Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water

Velasco Vélez, Juan Jesús; Bernsmeier, Denis; Mom, Rik V.; Zeller, Patrick; Shao‐Horn, Yang; Cuenya, Beatriz Roldan; Knop‐Gericke, Axel; Schlögl, Robert; Jones, Travis E.

doi:10.1002/aenm.202303407

Title: Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water

Journal Article · 11 March 2024 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202303407 · OSTI ID:2340916

^[1]; Bernsmeier, Denis ^[2];

^[3]; Zeller, Patrick ^[4];

^[5];

^[6]; Knop‐Gericke, Axel ^[7]; Schlögl, Robert ^[7];

^[8]

Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); Fritz Haber Institute of the Max Planck Society, Berlin (Germany); ALBA Synchrotron Light Source, Cerdanyola del Valles (Spain)
Technical Univ. of Berlin (Germany)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany); Leiden Univ. (Netherlands)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany); Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

A special membrane electrode assembly to measure operando X-ray absorption spectra and resonant photoemission spectra of mesoporous templated iridium oxide films is used. These films are calcined to different temperatures to mediate the catalyst activity. By combining operando resonant photoemission measurements of different films with ab initio simulations these are able to unambiguously distinguish µ₂-O (bridging oxygen) and µ₁-O (terminal oxygen) in the near-surface regions of the catalysts. The intrinsic activity of iridium oxide scales with the formation of µ1-O (terminal oxygen) is found. Importantly, it is shown that the peroxo species do not accumulate under reaction conditions. Rather, the formation of µ₁-O species, which are active in O-O bond formation during the OER, is the most oxidized oxygen species observed, which is consistent with an O-O rate-limiting step. Thus, the oxygen species taking part in the electrochemical oxidation of water on iridium electrodes are more involved and complex than previously stated. This result highlights the importance of employing theory together with true and complementary operando measurements capable of probing different aspects of catalysts surfaces during operation.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2340916

Report Number(s):: LA-UR--24-20648

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 19 Vol. 14; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Inorganic and Physical Chemistry
density functional theory
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operando X-ray photoelectron spectroscopy
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Title: Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water

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