Journal Article PUBDB-2025-01316

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Reactivity and Stability of Reduced Ir-Weight TiO$_2$ -Supported Oxygen Evolution Catalysts for Proton Exchange Membrane (PEM) Water Electrolyzer Anodes

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2024
ACS Publications Washington, DC

Journal of the American Chemical Society 146(46), 31444 - 31455 () [10.1021/jacs.4c07002]
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Abstract: Reducing the iridium demand in Proton Exchange Membrane Water Electrolyzers (PEM WE) is a critical priority for the green hydrogen industry. This study reports the discovery of a TiO$_2$-supported Ir@IrO(OH)$_x$ core–shell nanoparticle catalyst with reduced Ir content, which exhibits superior catalytic performance for the electrochemical oxygen evolution reaction (OER) compared to a commercial reference. The TiO$_2$-supported Ir@IrO(OH)$_x$ core–shell nanoparticle configuration significantly enhances the OER Ir mass activity from 8 to approximately 150 A g$_{Ir}$$^{–1}$ at 1.53 V$_{RHE}$ while reducing the iridium packing density from 1.6 to below 0.77 g$_{Ir}$ cm$^{–3}$. These advancements allow for viable anode layer thicknesses with lower Ir loading, reducing iridium utilization at 70% LHV from 0.42 to 0.075 g$_{Ir}$ kW$^{–1}$ compared to commercial IrO$_2$/TiO$_2$. The identification of the Ir@IrO(OH)$_x$/TiO$_2$ OER catalyst resulted from extensive HAADF-EDX microscopic analysis, operando XAS, and online ICP-MS analysis of 30–80 wt % Ir/TiO$_2$ materials. These analyses established correlations among Ir weight loading, electrode electrical conductivity, electrochemical stability, and Ir mass-based OER activity. The activated Ir@IrO(OH)$_x$/TiO$_2$ catalyst–support system demonstrated an exceptionally stable morphology of supported core–shell particles, suggesting strong catalyst–support interactions (CSIs) between nanoparticles and crystalline oxide facets. Operando XAS analysis revealed the reversible evolution of significantly contracted Ir–O bond motifs with enhanced covalent character, conducive to the formation of catalytically active electrophilic O$^{I–}$ ligand species. These findings indicate that atomic Ir surface dissolution generates Ir lattice vacancies, facilitating the emergence of electrophilic O$^{I–}$ species under OER conditions, while CSIs promote the reversible contraction of Ir–O distances, reforming electrophilic O$^{I–}$ and enhancing both catalytic activity and stability.

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Note: We acknowledge kind financial support by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Projects GZ: INST 131/789-1 FUGG, STR 596/21-1 (DaCapo), STR 596/11-1 (Iridium) and CH 1763/4-1; and by the German Ministry for Education and Research (BMBF) through consortium project “HyThroughGen” FKZ: 03HY108D within the technology platform H2GIGA.

Contributing Institute(s):
  1. FS DOOR-User (FS DOOR-User)
Research Program(s):
  1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
  2. SWEDEN-DESY - SWEDEN-DESY Collaboration (2020_Join2-SWEDEN-DESY) (2020_Join2-SWEDEN-DESY)
Experiment(s):
  1. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2024
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 Record created 2025-04-09, last modified 2025-06-25


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