Capturing electrochemical transformations by tip-enhanced Raman spectroscopy

Touzalin, Thomas; Joiret, S.; Maisonhaute, Emmanuel; Lucas, Ivan T.

doi:10.1016/j.coelec.2017.10.016

Cited by 23 publications

(18 citation statements)

References 62 publications

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“…So far, SERS is much easier to operate, shows higher enhancement factors and has shown much more advances than TERS. Indeed, apart from the delicate optical microscopy configurations [41], one challenge in TERS concerns the lack of reproducibility in the production of the tips. Moreover, the TERS hot spot is often altered during the time-consuming raster-scanning image acquisition.…”

Section: Raman Scattering Microscopiesmentioning

confidence: 99%

Electrochemistry and Optical Microscopy

Kanoufi

2021

Encyclopedia of Electrochemistry

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Electrochemistry exploits local current heterogeneities at various scales ranging from the micrometer to the nanometer. The last decade has witnessed unprecedented progress in the development of a wide range of electroanalytical techniques allowing to reveal and quantify such heterogeneity through multiscale and multifonctionnal operando probing of electrochemical processes. However most of these advanced electrochemical imaging techniques, employing scanning probes, suffer from either low imaging throughput or limited imaging size. In parallel, optical microscopies, which can image a wide field of view in a single snapshot, have made considerable progress in terms of sensitivity, resolution and implementation of detection modes. Optical microscopies are then mature enough to propose, with basic bench equipment, to probe in a non destructive way a wide range of optical (and therefore structural) properties of a material in situ, in real time: under operating conditions. They offer promising alternative strategies for quantitative high-resolution imaging of electrochemistry. The first sections recall the optical properties of materials and how they can be probed optically. They discuss fluorescence, Raman, surface plasmon resonance, scattering or refractive index. Then the different optical microscopes used to image electrochemical processes are examined along with some strategies to extract quantitative electrochemical information from optical images. Finally the last section reviews some examples of in situ imaging, at micro-to nanometer resolution, and quantification of electrochemical processes ranging from solution diffusion to the conversion of molecular interfaces or solids.]

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Section: Raman Scattering Microscopiesmentioning

confidence: 99%

Electrochemistry and Optical Microscopy

Kanoufi

2021

Encyclopedia of Electrochemistry

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“…To this respect, it was soon realized that the gain in sensitivity provided by Surface Enhanced Raman Spectroscopy (SERS) [5] would also benefit to electrochemistry. Nanoscale resolution is even nowadays accessible through Tip-Enhanced Raman Spectroscopy [7][8][9][10][11][12]. First SERS substrates were in fact roughened silver or gold electrodes [13,14], presenting randomly distributed "hot spots", i.e.…”

Section: Introductionmentioning

confidence: 99%

Long range self-organisations of small metallic nanocrystals for SERS detection of electrochemical reactions

Groni

Fave

Schöllhorn

et al. 2020

Journal of Electroanalytical Chemistry

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Gold electrodes were modified by silver and gold nanocrystals (NCs) that self-organize onto the surface. Their optical properties were explored by measuring electroreflectance spectra as a function of electrode potential. Below their oxidation potential, no shift of the reflectance maximum was observed for Ag NCs. This can be explained by a low interfacial capacitance resulting from the impossibility for the electrolyte to penetrate into the hydrophobic layer created by the NCs dodecanethiol ligands. Conversely, a non-monotonous evolution was observed with the electrode potential for oleylamine capped Au NCs. This behavior is suggesting a less dense hydrophobic layer, allowing significant electrolyte penetration. Next, electroactive compounds were adsorbed on the the Au NCs assemblies and characterized by Raman spectroelectrochemistry. In the first system displaying a single electron transfer with no coupled chemical reaction, only the spectrum intensity changed, because oxidation generated a Raman resonant radical cation. The second study considered 4-nitrothiophenol, for which up to 6 electrons and 6 protons may be transferred. In this case, the nitro band disappeared upon reduction, and the spectrum displayed typical features of the formed 4-aminothiophenol.

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“…The enhancement observed with a roughened Ag electrode 3 was orders of magnitude greater than that expected and was later attributed to electromagnetic 4 and chemical 5 effects, with the former now understood to provide most of the typically 10 6 -fold enhancement. In the many years since the initial discovery there have over 19,000 SERS papers published, most of which describe the development of new or improved SERS substrates 6 , further study of the SERS mechanism 7 , and the development of advanced SERS techniques, such as tip-enhanced Raman spectroscopy (TERS), as evidenced by the two most recent Faraday Discussions on SERS 8,9 and some of the reviews published in this journal 10,11,12 .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights into electrocatalytic reactions provided by SERS

Keeler

Salazar‐Banda

Russell

2019

Current Opinion in Electrochemistry

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In situ vibrational spectroscopy can provide molecular level mechanistic insights missing from purely electrochemical measurements. Surface enhanced Raman spectroscopy (SERS) is a particularly promising method and is employed in aqueous and non-aqueous studies of a variety of electrode reactions. Enhancement of the weak Raman signal is achieved by structuring the electrode surface or by use of SERS probes. This review article highlights the recent use of SERS to study several important electrode reactions; oxygen reduction and evolution, carbon monoxide oxidation and carbon dioxide reduction, and the electrocatalytic oxidation of small organic molecules such as formic acid. Figure 1:A schematic diagram of the study of electrochemical reaction mechanisms using SERS depicting the reactions covered in this review. The SERS substrate electrode must be structured in a manner to provide the SERS enhancement (see Figure 2) and the reactants, intermediates, and products detected must be located in the region in which the enhancement of the Raman signal is strong for effective detection.

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Capturing electrochemical transformations by tip-enhanced Raman spectroscopy

Cited by 23 publications

References 62 publications

Electrochemistry and Optical Microscopy

Electrochemistry and Optical Microscopy

Long range self-organisations of small metallic nanocrystals for SERS detection of electrochemical reactions

Mechanistic insights into electrocatalytic reactions provided by SERS

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