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Electrochemical surface-enhanced Raman spectroscopy

Nature Reviews Methods Primers volume 3, Article number: 79 (2023) Cite this article

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Abstract

Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) is a spectroelectrochemical method that has been in existence since the first SERS measurements were collected, yet it is a technique that has only recently become mainstream. EC-SERS measurements involve the collection of greatly enhanced Raman spectra at the electrified interface of nanostructured metal surfaces, most often coinage metals such as gold or silver. Owing to the surface sensitivity and selectivity of EC-SERS measurements, this technique can provide insight into various interfacial processes. Recent applications of EC-SERS investigations have included biosensing, catalysis and environmental analysis. This Primer seeks to introduce researchers with interdisciplinary backgrounds to key concepts of EC-SERS, including signal enhancement mechanisms, practical experimentation, electrode preparation and data collection and interpretation. Finally, a selection of recent applications and novel directions for future research are presented.

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Fig. 1: Surface-enhanced Raman spectroscopy mechanisms.
Fig. 2: Electrochemical surface-enhanced Raman spectroscopy optical path configurations.
Fig. 3: Miniaturization approaches in electrochemical surface-enhanced Raman spectroscopy.
Fig. 4: Electrochemical surface-enhanced Raman spectroscopy data cube.
Fig. 5: Procedures for performing mechanistic analyses of electrochemical surface-enhanced Raman spectroscopy measurements.
Fig. 6: Electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy study of interfacial water on a Pd single-crystal surface in a 0.1-M NaClO4 solution (pH 11).
Fig. 7: Electrochemical surface-enhanced Raman spectroscopy for characterization of battery materials.

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Acknowledgements

This work was supported by the Natural Sciences and Engineering Research Council of Canada (C.L.B.) and the Canada Research Chairs Program (C.L.B.). A.J.W. and P.B.J. acknowledge support from the Oak Ridge Associated Universities through a Ralph E. Powe Junior Faculty Enhancement Award and start-up funds from the University of Louisville. A.C. acknowledges the Ministerio de Ciencia e Innovación and Agencia Estatal de Investigación (MCIN/AEI/10.13039/501100011033, PID2020-113154RB-C21). J.V.P.-R. acknowledges Ministerio de Universidades and NextGenerationEU for his Maria Zambrano fellowship. B.R. and X.W. acknowledge the financial support of the National Natural Science Foundation of China (NSFC) (Grant Nos 22021001, 22227802 and 92061118).

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Authors and Affiliations

  1. Department of Chemistry, Saint Mary’s University, Halifax, Nova Scotia, Canada

    Christa L. Brosseau

  2. Department of Chemistry, Universidad de Burgos, Burgos, Spain

    Alvaro Colina & Juan V. Perales-Rondon

  3. Department of Chemistry, University of Louisville, Louisville, KY, USA

    Andrew J. Wilson & Padmanabh B. Joshi

  4. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (i-ChEM), Innovation Laboratory for Science and Technologies of Energy Material of Fujian Province (IKKEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Bin Ren & Xiang Wang

Authors
  1. Christa L. Brosseau
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  2. Alvaro Colina
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  3. Juan V. Perales-Rondon
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  4. Andrew J. Wilson
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  5. Padmanabh B. Joshi
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  6. Bin Ren
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  7. Xiang Wang
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Contributions

Introduction (C.L.B.); Experimentation (A.C., J.V.P.-R., C.L.B., B.R., X.W., A.J.W. and P.B.J.); Results (A.C., J.V.P.-R., B.R. and X.W.); Applications (C.L.B., B.R. and X.W.); Reproducibility and data deposition (C.L.B.); Limitations and optimizations (C.L.B.); Outlook (C.L.B.); Overview of the Primer (C.L.B.).

Corresponding authors

Correspondence to Christa L. Brosseau, Alvaro Colina, Andrew J. Wilson, Bin Ren or Xiang Wang.

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

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Glossary

Chemical enhancement mechanism

Charge-transfer processes between the adsorbate and the metal surface result in an enhancement of the Raman signal, typically in the order of 101–102.

Electrochemical Stark tuning

Changes in vibrational frequencies of adsorbed species as a function of applied potential that originates from potential-dependent metal–adsorbate bonding and from the influence of electric field on the adsorbed layer.

Electromagnetic enhancement

Excitation of localized surface plasmons on the nanoparticle surface leads to a generation of an enhanced electric field at the surface, which results in an E4 enhancement of the Raman-scattered photons.

Epi-illumination

An arrangement of optical components in microscopy that allows for illumination of the specimen from above.

Glancing angle geometry

In optics, the angle between the incident beam and the surface.

Localized surface plasmon resonance

Collective oscillation of conduction electrons present in metal nanoparticles on irradiation of light.

Potential of zero charge

(PZC). Potential at which the surface free charge of a particular metal is zero.

Savitzky–Golay smoothing

A digital data filter commonly used to smooth data.

Signal filtering

Process whereby unwanted components or features of a signal are removed.

VoltaRamangram

A plot of the spectral peak evolution in Raman spectroscopy as a function of the applied potential.

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Brosseau, C.L., Colina, A., Perales-Rondon, J.V. et al. Electrochemical surface-enhanced Raman spectroscopy. Nat Rev Methods Primers 3, 79 (2023). https://doi.org/10.1038/s43586-023-00263-6

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