Effect of Cations on the Electrooxidation of Alcohols and Polyols on Pt: Activity, Selectivity, and Mechanistic Insights

Victor Yukuhiro; Alan James Gibson; Elton  Sitta; Angel Cuesta Ciscar; Pablo S.  Fernández

doi:10.1016/j.coelec.2025.101705

Effect of Cations on the Electrooxidation of Alcohols and Polyols on Pt: Activity, Selectivity, and Mechanistic Insights

Victor Yukuhiro, Alan James Gibson, Elton Sitta, Angel Cuesta Ciscar, Pablo S. Fernández^* (Corresponding Author)

^*Corresponding author for this work

Universidade Estadual de Campinas

Research output: Contribution to journal › Article › peer-review

Abstract

Understanding the role of cations in the electro-oxidation of alcohols and polyols (EOAP) on Pt electrodes is essential for optimizing electrocatalytic processes in energy conversion and chemical production. This review explores how cations modulate activity, selectivity, and dynamic behavior during EOAP. Larger cations, such as K+, enhance reaction rates and facilitate C–C cleavage, whereas smaller cations like Li+ promote COad oxidation and the formation of inactive Pt oxides. The interplay between cations, adsorbed intermediates, and the electrode surface is analysed using complementary electrochemical and in situ spectroscopic techniques, covering proposed hypotheses to explain these observations. Despite progress, fundamental questions remain regarding the microscopic origins of cation effects, including the relative stabilities of key intermediates, how these stabilities influence their formation and oxidation, and ultimately how they govern the deactivation of Pt surfaces via the formation of inactive Pt oxides

Original language	English
Article number	101705
Journal	Current Opinion in Electrochemistry
Early online date	7 May 2025
DOIs	https://doi.org/10.1016/j.coelec.2025.101705
Publication status	E-pub ahead of print - 7 May 2025

Data Availability Statement

No data was used for the research described in the article.

Funding

VYY, ES, and PSF. acknowledge Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) [grant numbers: 2020/04431-0, 2023/02929-9, 2013/07296-2, and 2017/11986-5] and the support of Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas, and Biofuels Agency) through the R&D levy regulation. VYY and ES acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) [grant numbers: 141281/2023-5 and 310550/2022-0]. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001. AJG gratefully acknowledges the support of the Carnegie Trust for the Universities of Scotland through a PhD scholarship. AC acknowledges the continued support of the University of Aberdeen.

Funders	Funder number
Carnegie Trust for the Universities of Scotland

Keywords

Platinum
Cation effects
Alkaline and acidic media
Alcohols
Polyols
electrocatalysis

Access to Document

10.1016/j.coelec.2025.101705

Yukuhiro_etal_COiEC_Effect_of_Cations_AAM
This manuscript has been made open access under a Creative Commons Attribution (CC BY) licence under the terms of the University of Aberdeen Research Publications Policy. https://creativecommons.org/licenses/by/4.0/
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Cite this

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title = "Effect of Cations on the Electrooxidation of Alcohols and Polyols on Pt: Activity, Selectivity, and Mechanistic Insights",

abstract = "Understanding the role of cations in the electro-oxidation of alcohols and polyols (EOAP) on Pt electrodes is essential for optimizing electrocatalytic processes in energy conversion and chemical production. This review explores how cations modulate activity, selectivity, and dynamic behavior during EOAP. Larger cations, such as K+, enhance reaction rates and facilitate C–C cleavage, whereas smaller cations like Li+ promote COad oxidation and the formation of inactive Pt oxides. The interplay between cations, adsorbed intermediates, and the electrode surface is analysed using complementary electrochemical and in situ spectroscopic techniques, covering proposed hypotheses to explain these observations. Despite progress, fundamental questions remain regarding the microscopic origins of cation effects, including the relative stabilities of key intermediates, how these stabilities influence their formation and oxidation, and ultimately how they govern the deactivation of Pt surfaces via the formation of inactive Pt oxides",

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AU - Yukuhiro, Victor

AU - Gibson, Alan James

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AU - Cuesta Ciscar, Angel

AU - Fernández, Pablo S.

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AB - Understanding the role of cations in the electro-oxidation of alcohols and polyols (EOAP) on Pt electrodes is essential for optimizing electrocatalytic processes in energy conversion and chemical production. This review explores how cations modulate activity, selectivity, and dynamic behavior during EOAP. Larger cations, such as K+, enhance reaction rates and facilitate C–C cleavage, whereas smaller cations like Li+ promote COad oxidation and the formation of inactive Pt oxides. The interplay between cations, adsorbed intermediates, and the electrode surface is analysed using complementary electrochemical and in situ spectroscopic techniques, covering proposed hypotheses to explain these observations. Despite progress, fundamental questions remain regarding the microscopic origins of cation effects, including the relative stabilities of key intermediates, how these stabilities influence their formation and oxidation, and ultimately how they govern the deactivation of Pt surfaces via the formation of inactive Pt oxides

KW - Platinum

KW - Cation effects

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