Platinum/graphene nanosheet/SiC contacts and their application for hydrogen gas sensing

Pt/graphene nanosheet/SiC based devices are fabricated and characterized and their performances toward hydrogen gas are investigated. The graphene nanosheets are synthesized via the reduction of spray-coated graphite oxide deposited onto SiC substrates. Raman and X-ray photoelectron spectroscopies indicate incomplete reduction of the graphite oxide, resulting in partially oxidized graphene nanosheet layers of less than 10 nm thickness. The effects of interfaces on the nonlinear behavior of the Pt/graphene and graphene/SiC junctions are investigated. Current-voltage measurements of the sensors toward 1% hydrogen in synthetic air gas mixture at various temperatures ranging up to 100. ° C are performed. From the dynamic response, a voltage shift of ∼100 mV is recorded for 1% hydrogen at a constant current bias of 1 mA at 100. °C. © 2010 American Chemical Society.

Interaction of carbon monoxide with bimetallic overlayers

Interaction of carbon monoxide with a few chosen bimetallic overlayers has been investigated along with the core-level binding energies of the deposited metals by employing X-rays as well as UV photoelectron spectroscopies. Core-level binding energies of the deposited metals around monolayer coverages (0 similar to 1) are significantly different than those at high coverages or of the pure metals. Bimetallic overlayers such as Ni/Au and Cu/Pt showing large negative shifts in the surface core-level binding energy of the deposited metal interact strongly with carbon monoxide. In the case of Ni/Au (0(Ni) similar to 0.85), CO dissociates around 280 K. In contrast to this behavior, the interaction of CO with Pd/Mo or W, showing large positive shifts in the surface core-level binding energy, is very weak, and the CO desorption temperature is much lower than that from the clean Pd metal surface. The CO desorption temperature generally increases as the surface core-level shift of the deposited metal becomes more negative; the separation between the (5 sigma + 1 pi) and 4 sigma levels of CO also increases in this direction. These results suggest that the variation in the strength of interaction of CO with bimetallic overlayers is a chemical manifestation of the shift in the surface core-level binding energies of the deposited metals at monolayer coverages.

Single crystalline magnetite, maghemite, and hematite nanoparticles with rich coercivity

One-pot synthesis of amorphous iron oxide nanoparticles with two different dimensions (<5 nm and 60 nm) has been achieved using the reverse micelle method, with <5 nm nanoparticles separated from the stable colloid by exploiting their magnetic behaviour. The transformation of the as-prepared amorphous powders into Fe3O4 and Fe2O3 phases (gamma and alpha) is achieved by carrying out controlled annealing at elevated temperatures under different optimized conditions. The as-prepared samples resulting from micellar synthesis and the corresponding annealed ones are thoroughly characterized by powder X-ray diffraction, transmission electron microscopy (TEM), and by Raman and X-ray photoelectron spectroscopies. Expectedly, the magnetic characteristics of Fe3O4 and Fe2O3 phase (gamma and alpha) nanoparticles are found to have strong dependence on their phase, dimension, and morphology. The coercivity of Fe3O4 and Fe2O3 (gamma and alpha) nanoparticles is reasonably high, even though high resolution TEM studies bring out that these nanoparticles are single crystalline. This is in contrast with previous reports wherein poly-crystallinity of iron oxides nanoparticles has been regarded as a prerequisite for high coercivity.

Role of spectator ions in influencing the properties of dopant-free ZnO nanocrystals

Towards fundamental studies and potential applications, achieving precise control over the generation of defects in pure ZnO nanocrystals has been always intriguing. Herein, we explored the rote of spectator ions (Co2+ and Ni2+) in influencing the functional properties of ZnO nanocrystals. The crystalline quality, phase purity, and composition of as-prepared samples were thoroughly established by powder X-ray diffraction, electron microscopy (TEM and STEM), and by Raman and X-ray photoelectron spectroscopies (XPS). Despite the presence of Co2+ and Ni2+ ions in the reaction mixture, STEM-energy dispersive spectroscopy (EDS), XPS analysis, and inductively-coupled plasma mass spectrometry (ICP-MS) revealed that the ZnO nanocrystals formed are dopant-free. Even so, their luminescence and magnetic properties were substantially different from those of pure ZnO nanocrystals synthesized using a similar methodology. We attribute the origin of these properties to the defects associated with ZnO nanocrystals generated under different but optimized conditions.

射频磁控溅射法制备TiO2-xNX薄膜的结构性能研究

利用射频磁控溅射法室温下在Si（100）衬底上制备了N掺杂的TiO2薄膜，并且采用x射线衍射（XRD）、X射线光电子能谱（XPS）和透射光谱对薄膜进行了表征。XRD结果表明在纯Ar和N2（33．3％）／Ar气氛下制备的TiO2-xNx薄膜均为单一的金红石相，薄膜结晶性良好，呈高度（211）择优取向，而在N2（50．0％）／Ar下制备的薄膜结晶性明显变差；对于N掺杂的TiO2薄膜，XPS表明部分N原子进入TiO2晶格，并且以N—Ti—O、N—O键以及间隙式N原子形式存在；透射光谱表明掺N后的TiO2薄膜吸收边发生了红移。

The growth of ZnO on bcc-In2O3 buffer layers and the valence band offset determined by X-ray photoemission spectroscopy

This work was supported by the 863 High Technology R&D Program of China (Grant Nos. 2007AA03Z402 and 2007AA03Z451), the Special Funds for Major State Basic Research Project (973 program) of China (Grant No. 2006CB604907), and the National Science Foundation of China (Grant Nos. 60506002 and 60776015). The authors express their appreciation to Dr. Tieying Yang and Prof. Huanhua Wang (Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences) for XRD measurements and helpful discussions.

Characteristics of the conductive polyimide film surfaces induced by ultraviolet laser beam

A conducting layer with the conductivity of 1.2 Omega(-1)cm(-1) stripped in a solvent from KrF-laser-irradiated polyimide thin film is taken as a sample to determine the microstructure of the conducting layer. Fourier-transform infrared and X-ray photoelectron spectroscopies show the formation of the carbon-rich clusters after irradiation. The element analysis gives the atomic ratio of C:H:N:O for the carbon-rich cluster as 60:20:3:1. Wide-angle X-ray diffraction indicates that the conducting layer is mainly amorphous carbon with a small amount of the short-range ordered carbon-rich clusters. This study suggests a structural model with three-layer carbon sheets linked together in a random fashion for the short-range ordered carbon-rich clusters. The interplanar spacing is 3.87 Angstrom and the layer diameter 25 Angstrom. The transport model of variable-range hopping in three dimensions is used to explain the conducting behavior of the conducting layer. In our case, the short-range ordered carbon-rich clusters are assumed to be conducting islands dispersed in the amorphous carbon-rich cluster matrix.

Extrusion and characterization of functionalized cellulose whiskers reinforced polyethylene nanocomposites

The surface of ramie cellulose whiskers has been chemically modified by grafting organic acid chlorides presenting different lengths of the aliphatic chain by an esterification reaction. The occurrence of the chemical modification was evaluated by FTIR and X-ray photoelectron spectroscopies, elemental analysis and contact angle measurements. The crystallinity of the particles was not altered by the chain grafting, but it was shown that covalently grafted chains were able to crystallize at the cellulose surface when using C18. Both unmodified and functionalized nanoparticles were extruded with low density polyethylene to prepare nanocomposite materials. The homogeneity of the ensuing nanocomposites was found to increase with the length of the grafted chains. The thermomechanical properties of processed nanocomposites were studied by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA) and tensile tests. A significant improvement in terms of elongation at break was observed when sufficiently long chains were grafted on the surface of the nanoparticles. It was ascribed to improved dispersion of the nanoparticles within the LDPE matrix. (C) 2009 Elsevier Ltd. All rights reserved.

Black and green pigments based on chromium-cobalt spinels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Incorporation of Ca, P, and Si on bioactive coatings produced by plasma electrolytic oxidation: The role of electrolyte concentration and treatment duration

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigations of oxide superconductors by x-ray absorption, photoemission and cognate spectroscopies

X-ray absorption spectra, X-ray photoelectron spectra and Auger spectra of cuprate superconductors are discussed. The studies establish the absence of Cu3+ for all practical purposes, but point out the importance of oxygen holes. X-ray photoelectron spectra of BaBi0.25Pb0.75O3 and related compounds are also examined.

Spectroscopic investigation of the polymerisation of pyrrole and thiophene within zeolite channels

The reaction of pyrrole and thiophene monomers with copper- or nickel-exchanged mordenite has been investigated using X-ray photoelectron (XPS) and photoacoustic infrared (PAIRS) spectroscopies. Because of the differing oxidising powers of the cations studied, polymerisation occurred only with copper-exchanged mordenite. PAIRS and XPS data indicated that both polypyrrole and polythiophene were partially oxidised when synthesised within the zeolite structure. IR spectra of polythiophene and polythiophene and polypyrrole showed intense bands typical of ring vibrations which could couple to the large dipole change induced by charges moving along the polythiophene chain. In addition it was noted that only vibrations typical of oxidised polymer structures were recorded, suggesting that the charge carrier was located within these segments. Furthermore, N 1s spectra contained a high binding energy peak at 402.5 eV which was attributed to a positively charged nitrogen species, in agreement with IR data. Significantly, C 1s spectra confirmed that molecular wires were formed within the confines of the zeolite lattice. Depth-profiling experiments suggested that polypyrrole was distributed throughout the entire zeolite host. By contrast, polythiophene may have been restricted to the uppermost zeolite channels owing to the ability of sulfur species to bond to CuI sites [produced by reduction of copper(II) ions during the polymerisation process], thus obstructing movement along the channels.

Photoelectron spectroscopy of HCCN- and HCNC- reveals the quasilinear triplet carbenes, HCCN and HCNC

Negative ion photoelectron spectroscopy has been used to study the HCCN- and HCNC- ions. The electron affinities (EA) of cyanocarbene have been measured to be EA(HCCN (X) over tilde (3)Sigma(-)=2.003+/-0.014 eV and EA(DCCN (X) over tilde (3)Sigma(-))=2.009+/-0.020 eV. Photodetachment of HCCN- to HCCN (X) over tilde (3)Sigma(-) shows a 0.4 eV long vibrational progression in nu(5), the H-CCN bending mode; the HCCN- photoelectron spectra reveal excitations up to 10 quanta in nu(5). The term energies for the excited singlet state are found to be T-0(HCCN (a) over tilde (1)A('))=0.515+/-0.016 eV and T-0(DCCN (a) over tilde (1)A('))=0.518+/-0.027 eV. For the isocyanocarbene, the two lowest states switch and HCNC has a singlet ground state and an excited triplet state. The electron affinities are EA(HCNC (X) over tilde (1)A('))=1.883+/-0.013 eV and EA((X) over tilde (1)A(') DCNC)=1.877+/-0.010 eV. The term energy for the excited triplet state is T-0(HCNC (a) over tilde (3)A("))=0.050+/-0.028 eV and T-0(DCNC (a) over tilde (3)A("))=0.063+/-0.030 eV. Proton transfer kinetics in a flowing afterglow apparatus were used to re-measure the enthalpy of deprotonation of CH3NC to be Delta(acid)H(298)(CH3NC)=383.6+/-0.6 kcal mol(-1). The acidity/EA thermodynamic cycle was used to deduce D-0(H-CHCN)=104+/-2 kcal mol(-1) [Delta(f)H(0)(HCCN)=110+/-4 kcal mol(-1)] and D-0(H-CHNC)=106+/-4 kcal mol(-1) [Delta(f)H(0)(HCNC)=133+/-5 kcal mol(-1)]. (C) 2002 American Institute of Physics.

Negative-ion photoelectron spectroscopy, gas-phase acidity, and thermochemistry of the peroxyl radicals CH3OO and CH3CH2OO

Methyl, methyl-d(3), and ethyl hydroperoxide anions (CH3OO-, CD3OO-, and CH3CH2OO-) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer, gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities: EA[CH3OO, (X) over tilde (2)A"] = 1.161 +/- 0.005 eV, EA[CD3OO, (X) over tilde (2)A"] = 1.154 +/- 0.004 eV, and EA[CH3CH2OO, (X) over tilde (2)A"] = 1.186 +/- 0.004 eV. The photoelectron spectra yield values for the term energies: DeltaE((X) over tilde 2A"-(A) over tilde 2A')[CH3OO] = 0.914 +/- 0.005 eV, DeltaE((X) over tilde (2)A"-(A) over tilde 2A') [CD3OO] = 0.913 +/- 0.004 eV, and DeltaE((X) over tilde (2)A"-(A) over tilde (2)A')[CH3CH2OO] = 0.938 +/- 0.004 eV. A localized RO-O stretching mode was observed near 1100 cm(-1) for the ground state of all three radicals, and low-frequency R-O-O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow-selected ion flow tube k(FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Delta (acid)G(298)(CH3OOH) = 367.6 +/- 0.7 kcal mol(-1), Delta (acid)G(298)(CD3OOH) = 367.9 +/- 0.9 kcal mol(-1), and Delta (acid)G(298)(CH3CH2OOH) = 363.9 +/- 2.0 kcal mol(-1). From these acidities we have derived the enthalpies of deprotonation: Delta H-acid(298)(CH3OOH) = 374.6 +/- 1.0 kcal mol(-1), Delta H-acid(298)(CD3OOH) = 374.9 +/- 1.1 kcal mol(-1), and Delta H-acid(298)(CH2CH3OOH) = 371.0 +/- 2.2 kcal mol(-1). Use of the negative-ion acidity/EA cycle provides the ROO-H bond enthalpies: DH298(CH3OO-H) 87.8 +/- 1.0 kcal mol(-1), DH298(CD3OO-H) = 87.9 +/- 1.1 kcal mol(-1), and DH298(CH3CH2OO-H) = 84.8 +/- 2.2 kcal mol(-1). We review the thermochemistry of the peroxyl radicals, CH3OO and CH3CH2OO. Using experimental bond enthalpies, DH298(ROO-H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The "electron affinity/acidity/CBS" cycle yields Delta H-f(298)[CH3OO] = 4.8 +/- 1.2 kcal mol(-1) and Delta H-f(298)[CH3CH2OO] = -6.8 +/- 2.3 kcal mol(-1).