4.8 Article

Delivering the Full Potential of Oxygen Evolving Electrocatalyst by Conditioning Electrolytes at Near-Neutral pH

Journal

CHEMSUSCHEM
Volume 14, Issue 6, Pages 1554-1564

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.202002813

Keywords

electrocatalysis; iridium oxide; near-neutral pH; oxygen evolution reaction; reaction mechanism

Funding

  1. JSPS KAKENHI [19K23569]
  2. UTokyo-KAUST collaborative research OSR [4191]
  3. Grants-in-Aid for Scientific Research [19K23569] Funding Source: KAKEN

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This study explores the impact of buffer ions on OER performance using a model IrOx electrocatalyst, finding that the OER kinetics is more efficient with OH- oxidation compared to H2O. The research highlights how the presence of a buffer can significantly reduce overpotential and improve performance by facilitating local OH- supply kinetics.
This study reports on the impact of identity and compositions of buffer ions on oxygen evolution reaction (OER) performance at a wide range of pH levels using a model IrOx electrocatalyst. Rigorous microkinetic analysis employing kinetic isotope effects, Tafel analysis, and temperature dependence measurement was conducted to establish rate expression isolated from the diffusion contribution of buffer ions and solution resistance. It was found that the OER kinetics was facile with OH- oxidation compared to H2O, the results of which were highlighted by mitigating over 200 mV overpotential in the presence of buffer to reach 10 mA cm(-2). This improvement was ascribed to the involvement of the kinetics of the local OH- supply by the buffering action. Further digesting the kinetic data at various buffer pK(a) and the solution bulk pH disclosed a trade-off between the exchange current density and the Tafel slope, indicating that the optimal electrolyte condition can be chosen at a different range of current density. This study provides a quantitative guideline for electrolyte engineering to maximize the intrinsic OER performance that electrocatalyst possesses especially at near-neutral pH.

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