Surface-Enhanced Raman Spectroscopy-Scanning Electrochemical Microscopy: Observation of Real-Time Surface pH Perturbations

Understanding and controlling chemical dynamics at electrode interfaces is key to electrochemical applications in sensing, electrocatalysis, and energy storage. Here, we introduce colocalized surface-enhanced Raman scattering-scanning electrochemical microscopy (SERS-SECM) as a multimodal tool able...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2021-06, Vol.93 (22), p.7792-7796
Main Authors: Hatfield, Kendrich O, Gole, Matthew T, Schorr, Noah B, Murphy, Catherine J, Rodríguez-López, Joaquín
Format: Article
Language:English
Subjects:
Chemistry
Electrochemistry
Energy storage
Hydrogen evolution reactions
Interfaces
Microscopy
Nanoparticles
Perturbation
pH effects
Raman spectra
Raman spectroscopy
Real time
Scanning
Self-assembled monolayers
Self-assembly
Silver
Spectrum analysis
Substrates
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Summary:Understanding and controlling chemical dynamics at electrode interfaces is key to electrochemical applications in sensing, electrocatalysis, and energy storage. Here, we introduce colocalized surface-enhanced Raman scattering-scanning electrochemical microscopy (SERS-SECM) as a multimodal tool able to simultaneously probe and affect electrochemical interfaces in real time. As a model system to demonstrate SERS-SECM, we used a self-assembled monolayer of 4-mercaptopyridine (4MPy), a pH sensitive Raman indicator, anchored to silver nanoparticles as a substrate. We modulated the local pH at the surface with chronoamperometry, inducing the hydrogen evolution reaction (HER) at the SECM tip and observed subsequent Raman peak height changes in the 4MPy. We then performed cyclic voltammetry of HER at the SECM tip while measuring SERS spectra every 200 ms to highlight the technique’s real-time capabilities. Our results show the capability to sensitively interrogate and trigger chemical/electrochemical dynamic surface phenomena. We hope SERS-SECM will provide insight on the link between heterogeneous and homogeneous reactivity at electrochemical interfaces.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.1c00888