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In Situ Raman Spectroelectrochemistry Of Electron Transfer Between Glassy Carbon And A Chemisorbed Nitroazobenzene Monolayer.

T. Itoh, R. McCreery
Published 2002 · Chemistry, Medicine

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In situ Raman spectroscopy was used to monitor 4-nitroazobenzene (NAB) in an electrochemical cell, both as a free molecule and as a chemisorbed monolayer on a glassy carbon (GC) electrode surface. Reduction of free NAB exhibited two well-defined voltammetric couples in acetonitrile, and the accompanying spectral changes supported a mechanism involving two successive 1-e(-) transfers. Raman spectra of NAB chemisorbed to GC via diazonium ion reduction were obtained in acetonitrile with a high-sensitivity, line-focused CCD spectrometer. The chemisorbed NAB spectra were quite different from the free NAB spectra, and were sufficiently strong to monitor as a function of applied potential. In the potential range of +400 to -800 mV vs Ag/Ag(+), the intensity of the Raman bands associated with the phenyl-NO(2) moiety varied, implying an electronic interaction between the pi system of the graphitic substrate and the chemisorbed NAB molecules. Negative of -800 mV, a 1-e(-) voltammetric reduction peak was observed, which was reversible on the positive voltage scan. This peak was accompanied by significant spectral changes, particularly the loss of the N=N and NO(2) stretches. The spectra are consistent with formation of a quinoid structure containing a C=C double bond between the NAB and the graphitic surface. The electron transfer and spectral changes occurred over a wider potential range than expected for a conventional Nernstian equilibrium, but did not appear to be broadened by slow electron-transfer kinetics. The results imply a significant perturbation of electron transfer between the GC and the monolayer, caused by strong electronic coupling between the graphitic pi system and the NAB orbitals. Rather than a discrete electron transfer to a free molecule, the electron transfer to chemisorbed NAB is more gradual, and is presumably driven by the electric field at the electrode/solution interface.



This paper is referenced by
10.1016/J.JELECHEM.2005.12.026
Oxygen electroreduction on chemically modified glassy carbon electrodes in alkaline solution
Marko Kullapere (2007)
10.1073/pnas.1201557109
Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime
S. Y. Sayed (2012)
10.1016/j.talanta.2009.06.076
Screen-printed electrografted electrode for trace uranium analysis.
S. Betelu (2009)
10.1007/S00216-007-1192-4
In situ Raman spectroelectrochemistry of azobenzene monolayers on glassy carbon
T. Itoh (2007)
10.1016/J.ELECOM.2009.01.004
Microelectrodes modification through the reduction of aryl diazonium and their use in scanning electrochemical microscopy (SECM)
M. Janin (2009)
10.1002/cphc.200900416
Electron transport and redox reactions in molecular electronic junctions.
R. McCreery (2009)
10.1016/j.fob.2015.10.008
Disperse Orange 3 as a resonance Raman probe for measuring membrane order
Yuki Numakura (2015)
10.1016/J.ELECTACTA.2008.09.066
A stability comparison of redox-active layers produced by chemical coupling of an osmium redox complex to pre-functionalized gold and carbon electrodes
Susan Boland (2009)
10.3791/56653
Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds
Agata Blacha-Grzechnik (2018)
10.1007/128_2011_227
Molecular electronic junction transport: some pathways and some ideas.
G. Solomon (2012)
10.1002/9783527650446.CH5
Modification of Nano‐objects by Aryl Diazonium Salts
D. Guo (2012)
10.1366/000370207781269765
Normal and Surface-Enhanced Raman Spectroscopy of Nitroazobenzene Submonolayers and Multilayers on Carbon and Silver Surfaces
Haihe Liang (2007)
10.1366/000370209787392102
Optical Interference Effects in the Design of Substrates for Surface-Enhanced Raman Spectroscopy
L. Shoute (2009)
10.1016/j.chroma.2013.10.033
Grafting the sol-gel based sorbents by diazonium salts: a novel approach toward unbreakable capillary microextraction.
H. Bagheri (2013)
10.1007/978-3-319-49137-0_2
In Situ Spectroelectrochemical Fluorescence Microscopy for Visualizing Interfacial Structure and Dynamics in Self-assembled Monolayers
J. Casanova-Moreno (2017)
Diazonium salts induced anchoring process: mechanism, application(s)
A. Mesnage (2011)
10.1021/ACS.JPCC.5B11279
Spontaneous Modification of Free-Floating Few-Layer Graphene by Aryldiazonium Ions: Electrochemistry, Atomic Force Microscopy, and Infrared Spectroscopy from Grafted Films
Anna K Farquhar (2016)
10.1146/annurev-anchem-061010-113847
Analytical chemistry in molecular electronics.
A. Bergren (2011)
10.1021/ja809816x
Using a hydrazone-protected benzenediazonium salt to introduce a near-monolayer of benzaldehyde on glassy carbon surfaces.
Kristoffer Malmos (2009)
10.1039/B601163M
Electron transport and redox reactions in carbon-based molecular electronic junctions.
R. McCreery (2006)
10.1002/9783527650446.CH8
Electrografting of Conductive Oligomers and Polymers
J. Lacroix (2012)
10.1366/000370207782597094
Ultraviolet—Visible Spectroelectrochemistry of Chemisorbed Molecular Layers on Optically Transparent Carbon Electrodes
Hong Tian (2007)
10.1016/J.JELECHEM.2008.11.010
Biocatalytic fuel cells: A comparison of surface pre-treatments for anchoring biocatalytic redox films on electrode surfaces
Susan Boland (2009)
10.1201/B19196-4
Electrode Surface Modification Using Diazonium Salts
A. Berisha (2015)
Characterization and growth analysis of two types of thin films formed on copper surfaces: an inorganic chromium containing film and an organic film formed via reduction of diazonium ions
B. Hurley (2004)
10.1039/c9an02105a
Spectroelectrochemistry, the future of visualizing electrode processes by hyphenating electrochemistry with spectroscopic techniques.
J. J. A. Lozeman (2020)
10.1021/acs.analchem.6b04155
Direct Determination of Ascorbic Acid in a Grapefruit: Paving the Way for In Vivo Spectroelectrochemistry.
Jesus Garoz-Ruiz (2017)
10.1039/c1cs15208d
Vibrational spectroscopy as a probe of molecule-based devices.
A. B. Elliott (2012)
10.1021/la3011103
Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.
A. Mesnage (2012)
10.1149/1.1888369
Importance of Oxides in Carbon/Molecule/Metal Molecular Junctions with Titanium and Copper Top Contacts
William R. McGovern (2005)
10.1021/acs.analchem.7b00362
Characterization of Growth Patterns of Nanoscale Organic Films on Carbon Electrodes by Surface Enhanced Raman Spectroscopy.
Mustafa Supur (2017)
10.1021/ja208893q
Influence of electric field on SERS: frequency effects, intensity changes, and susceptible bonds.
S. Sriram (2012)
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