Interfacial spectroelectrochemical Raman study of the silver/1,10-phenanthroline system in chloride medium

Hajbi, Abdeslam El; Vante, N. Alonso; Chartier, P.; Goetz-Grandmont, G.J.; Heimburger, Robert F.; Leroy, M. J. F.

doi:10.1016/0022-0728(86)87067-x

Cited by 17 publications

(22 citation statements)

References 31 publications

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“…Although the conversion of phen to adsorbed carbon on an Ag electrode was previously reported 16,17 no evidence of this reaction is observed in our experiment; specifically, the broad band centered at approximately 1600 cm -1 due to disordered graphite 16,17 is not observed in any of our spectra. This implies that in our experiments the photochemistry produces relatively simple photoproducts in which a great deal of the molecular integrity of the original phen molecule is preserved.…”

Section: Obs ) Iσcontrasting

confidence: 72%

“…The SERS of 1,10-phenanthroline (phen), used extensively as a chelating ligand, has already been reported. Cooney et al 16 observed the carbonization of phen on Ag electrode surfaces by laser light; however, Hajbi et al 17 claim that only a portion of the adsorbed phen carbonizes on the Ag electrode surface mainly during the Ag 1 -Ag 0 oxidation-reduction process and that photographitization appears as a minor effect.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Surface Geometry on the Photochemical Reaction of 1,10-Phenanthroline Adsorbed on Silver Colloid Surfaces

1997

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The surface-enhanced Raman scattering spectra and the photochemistry of 1,10-phenanthroline (phen) adsorbed on silver colloid were studied using a flow cell. Phen adsorbed on fresh colloid is found to undergo almost no photochemistry while the same molecule adsorbed on aged colloid appears to photodecompose to a species in which the C−N ring bond in one or both of the heterocycles is broken to produce a CN moiety that binds to the silver surface. The contrast in the behavior of the two colloids is attributed to the differing bonding geometries of the adsorbate in the two cases. In the fresh colloid phen appears to bind with its C 2 axis normal to the local surface while on the aged colloid the molecule seems to bind flat on the surface. This difference in bonding strategy is ascribed to the existence of many surface defects on the surface of the fresh colloid that are ideal sites for bidentate chelation. These defects presumably significantly decrease in number as the surface heals with time. The photoproduct which forms upon irradiating phen adsorbed on aged colloid is subsequently observed to photodesorb at a rate significantly less rapid than that of the photodecomposition reaction. Both reactions are found to be one-photon processes; hence, the large photoreaction cross section in the visible is likely due to a metal-to-molecule charge-transfer transition.

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Section: Obs ) Iσcontrasting

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Effect of Surface Geometry on the Photochemical Reaction of 1,10-Phenanthroline Adsorbed on Silver Colloid Surfaces

1997

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“…78 On the other hand, the photoassisted route need not be a dominating carbonization process at the electrochemical interface: 1,10-phenanthroline carbonizes at a silver electrode in aqueous chloride medium either photoelectrochemically or (to a larger extent) by a dark charge transfer. 79 Different activated complexes were supposed for photo (9a) and dark (9b) reactions: Dark anodic oxidative carbonization of 1,2-diaminobenzene and some other amines also occurs at the Ag electrode. 14 It was even speculated that the carbon overlayer at silver is the actually SERS-active surface 13,14,[67][68][69][70][71][72][73][75][76][77]80,81 promoting adsorption 67,73,80,81 or intercalation 13,72 of the studied molecules.…”

Section: Oxidative Carbonizationmentioning

confidence: 99%

“…On the other hand, the photoassisted route need not be a dominating carbonization process at the electrochemical interface: 1,10-phenanthroline carbonizes at a silver electrode in aqueous chloride medium either photoelectrochemically or (to a larger extent) by a dark charge transfer . Different activated complexes were supposed for photo (9a) and dark (9b) reactions: Dark anodic oxidative carbonization of 1,2-diaminobenzene and some other amines also occurs at the Ag electrode .…”

Section: Oxidative Carbonizationmentioning

confidence: 99%

Electrochemical Carbon

Kavan

1997

Chem. Rev.

158

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“…Concerning this last most intense band, Alonso-Vante et al describe a redshift of this skeletal mode from 1406 to 1412 cm −1 upon coordination of phenanthroline on Ag electrodes in a similar fashion to what is discussed above for the 996 cm −1 band of bipyridine L1. 47,49 In the spectrum of L2, this band is originally located at 1406 cm −1 and may shift to 1424 cm −1 upon complexation. The main feature at 1424 cm −1 could rather be related to the nearby structure of L1 (1435−1445 cm −1 ).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Surface Modification of Au Nanoparticles with Heteroleptic Cu(I) Diimine Complexes

et al. 2020

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Gold colloidal nanoparticles (NPs) were functionalized in acetonitrile with a Cu(I) complex consisting of one 2,2′-bipyridine ligand possessing a lipoic acid moiety and one 2,9-dimesitylene-1,10-phenanthroline. UV electronic absorption, inductively coupled plasma-atomic emission spectroscopy, and scanning transmission electron microscopy with energy-dispersive X-ray analysis specifically targeting the Cu element were employed to confirm the grafting of the metallic complex on the Au NPs via Au–S bond formation and to probe its surface distribution and surface coverage. At the highest coverage achieved while retaining nanoparticle dispersibility, we estimate the molecular footprint of the complex at 0.71 nm2, corresponding to ∼7000 molecules over a 40 nm spherical particle. This is only four time less than what is reported for much smaller alkanethiols forming a compact self-assembled monolayer on similar gold nanoparticles. In the surface-enhanced Raman spectra (SERS), we underline a convenient marker band at ∼1000 cm–1; its frequency position is indicative of the complexation state of the surface-bound bipyridine molecules. From the analysis of the normal Raman spectra of the powders and the SERS data, the anchored tetrahedral complex is presumed to orient with the two polycyclic ligands predominantly normal to the surface and the most cumbersome substituted phenanthroline more peripherally placed.

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Interfacial spectroelectrochemical Raman study of the silver/1,10-phenanthroline system in chloride medium

Cited by 17 publications

References 31 publications

Effect of Surface Geometry on the Photochemical Reaction of 1,10-Phenanthroline Adsorbed on Silver Colloid Surfaces

Effect of Surface Geometry on the Photochemical Reaction of 1,10-Phenanthroline Adsorbed on Silver Colloid Surfaces

Electrochemical Carbon

Surface Modification of Au Nanoparticles with Heteroleptic Cu(I) Diimine Complexes

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