The adsorption of 2,2′:6′,2″-terpyridine, 4′-(5-mercaptopentyl)-2,2′:6′,2″-terpyridinyl, and perchlorate on silver and copper surfaces monitored by SERS

Sant’Ana, Antônio Carlos; Alves, Wendel A.; Santos, Regina Helena de Almeida; Ferreira, Ana Maria da Costa; Temperini, Márcia L. A.

doi:10.1016/s0277-5387(03)00325-5

Cited by 37 publications

(29 citation statements)

References 33 publications

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“…A study of ClO 4 -adsorption on copper electrode has shown that the Cu-O vibration shows up at 302 cm -1 as a weak band. 28 In the same work, the authors found that pure electrostatic interaction leads to a Cu-O stretching band at 177 cm -1 . It is reasonable to assume that coordination to copper in the hydroxide matrix is a stronger interaction than adsorption and, considering the three bands cited above, it also seems reasonable to assign the weak 345 cm -1 band to the Cu-O (perchlorate) vibration.…”

Section: Resultsmentioning

confidence: 89%

CuII hydroxy salts: characterization of layered compounds by vibrational spectroscopy

Pereira

Faria

Constantino

2006

J. Braz. Chem. Soc.

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Hidroxo-sais lamelares de composição Cu 2 (OH) 3 X (X = NO 3 -, CH 3 COO -e ClO 4 -) foram sintetizados através da coprecipitação (sais básicos de nitrato e acetato) e da troca iônica (sal básico de perclorato). Os sólidos cristalinos foram caracterizados por difratometria de raios X, análise termogravimétrica e espectroscopia vibracional. Bandas fracas em 336 e 345 cm -1 (espectro Raman) dos sais de nitrato e perclorato, respectivamente, foram tentativamente atribuídas ao νCu-O (ânion). Os ions nitrato possuem simetria C 2v no composto Cu 2 (OH) 3 NO 3 e, consequentemente, observa-se o desdobramento dos modos E'. A quebra da degenerescência também é observada nos modos F 2 do íon ClO 4 -livre, ocasionando o desdobramento das bandas em 630 e 1100 cm -1 no espectro do hidroxo-perclorato de cobre(II). A pequena diferença de energia entre os modos ν as C-O e ν s C-O (Δ=143 cm -1 ) do sal de acetato sugere a presença de ligação de hidrogênio entre o oxigênio não coordenado do grupo carboxilato e um íon hidroxila adjacente. Os íons nitrato, acetato e perclorato estão coordenados ao cobre(II) de modo monodentado.Copper hydroxy salts with a layer-type structure and general composition Cu 2 (OH) 3 X (X = NO 3 -, CH 3 COO -and ClO 4 -) were synthesized by co-precipitation (nitrate and acetate salts) and ion exchange (perchlorate salt) methods. The isolated polycrystalline solids were characterized by X-ray diffractometry, thermogravimetric analysis and vibrational spectroscopy. A weak band at 336 and 345 cm -1 (Raman spectrum) of the nitrate and perchlorate salts, respectively, was tentatively assigned to the nCu-O (anion). In Cu 2 (OH) 3 NO 3 the nitrate ion has a C 2v symmetry and, accordingly, a splitting in the E' modes is observed. The same happens to the hydroxy perchlorate salt with the degeneracy breakdown of the F 2 modes (free ClO 4 -) at 630 and 1100 cm -1 leading to band splitting. For the carboxylate salt, the small difference in the energy of ν as C-O and ν s C-O (Δ=143 cm -1 ) suggests that hydrogen bonding with neighbor OH group may be present. Nitrate, carboxylate and perchlorate are monocoordinated to copper(II) in the investigated salts.

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Section: Resultsmentioning

confidence: 89%

CuII hydroxy salts: characterization of layered compounds by vibrational spectroscopy

Pereira

Faria

Constantino

2006

J. Braz. Chem. Soc.

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“…[38][39][40] The activation of transition metal electrodes was done in the absence of phen. The final step was thoroughly rinsing the activated electrode with deionized water.…”

Section: Methodsmentioning

confidence: 99%

1,10-Phenanthroline Adsorption on Iron Electrode Monitored by Surface-Enhanced Raman Scattering (SERS). Comparison to SERS of Phen and Its Transition Metal Complex on Silver Electrode

Andrade

Temperini

2007

J. Phys. Chem. C

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The SER spectra of 1,10-phenanthroline (phen) adsorbed on Fe electrode in chloride medium as a function of applied potentials at 632.8 and 514.5 nm excitation wavelengths are presented. SERS spectra of phen on Co and Ni electrodes at 632.8 nm are also shown. The SER signatures of the surface complex indicate its similarity with the chemically prepared [M(phen) 3 ] 2+ , where M ) Fe 2+ , Co 2+ , or Ni 2+ . The same changes in relative intensities of the bands with applied potential are observed for phen on transition metals and for [M(phen) 3 ] 2+ on silver electrodes. These spectral changes at 632.8 nm excitation radiation resemble the spectral changes in the resonance Raman spectra of [M(phen) 3 ]Cl 2 at different excitation laser lines. At the potential of maximum intensity, the strongest band in phen on Ag SER spectrum is ca. 70 times higher than that in phen on Fe, while the phen on Fe SER excitation profile is ca. 5 times higher than that of phen on Ag. At 632.8 nm radiation, the band at 557 cm -1 for phen on Fe shows the highest profile in SER excitation profiles, while for phen on Ag the most enhanced band is at 1578 cm -1 . These results indicate that the CT excited states in phen on Fe and phen on Ag are different and that the SER CT mechanism in phen on Fe is more effective. The magnitude and dissimilarities in the [Fe(phen) 3 ]Cl 2 resonance Raman profiles as compared to the SER excitation profiles of [Fe(phen) 3 ] 2+ on Ag emphasize the different origins of the two enhancement processes.

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“…The spectrum is fully in agreement with literature data. 18 Curve d shows the spectrum for the hybrid material FeTPPZFeCN/PPy, where it can be seen that there is an overlap between the bands of the PPy (curve d) and FeTPPZFeCN (curve b) assigned to polypyridine ligands as already described. Moreover, the presence of bands assigned to -C N group at ca.…”

Section: Fetppzfecn/ppy Hybrid Materials (Curve D)mentioning

confidence: 56%

“…The presence of TPPZ in [Fe 2 (TPPZ)(SO 4 ) 3 ], FeTPPZFeCN and FeTPPZFeCN/PPy in curves a, b and d respectively, is revealed by the bands located at 3100-2900 cm -1 corresponding to the aromatic C-H stretching vibrations, those at 1650-1550 cm -1 to (C=N) and (C=C) stretchings (in the case of the hybrid material this region is a little obscured by absorptions of the PPy matrix), those at 1470-1020 cm -1 corresponding to (C-C) + (C-N) modes and those at 810-710 cm -1 assigned to aromatic C-H deformation vibrations. 18 Most of them are shifted to lower frequencies when compared to those of uncoordinated TPPZ suggesting the coordination of TPPZ ligand to metallic centers.…”

Section: Fetppzfecn/ppy Hybrid Materials (Curve D)mentioning

confidence: 99%

Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

Alves

Pfaffen

Ortiz

et al. 2008

J. Braz. Chem. Soc.

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Este trabalho descreve a caracterização espectroscópica por infravermelho e o estudo da dinâmica de compensação de cargas do filme supramolecular FeTPPZFeCN derivado do ligante tetra-2-piridil-1,4-pirazina (TPPZ) com hexacianoferrato, bem como o filme híbrido envolvendo FeTPPZFeCN e uma matriz de polipirrol (PPy). Para o filme supramolecular, foi observado um aumento no fluxo de ânion em solução contendo K + em relação ao Li + , que parece estar relacionado ao tamanho do raio iônico cristalino do K + . O processo de eletroneutralização é discutido em termos de interação eletrostática entre cátions e centros metálicos na matriz hospedeira. A natureza do processo de compensação de carga difere de outros eletrodos modificados derivados do azul da Prússia, onde somente cátions tais como K + participam no processo de eletroneutralização. No caso do filme híbrido FeTPPZFeCN/PPy, a magnitude do fluxo de ânions é também dependente da identidade do ânion em diferentes eletrólitos de suporte.This work describes the infrared spectroscopy characterization and the charge compensation dynamics in supramolecular film FeTPPZFeCN derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate, as well as the hybrid film formed by FeTPPZFeCN and polypyrrole (PPy). For supramolecular film, it was found that anion flux is greater in a K + containing solution than in Li + solution, which seems to be due to the larger crystalline ionic radius of K + . The electroneutralization process is discussed in terms of electrostatic interactions between cations and metallic centers in the hosting matrix. The nature of the charge compensation process differs from others modified electrodes based on Prussian blue films, where only cations such as K + participate in the electroneutralization process. In the case of FeTPPZFeCN/PPy hybrid film, the magnitude of the anions's flux is also dependent on the identity of the anion of the supporting electrolyte.

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The adsorption of 2,2′:6′,2″-terpyridine, 4′-(5-mercaptopentyl)-2,2′:6′,2″-terpyridinyl, and perchlorate on silver and copper surfaces monitored by SERS

Cited by 37 publications

References 33 publications

CuII hydroxy salts: characterization of layered compounds by vibrational spectroscopy

CuII hydroxy salts: characterization of layered compounds by vibrational spectroscopy

1,10-Phenanthroline Adsorption on Iron Electrode Monitored by Surface-Enhanced Raman Scattering (SERS). Comparison to SERS of Phen and Its Transition Metal Complex on Silver Electrode

Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

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