4.8 Article

A Dissolution/Precipitation Equilibrium on the Surface of Iridium-Based Perovskites Controls Their Activity as Oxygen Evolution Reaction Catalysts in Acidic Media

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 14, Pages 4571-4575

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201814075

Keywords

iridium dissolution; oxygen evolution reaction; perovskites; Pourbaix diagrams

Funding

  1. ANR MIDWAY [ANR-17-CE05-0008]
  2. Diamond Light Source [SP14239]
  3. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06C1111357]
  4. Paris Ile-de-France Region (RESPORE)

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Recently, Ir-V-based perovskite-like materials were proposed as oxygen evolution reaction (OER) catalysts in acidic media with promising performance. However, iridium dissolution and surface reconstruction were observed, questioning the real active sites on the surface of these catalysts. In this work, (Sr2MIrO6)-O-(V) (M = Fe, Co) and (Sr2Fe0.5Ir0.5O4)-O-(V) were explored as OER catalysts in acidic media. Their activities were observed to be roughly equal to those previously reported for La2LiIrO6 or Ba2PrIrO6. Coupling electrochemical measurements with iridium dissolution studies under chemical or electrochemical conditions, we show that the deposition of an IrOx layer on the surface of these perovskites is responsible for their OER activity. Furthermore, we experimentally reconstruct the iridium Pourbaix diagram, which will help guide future research in controlling the dissolution/precipitation equilibrium of iridium species for the design of better Ir-based OER catalysts.

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