Electrochemical Tip-Enhanced Raman Spectroscopy with Improved Sensitivity Enabled by a Water Immersion Objective

Analytical Chemistry
Sheng-Chao HuangBin Ren

Abstract

Electrochemical tip-enhanced Raman spectroscopy (EC-TERS) appears as a promising in situ nanospectroscopic tool for characterization and understanding of the electrochemical interfacial processes at the nanometer scale and molecular level. However, the wide application of EC-TERS is hampered by its low sensitivity as a result of the optical path distortion due to the refractive index mismatch of the multilayer media (air, glass, and electrolyte). Here, we propose a new side-illumination EC-TERS setup by coupling a water immersion objective with a high numerical aperture to a scanning tunneling microscope scanning head customized with a large open space and a compact spectroelectrochemical cell. It not only effectively eliminates the optical distortion but also increases the sensitivity remarkably, which allows sensitive monitoring of the electrochemical redox processes of anthraquinone molecules. More importantly, EC-TERS is able to independently control the tip position and laser illumination position. By utilizing this feature, we reveal that the irreversible reduction reaction of anthraquinone observed in EC-TERS is induced by the synergistic effect of the negative potential and laser illumination rather than the localized s...Continue Reading

References

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Jun 10, 2010·Organic & Biomolecular Chemistry·Björn Schüpbach, Andreas Terfort
Sep 10, 2015·Journal of the American Chemical Society·Zhi-Cong ZengBin Ren
Nov 19, 2015·Nano Letters·Dmitry KurouskiRichard P Van Duyne
Jun 15, 2016·Analytical Chemistry·Natalia Martín SabanésKatrin F Domke
Sep 10, 2016·Analytical Chemistry·Zhi-Cong ZengBin Ren
Dec 13, 2016·Nano Letters·Michael MatteiRichard P Van Duyne
Dec 21, 2016·Nature Materials·Vojislav R StamenkovicNenad M Markovic
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Citations

May 20, 2020·Chemical Society Reviews·Dmitry KurouskiAndrea Centrone
Aug 22, 2020·Applied Spectroscopy·Giovanni GiuzioKatrin F Domke
May 19, 2020·Applied Spectroscopy·Jeremy F SchultzNan Jiang
Jul 24, 2020·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Jeremy F SchultzNan Jiang
Aug 26, 2020·Nature Communications·Sheng-Chao HuangBin Ren
Jan 26, 2021·Journal of the American Chemical Society·Kai BraunAlfred J Meixner
Nov 11, 2020·The Journal of Chemical Physics·Matthew M SartinBin Ren
Jan 6, 2021·Annual Review of Physical Chemistry·Sheng-Chao HuangBin Ren
Sep 26, 2020·Analytical Chemistry·Bolin LiZhan Chen

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