Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper

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Title: Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper
Authors: Vidal-Iglesias, Francisco J. | Solla-Gullón, José | Orts Mateo, José M. | Rodes García, Antonio | Pérez Martínez, Juan Manuel
Research Group/s: Grupo de Espectroelectroquímica y Modelización (GEM) | Electroquímica de Superficies | Electroquímica Aplicada y Electrocatálisis
Center, Department or Service: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Keywords: Surface-enhanced raman scattering (SERS) spectra | Photoinduced catalytic formation | 4,4′-dimercaptoazobenzene | 4-aminobenzenethiol | Nanostructured copper
Knowledge Area: Química Física
Issue Date: 12-May-2015
Publisher: American Chemical Society
Citation: The Journal of Physical Chemistry C. 2015, 119(22): 12312-12324. doi:10.1021/acs.jpcc.5b01245
Abstract: Surface-enhanced raman scattering (SERS) spectra of self-assembled monolayers of 4-aminobenzenethiol (4-ABT) on copper (Cu) and silver (Ag) surfaces decorated with Cu and Ag nanostructures, respectively, have been obtained with lasers at 532, 632.8, 785, and 1064 nm. Density functional theory (DFT) has been used to obtain calculated vibrational frequencies of the 4-ABT and 4,4′-dimercaptoazobenzene (4,4′-DMAB) molecules adsorbed on model Cu surfaces. The features of the SERS spectra depend on the electrode potential and the type and power density of the laser. SERS spectra showed the formation of the 4,4′-DMAB on the nanostructured Cu surface independently of the laser employed. For the sake of comparison SERS spectra of a self-assembled monolayer of the 4-ABT on Ag surfaces decorated with Ag nanostructures have been also obtained with the same four lasers. When using the 532 and 632.8 nm lasers, the 4,4′-DMAB is formed on Cu surface at electrode potentials as low as −1.0 V (AgCl/Ag) showing a different behavior with respect to Ag (and others metals such as Au and Pt). On the other hand, the surface-enhanced infrared reflection absorption (SEIRA) spectra showed that in the absence of the laser excitation the 4,4′-DMAB is not produced from the adsorbed 4-ABT on nanostructured Cu in the whole range of potentials studied. These results point out the prevalence of the role of electron–hole pairs through surface plasmon activity to explain the obtained SERS spectra.
Sponsor: Financial support from Ministerio de Economía y Competitividad (Projects CTQ2013-48280-C3-3-R and CTQ2013-44083-P), Fondos Feder, and the University of Alicante are greatly acknowledged.
URI: http://hdl.handle.net/10045/47293
ISSN: 1932-7447 (Print) | 1932-7455 (Online)
DOI: 10.1021/acs.jpcc.5b01245
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2015 American Chemical Society
Peer Review: si
Publisher version: http://dx.doi.org/10.1021/acs.jpcc.5b01245
Appears in Collections:INV - EQSUP - Artículos de Revistas
INV - LEQA - Artículos de Revistas
INV - GEM - Artículos de Revistas

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