Superlattices formed by interaction of polar solvents with Pt(111) surfaces studied by LEED, Auger spectroscopy and thermal desorption mass spectrometry

Garwood, Gerald A.; Hubbard, Arthur T.

doi:10.1016/0039-6028(82)90025-5

Cited by 35 publications

(19 citation statements)

References 106 publications

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“…Such behavior indicates that there is a second electrode-passivation process. Hubbard and co-workers (20,21) have studied the interaction of aprotic solvents with single crystals of Pt in the gas phase and found that MeCN, Me2SO, pyr, and DMF chemisorb strongly and irreversibly on Pt, whereas water does not absorb to an appreciable extent. In another study (22) they observed that when a Pt electrode is immersed into pure Me2SO for 10 min, rinsed with H20, and transferred to an aqueous solution, adsorption of H2 and I2 on the Pt surface is prevented.…”

Section: Discussionmentioning

confidence: 99%

Determination of dissolved hydrogen and effects of media and electrode materials on the electrochemical oxidation of molecular hydrogen

Barrette¹,

Sawyer²

1984

Anal. Chem.

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Section: Discussionmentioning

confidence: 99%

Determination of dissolved hydrogen and effects of media and electrode materials on the electrochemical oxidation of molecular hydrogen

Barrette¹,

Sawyer²

1984

Anal. Chem.

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“…1, No. I , 1985 53 2 - ( 7 ) The directions of the electric field for s (out of plane) and p (in plane) polarizations are shown for incoming and outgoing propagation directions, designated by + and -superscripts, respectively. and equipped with stops and apertures to give an -f/15 beam focusing to an -3-mm spot.…”

Section: Methodsmentioning

confidence: 99%

“…IR spectra of adsorbates were taken by reflection of the incident beam at an angle of incidence of 87°(3°off glancing) using p-polarized radiation. A nitrogen-purged Digilab 15-B Fourier transform spectrometer was used with modified optics to permit focusing outside the instrument (7) Brown, N. M. D.; Floyd, R. B.; Walmsby, D. G. J. Chem. Soc., Faraday Trans.…”

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Spontaneously organized molecular assemblies. 2. Quantitative infrared spectroscopic determination of equilibrium structures of solution-adsorbed n-alkanoic acids on an oxidized aluminum surface

Allara¹,

1985

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Taken together, the data show that closest packed, oriented monolayers of n-alkanoic acids can be formed by adsorption from dilute solution. The formation of these quasi-two-dimensional organic surface phases is characterized by complicated kinetics in which surface and/or monolayer defects, as well as impurities, seemingly play important roles. The structures so obtained are dynamic in nature in that they undergo rapid exchange with comparable ligands in solution. These results, and those presented in the following paper, further suggest an important limitation to closest-packed, self-assembly on this substrate which is related directly to the length of the alkyl chain. The data further show that oleophobicity is an insufficiently sensitive probe to determine the formation of equilibrium closest packed structures. In a companion paper we describe these structures and their relationship to many of the above observations in detail. Registry No. n-Infrared reflection spectroscopy has been applied to the determination of the structures of adsorbed monolayer films of n-alkanoic acids on oxidized aluminum substrates. Acids of 16-22 carbons, terminated by methyl, vinyl, or propargyl groups, were absorbed from hexadecane solution at 25 O C , using immersion times up to several days. These results, together with those for perdeuterated acids, indicate that close-packed assemblies are formed with extended alkyl tails oriented with their chain axes tilted away from normal to the surface with a value of -10" for the longer chains. Frequency shifts to higher values are observed for CH stretching modes of the vinyl and propargyl terminal groups measured in monolayer films compared to the bulk acids. These shifts are of similar magnitude to gas-liquid phase shifts for these groups and imply the environment of the ambient-monolayer interface exhibits very diminished intermolecular interactions for these terminal groups compared to the bulk. The spectra clearly show that chemisorption occurs by proton dissociation to form carboxylate species. Examination of both line width and peak positions of the carboxylate stretching modes suggests a variety of binding geometries of the carboxylate groups to the surface exists. These results lend support to the general concept of forming stable, oriented and ordered two-dimensional organic films by solution adsorption and show the utility of applying surface vibrational spectroscopy to structural determination in these films.

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“…To this end, experiments have been carried out to investigate the interactions of these solvents with metal surfaces. Electrochemical studies have indicated that solvents interact with transition metal surfaces, affecting fundamental electrochemical properties and the rates of reactions at these electrodes. − Different solvents, such as DMSO, DMF, and THF, have distinct and electrode-dependent effects on the potential of zero charge (PZC), capacitance, and other fundamental surface electrochemical properties. ,− Differences in PZC and capacitance among different solvents, and metals, originate at least in part from differences in metal–solvent interactions, including possible chemisorption and its effect on interfacial solvent orientation. ,,− Spectroscopic experiments − have also been used to study solvent–metal interactions. For example, spectroscopic evidence indicates a strong chemisorption of DMSO on Pt, and also significant interaction with Au , and Ag, displaying preferential adsorption to step sites .…”

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Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

2021

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Interfaces between solvents and transition metals play a critical role in many catalytic and electrochemical systems. In this work, we use density functional theory (DFT) to study the interactions between several common nonaqueous solvents and a number of transition metal surfaces. We investigate trends in binding energies among the metals, and the influence of specific surface sites and facets. We examine the electrostatic field dependence of the most stable binding configurations, and shed light on experimentally observed field-dependent or potential-dependent adsorption structures. We demonstrate that the reorientation of DMSO on noble metal surfaces can occur with only a relatively small change in the surface dipole moment; this result is simultaneously consistent with experimental evidence for field-dependent reorientation and measurements of surprisingly low differential capacitance of DMSO on noble metals. These results contribute to understanding competitive adsorption effects in catalysis, and also have implications for fundamental surface properties such as the surface structure, solvated work function, and potential of zero charge.

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Superlattices formed by interaction of polar solvents with Pt(111) surfaces studied by LEED, Auger spectroscopy and thermal desorption mass spectrometry

Cited by 35 publications

References 106 publications

Determination of dissolved hydrogen and effects of media and electrode materials on the electrochemical oxidation of molecular hydrogen

Determination of dissolved hydrogen and effects of media and electrode materials on the electrochemical oxidation of molecular hydrogen

Spontaneously organized molecular assemblies. 2. Quantitative infrared spectroscopic determination of equilibrium structures of solution-adsorbed n-alkanoic acids on an oxidized aluminum surface

Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

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