<p>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.</p>

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Operando ultraviolet–visible optical spectroelectrochemistry of surfaces

  • Benjamin Moss,
  • Caiwu Liang,
  • Andrew Carpenter,
  • Lucas G. Verga,
  • Soren Scott,
  • Ryan J. R. Jones,
  • Karthish Manthiram,
  • Aron Walsh,
  • Reshma R. Rao,
  • Ifan E. L. Stephens,
  • James R. Durrant

摘要

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.