A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111) (2023)

Kumeda, T., Laverdure, L., Honkala, K., Melander, M. M., & Sakaushi, K. (2023). Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111). Angewandte Chemie, 62(51), Article e202312841. https://doi.org/10.1002/anie.202312841

JYU-tekijät tai -toimittajat

Laverdure, Laura
Honkala, Karoliina
Melander, Marko

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Kumeda, Tomoaki; Laverdure, Laura; Honkala, Karoliina; Melander, Marko M.; Sakaushi, Ken

Lehti tai sarja: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Julkaisuvuosi: 2023

Ilmestymispäivä: 20.11.2023

Volyymi: 62

Lehden numero: 51

Artikkelinumero: e202312841

Kustantaja: Wiley-VCH Verlag

Julkaisumaa: Saksa

Julkaisun kieli: englanti

DOI: https://doi.org/10.1002/anie.202312841

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/92133

Rinnakkaistallenteen verkko-osoite (pre-print): https://arxiv.org/abs/2205.00719

Tiivistelmä

The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt−O and Pt−OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt−O to Pt−OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

YSO-asiasanat: hapetus-pelkistysreaktio; pelkistys; elektrokatalyysi; platina; pintakemia; sähkökemia

Vapaat asiasanat: constrained DFT; electrocatalysis; energy conversion; kinetic isotope effects; Marcus theory

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