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Spectroelectrochemistry Applications Book

Guides | 2022 | MetrohmInstrumentation
RAMAN Spectroscopy, NIR Spectroscopy, UV–VIS spectrophotometry, Electrochemistry
Industries
Energy & Chemicals , Materials Testing
Manufacturer
Metrohm

Summary

Importance of Spectroelectrochemistry


Spectroelectrochemistry integrates electrochemical control with optical monitoring to deliver simultaneous electrical and spectroscopic data. This dual-signal capability enhances understanding of redox processes at electrode interfaces and enables detailed mechanistic, kinetic and thermodynamic analysis in a single experiment.

Objectives and Study Overview


This review surveys key applications of spectroelectrochemistry across different spectral regions (UV-Vis, NIR, Raman). It highlights instrumental advancements—particularly the SPELEC platform—that have democratized the technique, and it summarizes emerging trends in materials science, life sciences, energy conversion and environmental analysis.

Methodology and Instrumentation


Spectroelectrochemical setups couple a potentiostat/galvanostat with a spectrometer and light source. Three configurations prevail:
  • Normal (perpendicular light beam; reflection or transmission).
  • Parallel (light beam skims the electrode surface).
  • Bidimensional (simultaneous perpendicular and parallel beams).
UV-Vis (200–800 nm), NIR (800–2500 nm) and Raman (532, 638, 785 nm lasers) variants exploit different optical transitions—from electronic excitations to vibrational overtones and resonance‐enhanced scattering. Precise synchronization between optical acquisition and potential control is critical.

Main Results and Discussion


UV-Vis spectroelectrochemistry elucidates reaction pathways, quantifies intermediates and measures optical/electrochemical parameters. Applications span fundamental redox chemistry, biomedicine (DNA hybridization, neurotransmitter detection), electrocatalysis (water oxidation, hydrogen evolution), material science (nanoparticle band‐edge analysis, polymer doping) and environmental monitoring.

NIR spectroelectrochemistry, less hindered by water absorption when using organic solvents or ionic liquids, excels in studying electrochromic materials, quantum dots and conducting polymers, as well as resolving electronic transitions in coordination complexes and dyes.

Raman spectroelectrochemistry offers molecular fingerprinting of structural changes under potential control. Surface‐enhanced Raman scattering (SERS) boosts sensitivity for trace‐level sensing, mechanistic investigations in electrocatalysis (formic acid oxidation, CO₂ reduction), energy devices (battery electrodes) and corrosion studies.

Benefits and Practical Applications


  • In situ mechanism elucidation through correlated optical/electrochemical signals.
  • Quantitative determination of diffusion coefficients, standard potentials and absorptivity.
  • High‐sensitivity detection via SERS for environmental, pharmaceutical and biomedical analytes.
  • Characterization of nanomaterials, conducting polymers and energy storage materials.
  • Real‐time monitoring of electrochromic switching and corrosion inhibitors.

Instrumental Setup


The SPELEC family integrates potentiostat, light source and spectrometer into a compact, user-friendly system. Available in UV-Vis, NIR and Raman configurations, SPELEC software (DropView SPELEC) provides automated data acquisition and synchronized multi-response analysis with a single click.

Future Trends and Potential Applications


Advances in miniaturized flow-through cells, microelectrode arrays and wireless spectroelectrochemical sensors promise on-site and high-throughput screening. Integration with machine learning will enable automated interpretation of complex datasets. Emerging applications include operando studies of electrosynthesis, advanced battery diagnostics and real-time environmental surveillance.

Conclusion


Spectroelectrochemistry delivers unrivalled insight by combining optical and electrochemical measurements in tandem. Recent instrumental innovations and broad application scope—from fundamental research to industrial QC—underscore its growing importance. Continued integration with data-driven tools will further expand its impact.

References


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  3. Heras A, Colina A, Ruiz V, López-Palacios J. Electroanalysis 2003;15:702–708.
  4. Zhangyu Y, Tiande G, Mei Q. Anal. Chem. 1994;66:497–502.
  5. Nowicka AM, Zabost E, Donten M, Mazerska Z, Stojek Z. Bioelectrochemistry 2007;70:440–445.
  6. Syed SN, Schulze H, MacDonald D, et al. J. Am. Chem. Soc. 2013;135:5399–5407.
  7. Gonzalez-Dieguez N, Colina A, Lopez-Palacios J, Heras A. Anal. Chem. 2012;84:9146–9153.
  8. He JB, Yuan SJ, Du JQ, Hu XR, Wang Y. Bioelectrochemistry 2009;75:110–116.
  9. Nowicka AM, Zabost E, Donten M, Mazerska Z, Stojek Z. Electroanalysis 2007;19:214–219.
  10. Olmo F, Garoz-Ruiz J, Colina A, Heras A. Anal. Bioanal. Chem. 2020;412:6329–6339.
  11. Zhao X, Nilges MJ, Lu Y. Biochemistry 2005;44:6559–6564.
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  13. Redman DW, Rose MJ, Stevenson KJ. Langmuir 2017;33:9354–9360.
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  15. McSkimming A, Chan B, Bhadbhade MM, et al. Chem. Eur. J. 2015;21:2821–2834.

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