Polarizability-Induced Vibrational Shifts for Infrared Spectroscopy of Molecular Surfaces: Xe as a Surface Probe of Hexadecanethiol Self-Assembled Monolayers and Hexane Films on Au(111).

Adsorption of atomic and molecular species on several model film surfaces is shown to lead to systematic and reproducible spectral shifts for infrared absorption peaks associated with vibrations at the film/adsorbate interface. These shifts to lower frequencies are demonstrated to be versatile spectral signatures of this exposed interface. While this is found to occur for a wide variety of adsorbates, this work focuses on the adsorption of Xe onto molecular surfaces. By using the pre-Xe film reflectivity as a reference in calculating the spectra, the changes induced by Xe adsorption due to van der Waals forces are isolated from the conventional film spectrum which contains both surface and subsurface spectral contributions. A model-free algorithm containing two user-defined fitting parameters is described to reconstruct the spectrum of the surface from which these shifted features originate. The high surface sensitivity of the technique is exhibited for the case of a hexadecanethiol self-assembled monolayer (SAM), where the reconstruction algorithm successfully reproduces all peaks attributed to the methyl tail groups with minimal spectral contributions from the methylene groups composing the subsurface chain backbone; such methylene spectral features dominate the conventional surface infrared spectra. The algorithm is applied to films of hexane to demonstrate its application to disordered multilayer films as well. The technique and reconstruction algorithm are shown to extract spectroscopic information from the uppermost ∼0.3 nm of the film, representing the fundamental limit of vibrational surface sensitivity. Rudimentary modeling of a CO-Xe3 system using Morse/Lennard-Jones interactions demonstrates the expected distance dependence of the van der Waals interaction which gives rise to the observed vibrational spectral shifts.

Determination of the surface area of Pd and nanometric Au aggregates supported on a micrometric solid support by thiol adsorption and GC-MS.

A new sensitive and specific method to measure gold and palladium surface areas using alkanethiol adsorption coupled with analysis by gas chromatography with mass spectrometry detection has been developed. The effectiveness of the method was tested with metallic samples having a known surface area. The results have also been compared with BET specific surface area measurements. The results obtained with both methods show a good correlation.

Localization vs conduction: anionic excitations in alkanethiol self-assembled monolayers.

Low-energy (6-11 eV) electron injection into Xe-coated self-assembled alkanethiol monolayers (SAMs) is reported. At most energies, the presence of the Xe film has negligible effect on the incident electrons, which penetrate the overlayer and induce significant C--H bond rupture at the terminal methyl sites and the subsurface methylene sites of the organic substrates. However, irradiation at 7.7 +/- 0.2 eV can lead to resonant electronic excitations of the Xe adsorbates to create transient anionic states in the Xe overlayer. Transfer of anionic excitations from the Xe overlayer to the SAM initially prepares excited anionic states at the terminal CH3 groups and leads to highly selective dissociations at the methyl sites, with negligible conduction along the alkane chain which would lead to subsurface C-H bond rupture at the methylene sites. These results demonstrate that the mobility of electronically excited charged states along the alkanethiol chains is significantly less than that of simple excess electrons and that highly site-selective chemical modifications can be induced by low-energy electrons in these highly homogeneous organic films.

Gold film surface preparation for self-assembled monolayer studies.

Evaporated gold films are frequently used as substrates for the study of biomolecular adsorbates, nanoparticle systems, amd partial and full monolayer films. These studies often benefit from a predeposition cleaning of the surface that removes adventitiously adsorbed material from laboratory contaminants. Scanning tunneling microscopy (STM) is used in this study to explore the microscopic consequences of two pretreatment protocols used in literature reports of self-assembled monolayers, based on sulfochromic and piranha acid solutions. These measurements show that treatment of the Au/mica surface with piranha acid can lead to extensive and uncontrolled etching of the surface and severe disruption of the surface topography; extended exposure causes the precipitation of crystallites on the surface that are highly mobile during STM imaging processes. Exposure of Au/mica surfaces to sulfochromic acid leads to the formation of permanent etch pits of the surface that are exclusively one Au layer deep; extended exposure leads to progressive etching and oxidation of the surface, ultimately leading to the formation of 0.33-0.36 nm high islands on the otherwise flat Au/mica surface. The piranha acid solutions are significantly more likely to cause the Au film to delaminate from the mica support than are the sulfochromic acid solutions. These results show that sulfochromic surface preparation is a direct and reliable method for the elimination of organic residues from Au(111)-textured surfaces, while causing a minimum of structural and chemical surface damage.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.

The mechanism of hydrogen formation induced by low-energy electron irradiation of hexadecanethiol self-assembled monolayers.

The desorption of molecular hydrogen during low-energy electron irradiation of self-assembled monolayers containing n-alkanethiols has been previously reported, yet to date, there is no consensus as to the mechanism for the formation of this ubiquitous product. In this study, mixed monolayers containing known ratios of perhydrogenated and perdeuterated alkanethiols were chemisorbed to Au(111)/mica substrates and used as targets for low-energy electron irradiation; by measuring the electron-stimulated production of H(2), D(2), and HD as a function of the film composition, we unambiguously show that the desorbing molecular hydrogen is formed via a two-step bimolecular reaction process. The initial electron-molecule scattering event produces a reactive atomic fragment, which then abstracts a hydrogen atom from a nearby molecular site to produce the measured bimolecular yields; the contribution of one-step unimolecular dissociation channels to the overall molecular hydrogen yields is below the approximately 5% detection limit. The dependence of the electron-induced modifications to the film on the incident electron energy suggests that the primary event is dissociative electron attachment, and that the primary reactive fragment is most likely H(-). Quantitative analysis of the product yields shows that while approximately 80% of the molecular hydrogen is formed by this bimolecular mechanism within the film, the remaining 20% is formed from reactive atomic fragments that are ejected from the film and subsequently react with residual H(2)O adsorbed on the chamber walls.