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DOE OSTI · 1767062

Correlative operando microscopy of oxygen evolution electrocatalysts

Mefford, J. Tyler·Akbashev, Andrew R. (ORCID:0000000315731773)·Kang, Minkyung (ORCID:0000000332488496)·Bentley, Cameron L. (ORCID:0000000178676068)·Gent, William E. (ORCID:0000000176633988)·Deng, Haitao D.·Alsem, Daan Hein·Yu, Young-Sang (ORCID:0000000205459019)·Salmon, Norman J.·Shapiro, David A. (ORCID:0000000241866017)·Unwin, Patrick R. (ORCID:0000000331062178)·Chueh, William C. (ORCID:0000000270663470)
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Abstract

Transition metal (oxy)hydroxides are promising electrocatalysts for the oxygen evolution reaction.1–3 The properties of these materials evolve dynamically and heterogeneously4 with applied voltage through ion insertion redox reactions, converting inactive materials at open-circuit into active electrocatalysts during operation.5 Thus, the catalytic state is inherently far-from-equilibrium, complicating its direct observation. Here, we establish the link between the oxygen evolution activity and the local operational chemical, physical, and electronic nanoscale structure of single-crystalline β-Co(OH)2 platelet particles through a suite of newly developed correlative operando scanning probe and X-ray microscopy techniques. At pre-catalytic voltages, the particles swell to form an α-CoO2H1.5·0.5H2O-like structure with associated Co2.5+ oxidation state produced through hydroxide intercalation. With increasing voltage to drive oxygen evolution, interlayer water and protons de-intercalate to form contracted β-CoOOH particles with Co3+ species. While these transformations manifest heterogeneously through the bulk of the particles, the electrochemical current is primarily restricted to the particle edge facets. The observed Tafel behavior is correlated to the local concentration of Co3+ at these reactive edge sites, demonstrating the link between bulk ion-insertion and surface catalytic activity.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYelectrocatalysisenergymicroscopy

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Mefford, J. Tyler, Akbashev, Andrew R. (ORCID:0000000315731773), Kang, Minkyung (ORCID:0000000332488496), Bentley, Cameron L. (ORCID:0000000178676068), Gent, William E. (ORCID:0000000176633988), Deng, Haitao D., Alsem, Daan Hein, Yu, Young-Sang (ORCID:0000000205459019), Salmon, Norman J., Shapiro, David A. (ORCID:0000000241866017), Unwin, Patrick R. (ORCID:0000000331062178), Chueh, William C. (ORCID:0000000270663470). 2021-05-05. Correlative operando microscopy of oxygen evolution electrocatalysts. https://doi.org/10.1038/s41586-021-03454-x

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