Mapping Localized Peroxyl Radical Generation on a PEM Fuel Cell Catalyst Using Integrated Scanning Electrochemical Cell Microspectroscopy

Edgecomb, Joseph; Xie, Xiaohong; Shao, Yuyan; El‐Khoury, Patrick Z.; Johnson, Grant E.; Prabhakaran, Venkateshkumar

doi:10.3389/fchem.2020.572563

Cited by 11 publications

(6 citation statements)

References 53 publications

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“…There have already been significant developments in other fields of electrocatalysis, which confirm the advantages and feasibility of hybrid methods. For example, fluorescence spectroscopy has been used to detect reactive oxygen species in the SECCM meniscus during the oxygen reduction reaction, 67 and Raman spectroscopy has been combined with scanning electrochemical microscopy to study the impacts of structural heterogeneities, interfacial decomposition products, and layer number on the electron-transfer properties of graphene. 68 Since the lifetimes of some intermediate species are extremely short, these species are unlikely to be detected even by the most sensitive techniques available.…”

Section: Discussionmentioning

confidence: 99%

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂

et al. 2022

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Conspectus Electrochemical reduction of the greenhouse gas CO2 offers prospects for the sustainable generation of fuels and industrially useful chemicals when powered by renewable electricity. However, this electrochemical process requires the use of highly stable, selective, and active catalysts. The development of such catalysts should be based on a detailed kinetic and mechanistic understanding of the electrochemical CO2 reduction reaction (eCO2RR), ideally through the resolution of active catalytic sites in both time (i.e., temporally) and space (i.e., spatially). In this Account, we highlight two advanced spatiotemporal voltammetric techniques for electrocatalytic studies and describe the considerable insights they provide on the eCO2RR. First, Fourier transformed large-amplitude alternating current voltammetry (FT ac voltammetry), as applied by the Monash Electrochemistry Group, enables the resolution of rapid underlying electron-transfer processes in complex reactions, free from competing processes, such as the background double-layer charging current, slow catalytic reactions, and solvent/electrolyte electrolysis, which often mask conventional voltammetric measurements of the eCO2RR. Crucially, FT ac voltammetry allows details of the catalytically active sites or the rate-determining step to be revealed under catalytic turnover conditions. This is well illustrated in investigations of the eCO2RR catalyzed by Bi where formate is the main product. Second, developments in scanning electrochemical cell microscopy (SECCM) by the Warwick Electrochemistry and Interfaces Group provide powerful methods for obtaining high-resolution activity maps and potentiodynamic movies of the heterogeneous surface of a catalyst. For example, by coupling SECCM data with colocated microscopy from electron backscatter diffraction (EBSD) or atomic force microscopy, it is possible to develop compelling correlations of (precatalyst) structure–activity at the nanoscale level. This correlative electrochemical multimicroscopy strategy allows the catalytically more active region of a catalyst, such as the edge plane of two-dimensional materials and the grain boundaries between facets in a polycrystalline metal, to be highlighted. The attributes of SECCM-EBSD are well-illustrated by detailed studies of the eCO2RR on polycrystalline gold, where carbon monoxide is the main product. Comparing SECCM maps and movies with EBSD images of the same region reveals unambiguously that the eCO2RR is enhanced at surface-terminating dislocations, which accumulate at grain boundaries and slip bands. Both FT ac voltammetry and SECCM techniques greatly enhance our understanding of the eCO2RR, significantly boosting the electrochemical toolbox and the information available for the development and testing of theoretical models and rational catalyst design. In the future, it may be possible to further enhance insights provided by both techniques through their integration with in situ and in operando spectroscopy and microscopy methods.

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Section: Discussionmentioning

confidence: 99%

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂

et al. 2022

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“…316 Another interesting development is the use of fluorophores within the tip to identify reactive oxygen species, produced in the tip, during the oxygen reduction reaction. 317 This is a platform that could readily be expanded to other species and methods of detection. Battery Electrode Materials.…”

Section: Analyticalmentioning

confidence: 99%

“…Quad-barrel SECCM tips are available, which contain up to 2 solid electrodes that can be used to detect the products (and, in principle, intermediates) of local surface processes within the SECCM meniscus . Another interesting development is the use of fluorophores within the tip to identify reactive oxygen species, produced in the tip, during the oxygen reduction reaction . This is a platform that could readily be expanded to other species and methods of detection.…”

Section: High-throughput Scanning Electrochemical Cell Microscopymentioning

confidence: 99%

The New Era of High-Throughput Nanoelectrochemistry

Valavanis

Ciocci

et al. 2023

Anal. Chem.

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“…317 Another interesting development is the use of fluorophores within the tip to identify reactive oxygen species, produced in the tip, during the oxygen reduction reaction. 318 This is a platform that could readily be expanded to other species and methods of detection.…”

Section: Electrocatalysis: Single Particles and Pseudo-single Crystal...mentioning

confidence: 99%

The new era of high throughput nanoelectrochemistry

Valavanis

Ciocci

et al. 2022

Preprint

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Scanning electrochemical probe microscopies (SEPMs) have played a key role in advancing small-scale electrochemistry. SEPMs use an electrochemical probe (micro/nanoelectrode or pipet) to quantify and map local interfacial fluxes of electroactive species and have found increasingly wide applications. Our contribution to the Fundamental and Applied Reviews in Analytical Chemistry 2019 discussed how advances in SEPMs converged towards nanoscale electrochemical mapping. This inflection in experimental capability has opened up myriad opportunities for SEPMs in many types of systems, from material and energy sciences to the life sciences. The enhancement in the spatial resolution of imaging techniques, and instrumental developments, have resulted in significant increases in the size of electrochemical datasets from a typical experiment and served to speed up measurement throughput. Next generation nanoelectrochemistry will thus see an emphasis on “big data”, its analysis, storage and curation, high throughput analysis and parallelization, “intelligent” instruments and experiments, active control of nanoscale systems, and the integration of nanoelectrochemistry and nanoscale micro(spectro)scopy. For this review article, we focus on recent advances in frontier nanoscale electrochemistry, analysis and imaging techniques that are already addressing some of these key targets, and are well-placed to embrace other aspects in the near future. Our goal is to provide an overview of the present state-of-the-art in high throughput nanoelectrochemistry and imaging, and signpost promising new avenues for nanoscale electrochemical methods.

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Mapping Localized Peroxyl Radical Generation on a PEM Fuel Cell Catalyst Using Integrated Scanning Electrochemical Cell Microspectroscopy

Cited by 11 publications

References 53 publications

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂

The New Era of High-Throughput Nanoelectrochemistry

The new era of high throughput nanoelectrochemistry

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Mapping Localized Peroxyl Radical Generation on a PEM Fuel Cell Catalyst Using Integrated Scanning Electrochemical Cell Microspectroscopy

Cited by 11 publications

References 53 publications

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO2

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO2

The New Era of High-Throughput Nanoelectrochemistry

The new era of high throughput nanoelectrochemistry

Contact Info

Product

Resources

About

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO₂