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Operando ultraviolet–visible optical spectroelectrochemistry of surfaces

Nature Reviews Methods Primers volume 5, Article number: 73 (2025) Cite this article

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Abstract

Ultraviolet–visible spectroelectrochemistry (SEC) is a powerful and accessible operando technique for investigating redox-active interfaces such as electrodes. Its potential has not been fully realized owing to limitations in sensitivity, acquisition speed and analysis workflows. In this Primer, we describe how recent developments in optics, detection hardware and synchronization methods now allow for high-resolution, data-rich SEC measurements. We focus on practical strategies for building performant SEC set-ups, introduce a formalism based on differential coulometric attenuation for interpreting spectral changes and outline workflows for extracting redox stoichiometries, kinetics and coverage from complex data. Emphasizing process-sensitive over population-sensitive analysis, we show how this approach enables a clearer understanding of dynamic, disordered interfacial systems. Examples are provided from electrocatalysis, particularly the oxygen evolution reaction, but the principles described are broadly applicable. Throughout, we highlight pitfalls, assumptions and design choices to guide researchers looking to implement quantitative SEC in their own work.

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Fig. 1: A simplified example of overlapping processes that may occur at an interface.
Fig. 2: Typical spectroelectrochemistry experiments and example data.
Fig. 3: Example analysis of synthetic cyclic voltammetry-spectroelectrochemistry data.
Fig. 4: Example analysis of synthetic square-wave voltammetry-spectroelectrochemistry data.
Fig. 5: Example analysis of synthetic potential decay-spectroelectrochemistry data.
Fig. 6: Extraction of the binding and interaction energy from the rate-limiting intermediate for oxygen evolution reaction in iridium oxide.
Fig. 7: Tafel slope reconstruction using optical data in cobalt oxyhydroxide (CoOOH) oxygen evolution reaction catalysts.
Fig. 8: Active state quantification and analysis of charging/discharging kinetics in iron-incorporated nickel oxyhydroxide (NiFOOH) oxygen evolution reaction catalysts.
Fig. 9: Measurement of the spectra of charged ions of materials used in photovoltaics and organic electrochemical transistors.

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Acknowledgements

B.M. acknowledges the Lindemann Trust and Schmidt Sciences for funding. He is also indebted to K. K. Lim and X. Li for thoughtful discussion that clarified many points on this work. J.R.D. and I.E.L.S. acknowledge the BP International Centre for Advanced Materials (bp-ICAM) as well as the EPSRC grant EP/W033232/1, which made this research possible. This project was supported by the Royal Academy of Engineering under the Research Fellowship programme (R.R.R.). C.L. acknowledges the Imperial College London and China Scholarship Council for the IC–CSC joint scholarship.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

    Benjamin Moss, Ryan J. R. Jones & Karthish Manthiram

  2. Department of Materials, Imperial College London, London, UK

    Caiwu Liang, Lucas G. Verga, Aron Walsh, Reshma R. Rao & Ifan E. L. Stephens

  3. Andor Technology, Concord, MA, USA

    Andrew Carpenter

  4. University of Copenhagen, Copenhagen, Denmark

    Soren Scott

  5. Grantham Institute — Climate Change and the Environment, Imperial College London, London, UK

    Reshma R. Rao

  6. Department of Chemistry, Imperial College London, London, UK

    James R. Durrant

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Contributions

Introduction: B.M., C.L., L.G.V., S.S., R.R.R., I.E.L.S. and J.R.D.; Experimentation: B.M., C.L., A.C., L.G.V., S.S., K.M., R.R.R., I.E.L.S. and J.R.D.; Results: B.M., C.L., A.C., S.S., K.M., A.W., R.R.R., I.E.L.S., J.R.D. and R.J.R.J.; Applications: B.M., C.L., A.C., S.S., K.M., R.R.R., I.E.L.S. and J.R.D.; Reproducibility and data deposition: B.M., C.L., S.S., R.R.R., I.E.L.S. and J.R.D.; Limitations and optimizations: B.M., C.L., A.C., L.G.V., S.S., K.M., A.W., R.R.R., I.E.L.S. and J.R.D.; Outlook: B.M., C.L., A.C., L.G.V., S.S., R.R.R., I.E.L.S. and J.R.D.

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Correspondence to Benjamin Moss.

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Competing interests

A.C. is an employee of Oxford Instruments Andor (OIA) and contributed his perspective to discussions of the detector technologies with respect to the SEC spectroscopic methodology. No financial or commercial support has been provided by OIA. All other authors declare no competing interests.

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Nature Reviews Methods Primers thanks Evgenia Dmitrieva, Marcel Risch and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Moss, B., Liang, C., Carpenter, A. et al. Operando ultraviolet–visible optical spectroelectrochemistry of surfaces. Nat Rev Methods Primers 5, 73 (2025). https://doi.org/10.1038/s43586-025-00445-4

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