Effect of cations on the electro-oxidation of alcohols and polyols on Pt: Activity, selectivity, and mechanistic insights

Author(s)

Yukuhiro, Victor Y. ; Gibson, Alan J. ; Sitta, Elton ; Cuesta, Angel ; Fernandez, Pablo S.

• Document type: Journal article
• Source: CURRENT OPINION IN ELECTROCHEMISTRY; v. 52, p. 8-pg., 2025-08-01.

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 the EOAP. Larger cations, such as K+, enhance reaction rates and facilitate C-C bond 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 hypotheses proposed 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. (AU)

• FAPESP's process: 20/04431-0 - Perovskite oxides for the continuous and/or simultaneous production of energy and/or dense energy carriers
• Grantee: Pablo Sebastián Fernández
• Support Opportunities: Program for Research on Bioenergy (BIOEN) - Regular Program Grants
• FAPESP's process: 23/02929-9 - Boosting green hydrogen production by the electrooxidation of glycerol. Minimizing the use of Platinum Group Metals elements
• Grantee: Pablo Sebastián Fernández
• Support Opportunities: Regular Research Grants
• FAPESP's process: 13/07296-2 - CDMF - Center for the Development of Functional Materials
• Grantee: Elson Longo da Silva
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 17/11986-5 - Generation and storage of New Energy: bringing technological development for the country
• Grantee: Ana Flávia Nogueira
• Support Opportunities: Research Grants - Research Centers in Engineering Program