmission Electron Microscopy (in situ EC-TEM) methodology for studying electrocatalysts of the oxygen evolution reaction (OER) during operation, by using model cobalt oxide Co3O4 nanoparticles. The observation conditions were optimized to mimic standard electrochemistry experiments in a regular electrochemical cell, allowing cyclic voltammetry and chronopotentiometry to be performed in similar conditions in situ and ex situ. This in situ EC-TEM method enables us to observe the chemical, morphological, and structural evolutions occurring in the initial nanoparticle-based electrode exposed to different aqueous electrolytes and under OER conditions. The results show that surface amorphization occurs, yielding a nanometric cobalt (oxyhydr)oxide-like phase during OER. This process is irreversible and occurs to an extent that has not been described before. Furthermore, we show that the pH and counterions of the electrolytes impact this restructuration, shedding light on the materials properties in neutral phosphate electrolytes. In addition to the structural changes followed in situ during the electrochemical measurements, this study demonstrates that it is possible to rely on in situ electrochemical TEM to reveal processes in electrocatalysts while preserving a good correlation with ex situ regular electrochemistry.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.9b04745.

  • Figures S1 and S2: impact of the (S)TEM beam on the in situ electrochemical measurements. Figure S3: effect of beam current on the in situ observations in STEM. Figure S4: EELS, electron diffraction and size distribution after irradiation in the electrolyte. Figures S5, S6, and S7: additional ex situ and in situ cyclic voltammograms used to calibrate the internal reference, stability of the electrochemical response during in situ cyclic voltammetry and in situ chronopotentiometry, respectively. Figure S8: comparison between post mortem samples from the in situ setup and from a classical rotating GC disc. Figures S9, S10, and S11: additional electrochemical measurements in KPi and KCl electrolytes. Figures S12, S13, S14, and S15: additional HRTEM, EDX and electron diffraction data of the post mortem samples in KPi and KCl electrolytes (PDF)

  • Movie S1: STEM-bright field movie recorded in situ during chronopotentiometry experiment at 10 mA cm–2GC in aqueous 0.1 M KOH electrolyte first 176 s accelerated at 300 fps (AVI)

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