4.6 Article

Carbonate formation lowers the electrocatalytic activity of perovskite oxides for water electrolysis

Journal

JOURNAL OF MATERIALS CHEMISTRY A
Volume 9, Issue 35, Pages 19940-19948

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta03205d

Keywords

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Funding

  1. European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant [796142]
  2. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering [DE-AC02-76SF00515]
  3. National Science Foundation [ECCS-1542152]
  4. Advanced Light Source, a U.S. DOE Office of Science User Facility [DE-AC02-05CH11231]
  5. Marie Curie Actions (MSCA) [796142] Funding Source: Marie Curie Actions (MSCA)

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The study demonstrates that exposure to air can alter the chemical environment of oxide electrocatalysts, affecting their activity. It is necessary to consider the effects of air exposure on transition metal oxide catalysts.
The study of oxide electrocatalysts is often complicated by the formation of complex and unknown surface species as well as the interaction between the catalysts and common support materials. Because unknown surface species may result from air exposure, we developed a clean transfer system for the air-free electrochemical investigation of epitaxial thin films fabricated under typical surface science conditions. LaNiO3 electrocatalysts exposed to ambient air exhibit a lower activity towards the oxygen evolution reaction than samples probed without air exposure. We demonstrate that this decrease in activity is connected to an alteration of the chemical environment of the electrocatalytically active sites through carbonate formation on exposure to CO2. Our study therefore shows that (1) the effects of air exposure must be considered for transition metal oxide catalysts and (2) that for the perovskite oxide LaNiO3 the clean surface is more active than the air-exposed surface.

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