Electrochemical, surface enhanced Raman scattering and surface plasmon resonance investigations on the coordination of cyanopyridine to ruthenium on surface

Abreu, Dieric S.; Paulo, Tércio F.; Temperini, Márcia L. A.; Diógenes, Izaura C.N.

doi:10.1016/j.electacta.2013.10.132

Cited by 4 publications

(12 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Assuming a gold–sulfur interaction, the intensity decrease of this band in the SERS spectrum is assigned to the distance to the surface, whereas the shift to higher frequency is ascribed to electron delocalization toward the gold surface which decreases the population of the antibonding orbitals, thus increasing the bond order of the CN bonding. Similar behaviors have been observed for molecules containing the nitrile fragment, which are adsorbed on gold via the sulfur atom. , …”

Section: Resultssupporting

confidence: 73%

“…By analogy to monosubstituted pyridines, the signal at 1101 cm –1 in the NR spectrum of HS2PCN is assigned to the X-sensitive band because of the dependence of its intensity and frequency on the trans substituents of the aromatic ring. , The relative intensification of this mode, as well as the observed downshift to 1085 cm –1 in the SERS spectrum, indicates that the adsorption to the gold surface occurs through the sulfur atom, as expected for the adsorption of sulfur containing compounds on gold. ,,,− …”

Section: Resultsmentioning

confidence: 86%

“…Similar behaviors have been observed for molecules containing the nitrile fragment, which are adsorbed on gold via the sulfur atom. 35,39 The stability of SAMs formed with sulfur-containing molecules on gold has been indirectly estimated through the measurement of the strength of the Au−S bond by means of reductive desorption in alkaline media. 9,46−50 Accordingly, a single wave is expected due to the following electrode reaction: Au−SR + e − → Au + SR − which occurs at E rd (reductive desorption potential).…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

et al. 2018

View full text Add to dashboard Cite

Tuning the energy of the frontier orbitals of an adsorbed molecule to match the Fermi level of the electrode is a fundamental requirement for efficient charge injection in molecular electronic devices. In this paper, we present electrochemical, impedimetric, spectroscopic, and scanning electrochemical microscopy (SECM) data that were used to study the effects of the adsorption of 4′-mercaptobiphenylcarbonitrile (HS2PCN) on the work function of gold. The adsorption process was studied and indicated the formation of a loosely packed self-assembled monolayer (SAM, ΔG ads = −43.3 kJ mol–1) following the immersion of the gold substrate in an ethanolic solution of HS2PCN. An increase in the immersion time resulted in the accumulation of negative charge density on the gold surface ascribed to the bonding dipoles resulting from the charge rearrangement at the metal–SAM interface that generates interfacial dipoles as a result of a charge-transfer process. As a consequence, a modification of about 1.2 eV is estimated in the work function of the gold surface modified with HS2PCN. Electron-transfer rate constants (k 0), as measured via SECM, showed a strong dependence on the net charge of the redox probes and increased on going from negatively (ca. 1.14 × 10–3 cm s–1) to positively charged species (>1.0 cm s–1). Such behavior is ascribed to the polarity of the interface of the HS2PCN SAM on gold, which is negatively charged because of the electron-withdrawing property of the nitrile fragment.

show abstract

Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 86%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

et al. 2018

View full text Add to dashboard Cite

show abstract

“…3e) colours were obtained for Pt, Pd and Ru, respectively. Apparently, these colours are related to the plasmon absorption of the corresponding metal nanoparticles [35][36][37]. These data are in agreement with the data obtained for non-immobilized nanopartlces of Au, Pt, Pd, and Ru, respectively, and support the formation of their respective NPs on the silica surface.…”

Section: Formation Of Noble Metal Nanoparticles On the Silica Surfacesupporting

confidence: 90%

In situ production of high purity noble metal nanoparticles on fumed silica and catalytic activity towards 2-nitrophenol reduction

Korobeinyk

Whitby

Mikhalovsky³

et al. 2019

Journal of Physics and Chemistry of Solids

View full text Add to dashboard Cite

In-situ synthesis of chemically pure noble metal (Au, Pt, Pd, Ru) nanoparticles was performed via redox reaction under ambient conditions from aqueous noble metal salt solutions on non-porous fumed silica. Nanoparticles of average sizes < 5 and up to 19 nm were obtained. The nanostructured fumed silica with surface modified by triethoxysilane has been proven an effective support for noble metal nanoparticles synthesis. The silicon-hydride groups on the silica surface not only directly reduce noble metal ions from solution, but they also stabilize metal nanoparticles by bonding with the solid matrix. The nanocomposites were studied for the reduction of 2-nitrophenol showing very high activity at room temperature following the order Pd>Au>Ru>Pt.

show abstract

“…For the [Ru(NH 3 ) 4 (CNpy)(pyS)] 2+ complex in solution, the results of electrochemistry and electronic spectroscopy suggest similar π acid strength for the CNpy and pyS ligands. More recently, 13 we published a paper on the in situ formation of the SAM of [Ru(NH 3 ) 4 (CNpy)(pyS)] 2+ on gold. Based on electrochemical, SERS, and SPR (surface plasmon resonance) results, it was possible to follow the formation of this SAM since the selfassembling of the sulfate starting complex [Ru(SO 4 )-(NH 3 ) 4 (pyS)] + that, upon reduction of the metal center, undergoes the substitution reaction of (SO 4 ) 2− by H 2 O which, in turn, is replaced by CNpy.…”

Section: ■ Introductionmentioning

confidence: 99%

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

et al. 2014

Self Cite

View full text Add to dashboard Cite

The results presented in this work definitely show that the stability of the SAM formed with [Ru-(NH 3 ) 4 (CNpy)(pyS)] 2+ on gold, where CNpy = 4-cyanopyridine and pyS = 4-mercaptopyridine, is dependent on the applied potential and on the chemical properties of the solution in the solid/liquid interface. By means of SERS spectroscopy, it was found that CNpy ligand is released from the coordination sphere if no reducing condition is imposed to the system, i.e., citrate solution or applied potential lower than the formal potential of the complex. Theoretical Raman spectra obtained from DFT presented reasonable correlation with the experimental spectra and gave support for the assignments. The relative intensities of the bands in the SERS spectra showed to be dependent on the applied potential as well as on the wavelength of the exciting radiation, indicating the contribution of a charge transfer process to the SERS intensification. In fact, the shift of the potential of maximum SERS intensity (E max ) to negative values as the radiation energy increases indicates a charge transfer process from the HOMO orbitals of the complex to the Fermi level.

show abstract

Electrochemical, surface enhanced Raman scattering and surface plasmon resonance investigations on the coordination of cyanopyridine to ruthenium on surface

Cited by 4 publications

References 36 publications

Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

In situ production of high purity noble metal nanoparticles on fumed silica and catalytic activity towards 2-nitrophenol reduction

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Contact Info

Product

Resources

About