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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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).
The authors declare no competing interests.
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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.
- 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.
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.
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