Journal Article FZJ-2021-00433

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Oxygen reduction reaction kinetics on Pt in mixtures of proton conducting ionic liquids (PILs) and water: The influence of cation acidity

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2021
Soc. Washington, DC

The journal of physical chemistry <Washington, DC> / C 125(8), 4423 - 4435 () [10.1021/acs.jpcc.0c11374]

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Abstract: The aim of this study is to investigate the effect of the acidity of proton-conducting ionic liquids (PILs) on the oxygen reduction reaction (ORR) kinetics at polycrystalline platinum electrodes. Three PILs ([2-SEMA][TfO], [1-EIm][TfO], and [DEMA][TfO]) with different cation acidities (aqueous pKa = 0.94, 7.30 and 10.55) are investigated. The ORR kinetics are evaluated by simulating cyclic voltammograms recorded under an oxygen atmosphere. An associative mechanism, including H3O+ as the dominant proton donor, is used for the simulations. The dependencies of the rate constants k1 and the charge transfer coefficients α1 of the r.d.s. (O2 + e– → O2–) on the cation acidity, the water content (≈3–50 mol %), and the temperature (30–90 °C) are analyzed. The rate constant k1, the pre-exponential factor of k1, and the current density are observed to increase with the acidity of the PIL cation, whereas α1 shows the opposite behavior. At low water concentrations, the [2-SEMA+] cation is a remarkably good proton donor in ORR, contrary to the former results obtained from the HUPD reaction. This leads to a minimum of ≈30 mol % in the plots of the current density and k1 vs the water content, which correlates with a similar dependency of the pseudo capacitance C2.

Classification:

Contributing Institute(s):
  1. Elektrochemische Verfahrenstechnik (IEK-14)
Research Program(s):
  1. 1231 - Electrochemistry for Hydrogen (POF4-123) (POF4-123)

Appears in the scientific report 2021
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Medline ; Embargoed OpenAccess ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF < 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection
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 Record created 2021-01-19, last modified 2024-07-12


Published on 2021-02-18. Available in OpenAccess from 2022-02-18.:
Influence of PIL acidity on the ORR kinetics Revised Manuscript - Download fulltext PDF
Influence of PIL Acidity Supporting Information Revised - Download fulltext PDF
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