Federico J. Williams

Surface Study of Lithium–Air Battery Oxygen Cathodes in Different Solvent–Electrolyte pairs

The O2/Li2O2 electrode reaction has been studied on low surface area Au electrodes in three solvent-electrolyte pairs (0.1 M LiPF6/DMSO, LiPF6/ACN, and LiBF4/ACN) using an electrochemical cell coupled to UHV XPS spectrometer, EQCM, AFM, and DEMS. The XPS spectra of the surfaces after treatment at selected electrode potentials for the O2 reduction and reoxidation of the surface show the presence of C and S from solvent decomposition and of F and P from electrolyte decomposition. Furthermore, Li 1s and O 1s peaks due to Li2O2 and decomposition products such as carbonate, organics, LiF, high oxidation sulfur, and phosphorus compounds were also observed. Using ACN instead of DMSO results in less solvent decomposition, whereas using LiBF4 results in less electrolyte decomposition. XPS, AFM, and EQCM show that O2 reduction products removal only takes place at very high overpotentials. In agreement with XPS which shows removal of carbonate surface species, DEMS confirms evolution of CO2 and consumption of O2 at 4.5 V, but LiF cannot be removed completely in a round trip of the Li-O2 battery cathode.

Some Evidence for the Formation of an Azo Bond during the Electroreduction of Diazonium Salts on Au Substrates

Molecular films obtained by electrochemical reduction of diazoniuim tetrafluoroborate salts [4-carboxybenzene (PhCOOH) and 4-amino-(2,3,5,6-tetrafluoro)-carboxybenzene (PhF(4)COOH)] on Au substrates and post-functionalization with an osmium pyridil-bipyridine complex are studied by a combination of X-ray photoelectron (XPS) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS). The spectroscopic evidence suggests the formation of N=N bonds tethering the complexes to Au. The surface coverage of the azo-bonded osmium complexes strongly depends on the electrode potential. The resulting tethered osmium redox centres were characterized by cyclic voltammetry and impedance spectroscopy. Similar electron transfer-rate constants were measured for both fluorinated and non fluorinated benzene-linked Os complexes.

Study of the oxygen vacancies changes in SnO2 polycrystalline thick films using impedance and photoemission spectroscopies

Changes in the concentration of oxygen vacancies within the grains of polycrystalline SnO2, due to different atmosphere exposures, were detected using impedance and photoemission spectroscopies. From measured capacitance values, variations of the potential barrier widths could be determined. It is shown that under the presence of an oxygen rich atmosphere, at relatively low temperature, the width of intergranular potential barriers increase to the point that grains become completely depleted of carriers. With subsequent exposure to vacuum, capacitance adopts a higher value, indicative of intergranular barriers and quasi-neutral regions at the center of the grains. X-ray and ultraviolet photoemission spectroscopy measurements showed that SnO2 samples treated in oxidizing or reducing environments have similar barrier heights and different work functions. Results are especially relevant in the study of mechanisms responsible for metal oxide gas sensing.

Monte Carlo simulations of monatomic steps dynamics on Si(100)-(2 × 1)

Abstract By means of Monte Carlo simulations the frozen pattern of a B -type step edge in the Si(100)-(2 × 1) surface is simulated. Sets of two dimers are attached and detached from the step according to the number of nearest and next-nearest neighbors. Average kink length, average kink separation and correlation length from experiments and modeling are presented in order to check the quality of our results. Experimental results are well reproduced by using measured experimental rates. The characteristics of the resulting step profile are also analyzed as a function of the step width.

A Monte Carlo simulation of the NO+CO reaction on Na-promoted platinum

An irreversible surface reaction lattice-gas model for the reaction of carbon monoxide and nitric oxide on an Na-modified Pt(111) surface is presented. The eVect of Na adatoms on the reaction kinetics is examined in terms of a ‘‘local’’ (i.e. short-range) model for alkali-promoted NO dissociation. Within this framework we also study the eVects of extending the range of alkali-induced NO dissociation from nearest neighbour to next nearest neighbour sites. The influence of varying amounts of sodium on overall catalytic activity, reaction kinetics, and on the N 2 /N 2 O selectivity are investigated by means of Monte Carlo simulations. It is found that the principal features of recent experimental data involving electrochemical promotion by Na of the CO+NO reaction over Pt are satisfactorily accounted for in terms of this model.

Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)

The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV).

Adsorption of 4,4′-Dithiodipyridine Axially Coordinated to Iron(II) Phthalocyanine on Au(111) as a New Strategy for Oxygen Reduction Electrocatalysis

The coordination of PySSPy to FePc was monitored by UV/Vis spectroscopy while the adsobed FePc, anchored by PyS-Au(111), was examined by in situ STM in 0.1 M HClO4 and X-ray photoelectron spectroscopy (XPS). Rotating-disc-electrode (RDE) and linear-sweep-voltammetry (LSV) studies on the resulting FePc-modified Au(111) electrodes in an oxygen-saturated 0.1 M NaOH electrolyte exhibit excellent electrocatalytic properties for the oxygen reduction reaction (ORR), with a smaller overpotential than that observed for Au(111) with FePc deposited by direct adsorption from a benzene solution.