Interfacial structure of dimethylsulfoxide at Ag electrodes from surface enhanced Raman scattering and differential capacitance

Shen, Aijin; Pemberton, Jeanne E.

doi:10.1016/s0022-0728(99)00427-1

Cited by 25 publications

(33 citation statements)

References 39 publications

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“…On the other hand, the S–O stretching band frequency is significantly downward shifted by more than 30 cm –1 , suggesting a decrease of the S–O bond order. Unexpectedly for gold, this is consistent with the interaction of DMSO with a gold surface preferentially in the O-bonded configuration. − …”

Section: Resultssupporting

confidence: 57%

Tailoring the Shape of Anisotropic Core–Shell Au–Ag Nanoparticles in Dimethyl Sulfoxide

et al. 2019

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Shape and size control of metal nanoparticles at the nanoscale is a crucial step in the development of diverse applications ranging from catalysis to plasmonics and surface-enhanced Raman spectroscopy (SERS). For the seed-mediated growth of nanocrystals, it is well established that the final morphology is dictated not only by the crystallinity of the seed but also by surfactant and additives. However, the systematic study of the impact and the fate of these additives to elucidate the growth mechanism remains challenging. Here, we show that the addition of dimethyl sulfoxide (DMSO) for the silver growth on gold nanorod seeds allows tailoring the shape of core–shell Au@Ag from truncated cuboids to octahedra. The combination of surface enhanced Raman scattering and X-ray photoelectron spectroscopies revealed the key role played by DMSO and its fate upon silver reduction.

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Section: Resultssupporting

confidence: 57%

Tailoring the Shape of Anisotropic Core–Shell Au–Ag Nanoparticles in Dimethyl Sulfoxide

et al. 2019

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“…For the multilayer formed on gold, the SERS spectra (red curves in Figure 1b and Figure S3), compared with that of DSBD powder, showed the disappearance of bands associated with the NN + groups at 2267 cm −1 (Figure S3) and the C−NN + group at 635 cm −1 , indicating that diazonium cations were electrochemically reduced to the aryl radicals coupled to the release of gaseous N 2 , 28 while other bands associated with both the phenyl (997, 1071, 1138, 1186, 1573, and 1590 cm −1 ) and the S−S (532 and 545 cm −1 ) groups remained, but with frequencies slightly shifted due to immobilization on gold after electrografting. In addition, some new bands have been identified and assigned as following: Bands at 333, 382, 670, 694, and 1023 cm −1 are due to the DMSO solvent 29 used in the SERS study, the band at 495 cm −1 is associated with the out-ofplane benzene ring vibration mode upon grafting, 30 the bands of 1239 and 1284 cm −1 are associated with the ring breathing modes in the linked phenyl groups, suggesting the formation of multilayer structure, 12 and the bands at 1389 and 1428 cm −1 are associated with the NN group and phenyl-NN group, indicating the azo group coupling during the multilayer formation, 31 which has been ascertained by Mesnage et al 32 Apart from these bands associated with DSBD multilayers and DMSO solvents, an important feature of the SERS spectrum is the appearance of a new band at 419 cm −1 , which is assigned to the Au−C stretch vibration based on the reported results of spontaneous reduction of nitrophenyl diazonium salt on gold nanoparticles 12 and nanorods 13 and on the chemical reduction of aminotriazole diazonium salt on gold nanoparticles. 33 The electrografted multilayer has a structure of Au−(Ar−S− S−Ar) n that can be further degraded to a monolayer of Au− Ar−S − by chemical or electrochemical cleavage of the S−S bonds within the multilayer.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Spectroscopic Identification of the Au–C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold

Guo

Zhang

et al. 2016

Langmuir

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Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar), which can be further degraded to a monolayer of Au-Ar-S by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

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“…For example, a pair of peaks at 666 and 698 cm −1 can be assigned to the CSC symmetric and asymmetric stretching mode of the DMSO, respectively, while that at 1044 cm −1 is assigned to the S−O stretching mode of the DMSO. 29,30 Some new spectral features appear as the potential is swept negative. As shown Figure 3a, two broad Raman peaks appear around 490 and 1105 cm −1 at 2.62 V. The peak intensities increase with the potential, while the peak positions gradually shift to a lower frequency region.…”

Section: Articlementioning

confidence: 99%

In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery

2015

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To develop a lithium−oxygen (Li-O 2 ) battery with an extremely high specific energy, mechanisms for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) on a flat gold electrode in the aprotic polar solvent of dimethyl sulfoxide (DMSO) has been systematically investigated by electrochemistry in combination with in situ UV−vis absorption spectroscopy, surface-enhanced Raman vibrational spectroscopy (SERS), and ex situ infrared spectroscopy. In the Li-free DMSO solution, O 2 is efficiently reduced to the superoxide, which forms an ion-pair with the tetrabutylammonium (TBA) cation and shows an excellent stability in DMSO. The adsorption of the superoxide on the gold electrode surface has been observed by an in situ SERS measurement. When the Li-ion is included in the DMSO, O 2 can be further electrochemically reduced to lithium peroxide (Li 2 O 2 ) and deposited on the electrode surface, although a large amount of superoxide is still produced in the solution. The latter oxide shows a UV−vis absorption spectrum similar to that polarized in the Li-free DMSO solution, implying that Li-ions solvated by DMSO make ion-pairs with superoxide (denoted as LiO 2 ) in solution.No evidence for the disproportionation reaction of LiO 2 to Li 2 O 2 , one of the known reaction mechanisms proposed before, has been obtained in the bulk solution and on the electrode surface in the present study. The formation of Li 2 O 2 is controlled by reaction kinetics and Li-ion diffusion. The Li 2 O 2 thin-film is terminated at a certain film thickness on the electrode surface. On the basis of the quantitative analyses of the in situ spectroscopic observations, the partial yields for LiO 2 and Li 2 O 2 have been estimated to elucidate the mechanism for the ORR/OER processes. The present results are discussed in comparison to previous observations on porous carbon cathodes regarding the surface area, morphology, and three-phase interface on the electrode and solution interface.

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Interfacial structure of dimethylsulfoxide at Ag electrodes from surface enhanced Raman scattering and differential capacitance

Cited by 25 publications

References 39 publications

Tailoring the Shape of Anisotropic Core–Shell Au–Ag Nanoparticles in Dimethyl Sulfoxide

Tailoring the Shape of Anisotropic Core–Shell Au–Ag Nanoparticles in Dimethyl Sulfoxide

Spectroscopic Identification of the Au–C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold

In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery

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