Electronic-structures of h2o.bf3 and related n-v addition-compounds - a combined eels-ups study in vapor-phase

The detailed electronic structure of the n-v addition compound H2O·BF3 has been investigated for the first time by a combined use of electron energy loss spectroscopy (EELS) and UV photoelectron spectroscopy (UPS) augmented by MO calculations. The calculated molecular orbital energies of H2O·BF3 agree well with the UPS results and have been used to assign the electronic transitions obtained from EELS and to construct an orbital correlation diagram. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

Depth profile composition studies of thin film CdS: Cu,S solar cells using XPS and AES

Surface composition and depth profile studies of hemiplated thin film CdS:CuzS solar cells have been carried out using x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques. These studies indicate that the junction is fairly diffused in the as-prepared cell. However, heat treatment of the cell at 210°C in air relatively sharpens the junction and improves the cell performance. Using the Cu(2p3p)/S(2p) ratio as well as the Cu(LVV)/(LMM) Auger intensity ratio, it can be inferred that the nominal valency of copper in the layers above the junction is Cut and it is essentially in the CUSS form. Copper signals are observed from layers deep down in the cell. These seem to appear mostly from the grain boundary region. From the observed concentration of Cd, Cu and S in these deeper layers and the Cu(LVV)/(LMM) ratio it appears that the signals from copper essentially originate partly from copper in CuS and partly from Cu2t trapped in the lattice. It is significant to note that the nominal valence state of copper changes rather abruptly from Cut to Cuz+ across the junction.

Bismuth tungsten-oxide bronzes - a study of intergrowth phases and related aspects

Reaction of bismuth metal with WO$_3$ in the absence of oxygen yields interesting bronze-like phases. From analytical electron microscopy and X-ray photoelectron spectroscopy, the product phases are found to have the general composition Bi$_x$ WO$_3$ with bismuth in the 3+ state. Structural investigations made with high resolution electron micrscopy and cognate techniques reveal that when x < 0.02, a perovskite bronze is formed. When x $\geqslant$ 0.02, however, intergrowth tungsten bronzes (i.t.b.) containing varying widths of the WO$_3$ slab are formed, the lattice periodicity being in the range 2.3-5.1 nm in a direction perpendicular to the WO$_3$ slabs. Image-matching studies indicate that the bismuth atoms are in the tunnels of the hexagonal tungsten bronze (h.t.b.) strips and the h.t.b. strips always remain one-tunnel wide. Annealed samples show a satellite structure around the superlattice spots in the electron diffraction patterns, possibly owing to ordering of the bismuth atoms in the tunnels. The i.t.b. phases show recurrent intergrowths extending up to 100 nm in several crystals. The periodicity varies considerably within the same crystal wherever there is disordered intergrowth, but unit cell dimensions can be assigned from X-ray and electron diffraction patterns. The maximum value of x in the i.t.b. phases is ca. 0.07 and there is no evidence for the i.t.b. phase progressively giving way to the h.t.b. phase with increase in x. Hexagonal tungsten bronzes that contain bismuth with x up to 0.02 can be formed by starting from hexagonal WO$_3$, but the h.t.b. phase seems to be metastable. Optical, magnetic and electron transport properties of the i.t.b. phases have been measured and it appears that the electrons become itinerant when x > 0.05.

X-ray spectroscopic study of chromium, nickel, and molybdenum compounds

Chemical shifts in the K-absorption edges, AE, of a series of chromium, nickel, and molybdenum compounds have been investigated. The AE values in a given series vary in the same direction as the metal-core-level binding energies obtained from X-ray photoelectron spectroscopy. The AI3 values are related to the effective atomic charge of the metal by a parabolic relation. In the case of molybdenum compounds, the chemical shifts of the K, emission lines vary in the same manner as M.

XPES studies of oxides of second- and third-row transition metals including rare earths

X-ray photoelectron spectroscopy has been employed to investigate oxides of second- and third-row transition metals, including those of rare earths. Systematics in the spin—orbit splittings and binding energies of core levels of the metals are described. In most of the cases studied, the dependence of the spin—orbit splittings on the atomic number Z is given by the relation ΔE = a(Z - Z0)4, where a is the quantum defect parameter and Z0 is the effective screening. Core-level binding energies are found to increase with the oxidation state of the metal. Most of the core-level binding energies are related to the atomic number Z by the expression E = x(Z - Z0)2, giving rise to linear plots of ln E versus ln Z. Specific features of individual oxides, with respect to satellites, multiplet structure, configuration mixing, and other properties are also discussed. The spectra of PrO2, Pr6O11, TbO2 and Tb4O7 are reported for the first time.

Molecularly adsorbed oxygen on metals: electron spectroscopic studies

Oxygen is shown to adsorb molecularly on gold as well as on Ag and Pt. UV and X-ray photoelectron spectroscopy and Auger electron spectroscopy have been employed to investigate electron states of molecularly adsorbed oxygen.

Surface electronic structure of the high-Tc oxides

Electron energy loss spectroscopy (EELS) has been employed to monitor surface conductivity changes in YBa2Cu3O7 as a function of temperature. Concomitant use of x-ray photoelectron spectroscopy (XPS) establishes that the formation of oxygen dimers with lowering of temperature is accompanied by a simultaneous increase of surface conductivity.

Nondeactivating Nanosized Ionic Catalysts for Water-Gas Shift Reaction

The water-gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nanosized catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2, and Ce1-xTixO2-delta. These catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), and it has been shown that Pt2+ in these reducible oxides result in solid solutions like Ti0.99Pt0.01O2-delta, Ce0.8Ti0.15Pt0.02O2-delta, and Ce0.98Pt0.02O2-delta. These catalysts were tested for the water gas shift reaction both ill the presence and absence of hydrogen. It was shown that Ti0.99Pt0.01O2-delta exhibited higher catalytic activity than Ce0.83Ti0.15Pt0.02O2-delta and Ce0.98Pt0.02O2-delta. Further, experiments were conducted to determine the deactivation of these catalysts. There was no sintering of Pt and no carbonate formation; therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ti4+ ions in the catalysts.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Plasma-enhanced synthesis of bioactive polymeric coatings from monoterpene alcohols: A combined experimental and theoretical study

This paper describes the synthesis and characterization of a novel organic polymer coating for the prevention of the growth of Pseudomonas aeruginosa on the solid surface of three-dimensional objects. Substrata were encapsulated with polyterpenol thin films prepared from terpinen-4-ol using radio frequency plasma enhanced chemical vapor deposition. Terpinen-4-ol is a constituent of tea tree oil with known antibacterial properties. The influence of deposition power on the chemical structure, surface composition, and ultimately the antibacterial inhibitory activity of the resulting polyterpenol thin films was studied using X-ray photoelectron spectroscopy (XPS), water contact angle measurement, atomic force microscopy (AFM), and 3-D interactive visualization and statistical approximation of the topographic profiles. The experimental results were consistent with those predicted by molecular simulations. The extent of bacterial attachment and extracellular polymeric substances (EPS) production was analyzed using scanning electron microscopy (SEM) and confocal scanning laser microscopy (CSLM). Polyterpenol films deposited at lower power were particularly effective against P. aeruginosa due to the preservation of original terpinen-4-ol molecules in the film structure. The proposed antimicrobial and antifouling coating can be potentially integrated into medical and other clinically relevant devices to prevent bacterial growth and to minimize bacteria-associated adverse host responses.

Radio frequency plasma enhanced synthesis of antifouling polymeric coatings from monoterpene alcohols

Radio frequency plasma enhanced chemical vapor deposition is currently used to fabricate a broad range of functional coatings. This work described fabrication and characterization of a novel bioactive coating, polyterpenol, for encapsulation of three-dimensional indwelling medical devices. The materials are synthesized from monoterpene alcohols under different input power conditions. The chemical composition and structure of the polyterpenol thin films were determined by Xray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, and atomic force microscopy (AFM). The application of polyterpenol coating to the substrate reduced surface roughness from 1.5 to 0.4 of a nanometer, and increased the water contact angle from to 9 to 72 degrees. The extent of attachment and extracellular polysaccharide (EPS) production of two medically relevant pathogens, Staphylococcus aureus and Staphylococcus epidermis were analyzed using scanning electron microscopy (SEM) and confocal scanning laser microscopy (CSLM). Application of polyterpenol coating fabricated at 10 W significantly inhibited attachment and growth of both pathogens compared to unmodified substrates, whilst addition of 50 W films resulted in an increased attachment, proliferation and EPS production by both types of bacteria when compared to unmodified surface. Marked dissimilarity in bacterial response between two coatings was attributed to changes in surface chemistry, nano-architecture and surface energy of polymer thin films deposited under different input power conditions.

Time evolution of graphene growth on SiC as a function of annealing temperature

We followed by X-ray Photoelectron Spectroscopy (XPS) the time evolution of graphene layers obtained by annealing 3C SiC(111)/Si(111) crystals at different temperatures. The intensity of the carbon signal provides a quantification of the graphene thickness as a function of the annealing time, which follows a power law with exponent 0.5. We show that a kinetic model, based on a bottom-up growth mechanism, provides a full explanation to the evolution of the graphene thickness as a function of time, allowing to calculate the effective activation energy of the process and the energy barriers, in excellent agreement with previous theoretical results. Our study provides a complete and exhaustive picture of Si diffusion into the SiC matrix, establishing the conditions for a perfect control of the graphene growth by Si sublimation.

Simultaneous adsorption of Cd(II) and phosphate on Al13 pillared montmorillonite

Al13 pillared montmorillonites (AlPMts) prepared with different Al/clay ratios were used to remove Cd(II) and phosphate from aqueous solution. The structure of AlPMts was characterized by X-ray diffraction (XRD), Thermogravimetric analysis (TG), and N2 adsorption–desorption. The basal spacing, intercalated amount of Al13 cations, and specific surface area of AlPMts increased with the increase of the Al/clay ratio. In the single adsorption system, with the increase of the Al/clay ratio, the adsorption of phosphate on AlPMts increased but that of Cd(II) decreased. Significantly enhanced adsorptions of Cd(II) and phosphate on AlPMts were observed in a simultaneous system. For both contaminants, the adsorption of one contaminant would increase with the increase of the initial concentration of the other one and increase in the Al/clay ratio. The enhancement of the adsorption of Cd(II) was much higher than that of phosphate on AlPMt. This suggests that the intercalated Al13 cations are the primary co-adsorption sites for phosphate and Cd(II). X-ray photoelectron spectroscopy (XPS) indicated comparable binding energy of P2p but a different binding energy of Cd3d in single and simultaneous systems. The adsorption and XPS results suggested that the formation of P-bridge ternary surface complexes was the possible adsorption mechanism for promoted uptake of Cd(II) and phosphate on AlPMt.

Photo-Electron Spectroscopic Studies Of The Adsorption Of Organic-Molecules With Lone Pair Orbitals On Transition-Metal Surfaces

Ultraviolet and x-ray photoelectron spectroscopy have been employed to investigate the adsorption of methanol, ethanol, diethylether, acetaldehyde, acetone, methyl acetate and methylamine on surfaces of Fe, Ni and Cu. All these molecules adsorb molecularly at low temperatures (≤100 K). Lone pair orbitals of these molecules are stabilized on these metal surfaces (by 0·4–1·0eV) due to molecular chemisorption. The molecules generally undergo transformations as the temperature is raised to 120 K or above. The new species produced seems to depend on the metal surface. Some of the product species identified are methoxy species, formaldehyde and carbon monoxide in the case of methanol and methyl acetate, ethoxy species in the case of ethanol and 2-propanol in the case of acetone.