Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates

Abstract This study employs Rapid Scan Cyclic Voltammetry (RSCV) with a gold ultramicroelectrode (Au UME) to investigate transient species in the oxygen reduction reaction (ORR) under alkaline conditions. Gold was purposefully chosen as the electrode material due to its ability to generate peroxide...

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Main Authors: Sharon Benny Alex, Linsha Vazhayal, Santosh K. Haram
Format: Article
Language:English
Published: Springer 2025-05-01
Series:Discover Electrochemistry
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Online Access:https://doi.org/10.1007/s44373-025-00034-w
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author Sharon Benny Alex
Linsha Vazhayal
Santosh K. Haram
author_facet Sharon Benny Alex
Linsha Vazhayal
Santosh K. Haram
author_sort Sharon Benny Alex
collection DOAJ
description Abstract This study employs Rapid Scan Cyclic Voltammetry (RSCV) with a gold ultramicroelectrode (Au UME) to investigate transient species in the oxygen reduction reaction (ORR) under alkaline conditions. Gold was purposefully chosen as the electrode material due to its ability to generate peroxide radicals via a two-electron transfer mechanism. RSCV on Au UME shows cathodic peaks, C1 and C2, linked to the sequential reduction of oxygen to peroxide anion and then to hydroxyl anion, and along with an anodic peak, A1, corresponding to peroxide anion oxidation back to oxygen. Quantitative analysis of these peaks, performed by integrating the peak areas, enabled rate determination for the formation of transient species. Thermodynamic and kinetic analyses further show a preference for decomposition over reduction, attributed to lower activation energy requirements. These findings demonstrate RSCV-UME’s effectiveness for real-time ORR intermediate detection and highlight how scan rate adjustments can alter reaction pathways, offering a powerful approach for exploring electrochemical mechanisms relevant to electrocatalysis and energy conversion technologies.
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spelling doaj-art-a465ee7f3a66421abf5f2c3e9e2d0e462025-08-20T03:16:34ZengSpringerDiscover Electrochemistry3005-12152025-05-01211810.1007/s44373-025-00034-wRapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediatesSharon Benny Alex0Linsha Vazhayal1Santosh K. Haram2Department of Chemistry, Savitribai Phule Pune UniversityDepartment of Chemistry, Savitribai Phule Pune UniversityDepartment of Chemistry, Savitribai Phule Pune UniversityAbstract This study employs Rapid Scan Cyclic Voltammetry (RSCV) with a gold ultramicroelectrode (Au UME) to investigate transient species in the oxygen reduction reaction (ORR) under alkaline conditions. Gold was purposefully chosen as the electrode material due to its ability to generate peroxide radicals via a two-electron transfer mechanism. RSCV on Au UME shows cathodic peaks, C1 and C2, linked to the sequential reduction of oxygen to peroxide anion and then to hydroxyl anion, and along with an anodic peak, A1, corresponding to peroxide anion oxidation back to oxygen. Quantitative analysis of these peaks, performed by integrating the peak areas, enabled rate determination for the formation of transient species. Thermodynamic and kinetic analyses further show a preference for decomposition over reduction, attributed to lower activation energy requirements. These findings demonstrate RSCV-UME’s effectiveness for real-time ORR intermediate detection and highlight how scan rate adjustments can alter reaction pathways, offering a powerful approach for exploring electrochemical mechanisms relevant to electrocatalysis and energy conversion technologies.https://doi.org/10.1007/s44373-025-00034-wOxygen reduction reactionUltramicroelectrodeRapid scan cyclic voltammetryHydrogen peroxide
spellingShingle Sharon Benny Alex
Linsha Vazhayal
Santosh K. Haram
Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
Discover Electrochemistry
Oxygen reduction reaction
Ultramicroelectrode
Rapid scan cyclic voltammetry
Hydrogen peroxide
title Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
title_full Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
title_fullStr Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
title_full_unstemmed Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
title_short Rapid Scan Cyclic Voltammetry (RSCV) investigation of oxygen reduction reaction (ORR) on gold ultramicroelectrode (UME): a novel methodology to study kinetics of formation of transient intermediates
title_sort rapid scan cyclic voltammetry rscv investigation of oxygen reduction reaction orr on gold ultramicroelectrode ume a novel methodology to study kinetics of formation of transient intermediates
topic Oxygen reduction reaction
Ultramicroelectrode
Rapid scan cyclic voltammetry
Hydrogen peroxide
url https://doi.org/10.1007/s44373-025-00034-w
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