Formation and decomposition of thin rhodium oxide films

Interaction of O₂ with Rh (poly) and Rh (100) has been studied by Auger Electron Spectroscopy and thermal desorption method at O₂ pressures of 10^–5–10³ Pa and at 400–1600 K. At P(O₂)<10^–5 Pa chemisorption of O₂ occurs, at P(O₂)=10^–5–10^–1 Pa surface oxides are formed, at P(O₂)>1.0 Pa a bulk Rh₂O₃ oxide starts to grow. The growth of rhodium oxide film proceeds via the Cabrera-Mott mechanism. Its decomposition occurs via a mechanism including electron transfer across the oxide film, O₂ desorption from the surface layer and rearrangement of the oxide layer.     

Synthesis and characterization of ZnO nanoparticles by thermal decomposition of a curcumin zinc complex

ZnO nanoparticles were generated by thermal decomposition of a binuclear zinc (II) curcumin complex as single source precursor. Thermal behavior of the precursor showed a considerable weight loss at about 374 °C by an exothermic reaction with a maximum weight loss rate of 14%/min. Complete decomposition of precursor was observed within 49 min with a heating rate of 10 °C/min. Synthesized nanoparticles have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and selected area electron diffraction microscopy. Results revealed monodispersed hexagonal zincite structure with an average size of 117 ± 4 nm.     

Hydrothermal synthesis of 2D ordered macroporous ZnO films

The ZnO films with two-dimensional ordered macroporous structure were successfully fabricated through hydrothermal crystal growth of ZnO on the ZnO substrate covered with a monolayer of polystyrene (PS) spheres as template. The precursor solution of hydrothermal crystal growth of ZnO were prepared by equimolar solution of Zn(NO₃)₂·6H₂O and hexamethylenetramine (HMT). The confinement effect of the PS spheres template on the growth of ZnO nanorods and the influence of sodium citrate on the crystal growth of ZnO had been studied. The film surface morphology and the preferential growth of ZnO crystal were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Also, the photoluminescence spectrum of ZnO films had been measured, and the corresponding mechanism was discussed. __________ Translated from Chemistry, 2007, 70 (8): 587–592 [译自: 化学通报]     

Fast synthesis of ZnO nanostructures by laser-induced decomposition of zinc acetylacetonate

A CO2 laser (lambda = 10.6 microm) was used to heat a solution of water and alcohol saturated by Zn(AcAc)2 on a fused quartz substrate in open air. After only a few seconds of irradiation, various zinc oxide (ZnO) nanostructures including nanorods and nanowires are formed near the center of the irradiated zone, surrounded by a porous thin film of ZnO nanoparticles. The type of structures produced and their localization on the substrate can be varied by selecting adequate irradiation time and laser power ranges. The deposits have been analyzed using SEM, TEM, EDS, XRD, and Raman spectroscopy, revealing that the nanorods (aspect ratio ~6) and nanowires (aspect ratio ~94) are single-crystalline structures which grow along the c axis of wurtzite ZnO. The nanoparticles are also single-crystalline and have an average diameter of 16 nm. A qualitative model for nanostructure growth is proposed, based on previous studies of aqueous solution and hydrothermal processing.     

Formation of complex films with water-soluble CTAB molecules

This communication reports the formation of complex Langmuir monolayer at the air-water interface with the water-soluble N-cetyl N,N,N-trimethyl ammonium bromide (CTAB) molecules when interacted with the stearic acid (SA) molecules. The reaction kinetics of the formation of the CTAB-SA complex was monitored by observing the surface pressure versus time graph. Multilayered LB films of this complex doped with Congo red was successfully formed onto a quartz substrate. UV-Vis absorption and steady-state fluorescence spectroscopic characteristics of this doped LB films confirms the successful incorporation of Congo red molecules in to the CTAB-SA complex films.     

ZnO twin-cones: synthesis, photoluminescence, and catalytic decomposition of ammonium perchlorate

ZnO twin-cones, a new member to the ZnO family, were prepared directly by a solvothermal method using a mixed solution of zinc nitrate and ethanol. The reaction and growth mechanisms of ZnO twin-cones were investigated by X-ray diffraction, UV-visible spectra, infrared and ion trap mass spectra, and transmission electron microscopy. All as-prepared ZnO cones consisted of tiny single crystals with lengths of several micrometers. With prolonging of the reaction time from 1.5 h to 7 days, the twin-cone shape did not change at all, while the lattice parameters increased slightly and the emission peak of photoluminescence shifted from the green region to the near orange region. ZnO twin-cones are also explored as an additive to promote the thermal decomposition of ammonium perchlorate. The variations of photoluminescence spectra and catalytic roles in ammonium perchlorate decomposition were discussed in terms of the defect structure of ZnO twin-cones.     

Formation process of indium oxide transparent conducting films via thermal decomposition

Indium 2-ethylhexanoate monohydroxide, In(OH)(O₂CCH(CH₂CH₃)(CH₂)₃CH₃)₂, is a precursory material to fabricate In₂O₃-based transparent conducting films by dip-coating process. Formation process of indium oxide transparent conducting films was investigated using an ultra-low acceleration voltage FE-SEM. The nanostructure change of the precursory layer was observed during the electron beam irradiation in vacuum. A flat and homogeneous surface of the as-coated layer changed to porous and net-work like nanostructure after 80 s; the pore diameter increased and the pore distance decreased although the number of pores remained unchanged. These processes were interpreted as the preliminary step to form porous films composed of nm-sized inter-linked oxide particles as reported in the previous papers by the authors.     

Formation of complex Langmuir and Langmuir-Blodgett films of water soluble rosebengal

This communication reports the formation of complex Langmuir monolayer at the air-water interface by charge transfer types of interaction with the water soluble N-cetyl N,N,N-trimethyl ammonium bromide (CTAB) molecules doped with rosebengal (RB), with the stearic acid (SA) molecules of a preformed SA Langmuir monolayer. The reaction kinetics of the formation of RB-CTAB-SA complex monolayer was monitored by observing the increase in surface pressure with time while the barrier was kept fixed. Completion of interaction kinetics was confirmed by FTIR study. This complex Langmuir films at the air-water interface was transferred onto solid substrates at a desired surface pressure to form multilayered Langmuir-Blodgett films. Spectroscopic characterizations reveal some molecular level interactions as well as formation of microcrystalline aggregates depending upon the molar ratios of CTAB and RB within the complex LB films. Presence of two types of species in the complex LB films was confirmed by fluorescence spectroscopy.     

Formation of volatile organic compounds in the heterogeneous oxidation of condensed-phase organic films by gas-phase OH

The yield of volatile organic compounds (VOCs) from the heterogeneous oxidation of condensed-phase organic and hydrocarbon soot films by gas-phase OH has been studied in a coated-wall flow tube at room temperature. Simultaneously, OH concentrations are measured using a chemical-ionization mass spectrometer (CIMS) operated in negative ion mode and VOCs are measured using a commercial proton-transfer-reaction mass spectrometer (PTR-MS). It is observed that a variety of aldehydes/carbonyls and carboxylic acids are formed. Specifically, detailed experiments were conducted with stearic acid, where products are observed that contain as many as 13 carbon atoms with the average carbon number of the products between 3 and 5. The yield of VOCs, relative to the loss of OH radicals, is strongly dependent on the partial pressure of O2 in the carrier gas, ranging from 0.08 +/- 0.03 in a nominally pure He carrier gas to 0.34 +/- 0.14 in 6 Torr of pure O2. Yields from other organics are somewhat lower than those from stearic acid, ranging in conditions of pure O2 from 0.10 +/- 0.04 for BES (bis(ethylhexyl)sebacate), to 0.03 +/- 0.01 for n-hexane soot, to 0.01 +/- 0.005 for pyrene. Under atmospheric conditions, OH oxidation of select organics may be an efficient source of small VOCs. In particular, formic acid is formed in significant yield from all the surfaces.     

Large-scale synthesis of hexagonal pyramid-shaped ZnO nanocrystals from thermolysis of Zn-oleate complex

We report the large-scale synthesis of uniform-sized hexagonal pyramid-shaped ZnO nanocrystals by the thermolysis of Zn-oleate complex, which was prepared from the reaction of inexpensive and environmentally friendly reagents such as zinc chloride and sodium oleate. Under optimized reaction conditions, we were able to synthesize as much as 2.83 g using 300 mL of oleylamine and 90 mL (284 mmol) of oleic acid (OA) as both solvents and stabilizing surfactants. The UV-vis spectrum showed the absorption onset of 380 nm, and the photoluminescence spectrum showed a near band-edge emission at 387 nm and a broad blue-green emission band above 468 nm.     

Formation and decomposition of C3 metallacycles from ethylene and methylene on MoAl alloy thin films

The reaction between adsorbed ethylene and methylene species has been investigated on a molybdenum-aluminum alloy grown from Mo(CO)(6) on a planar alumina film formed on a Mo(100) single crystal in ultrahigh vacuum. Di-sigma-bonded ethylene reacts with carbene species, formed on the surface from methylene iodide, to form a C(3) metallacycle. This predominantly decomposes to yield propylene, while a smaller portion yields cross-metathesis products since (12)C(13)CH(4) is formed from reaction between (13)C(2)H(4) and (12)CH(2). This work demonstrates for the first time that the reaction proceeds in heterogeneous phase via a C(3) metallacycle as proposed in the Hérisson-Chauvin mechanism.     

Zn-containing double complex salts formed by Keggin type polyoxotungstates: Synthesis and crystal structure

Novel double complex salts, [Zn(DMF)₆]₂[SiW₁₂O₄₀] · 2H₂O (I) and [Zn(H₂O)₂(DMF)₄][Zn(DMF)₆]₂[PW₁₂O₄₀]₂ · 6DMF (II) (DMF = N,N-dimethylformamide), were prepared by the reaction of Zn²⁺ and heteropoly acids H_x[EW₁₂O₄₀] · xH₂O (E = P, X = 3, E = Si, X = 4) in DMF. Compounds I and II were studied by X-ray diffraction (СIF files CCDC nos. 1497570 (I) and 1497571 (II)) and IR spectroscopy.     

Photostable and luminescent ZnO films: synthesis and application as fluorescence resonance energy transfer donors

Photostable and luminescent ZnO films are effectively engineered from the corresponding nanocrystalline ZnO solutions, and they successfully demonstrated their capability as fluorescence resonance energy transfer (FRET) donors.     

Use of a superabsorbent polymer for the preconcentration of volatile components from complex matrices

A polymeric material commonly used as a superabsorbent in the sanitary industry is proposed for the first time for analytical purposes. Specifically, we have evaluated in this work the possibility of using this material in a programmed-temperature vaporizer (PTV) injector for the introduction of large volume samples. To that end, the viability of this superabsorbent polymer as a retaining material was first studied by testing the stability of its absorption capacity in the presence of various solvents and at various temperatures. Subsequently, its effectiveness in the isolation of menthol and its isomers from Mentha piperita essential oil as well as gamma-lactones from peach essential oil was assessed. For that purpose, optimization of different variables, namely PTV temperatures during sampling, purge times, and desorption temperatures, involved in the solvent elimination was performed. Additionally, the information obtained was compared with that acquired for the adsorbent material Tenax TA. The results shown in this work proved not only the viability of using this superabsorbent polymer in analytical procedures but also demonstrated its advantages over the adsorbent Tenax TA in attaining internal GC concentration of a sample by introducing large volumes via PTV.     

Electrochemical synthesis of nanostructured ZnO films utilizing self-assembly of surfactant molecules at solid-liquid interfaces

An electrochemical synthesis strategy for the production of nanostructured films was developed by combining self-assembly of surfactant-inorganic aggregates at solid-liquid interfaces and an electrodeposition process. Through this approach high quality nanostructured ZnO films were cathodically deposited from a plating solution containing 0.1 wt % of sodium dodecyl sulfate (SDS). The resulting ZnO films possess lamellar structures with two different repeat distances, d001 = 31.7 A and d001* = 27.5 A, both of which feature well-defined long range order. Due to kinetically controlled surfactant-inorganic assembly during the deposition process, the film exhibits a wide distribution of the stacking directions of the ZnO layers, which will allow facile access of the guest molecules and analytes to the interlayers. The synthetic mechanism used here can be generalized to generate nanostructured films of other semiconducting and metallic materials with architectures that cannot be assembled by other means.     

Formation of nanocrystalline ZnO particles into bacterial cellulose pellicle by ultrasonic-assisted in situ synthesis

Nanocrystalline zinc oxide particles were synthesized and simultaneously incorporated into a three-dimensional nanofibrous matrix of bacterial cellulose (BC) pellicles by a newly created method called “ultrasonic-assisted in situ synthesis”. The BC pellicles were first immersed in a zinc acetate solution. Then the Zn²⁺-absorbed BC pellicle was further immersed in ammonium hydroxide solution with simultaneous ultrasonic treatment. The effect of immersion time of the BC pellicles in zinc acetate solution and ultrasonic treatment time on crystalline size and percent incorporation of ZnO into the BC pellicles were determined. The crystalline size of ZnO incorporated in BC pellicles was in the range of ~54–63 nm that were similar to the diameter of BC nanofibrils. The amount of ZnO into the BC pellicles was found to increase with increasing immersion time. A longer ultrasonic treatment time resulted in smaller crystalline size of the incorporated ZnO. The particle size, morphology and dispersion of the synthesized ZnO in the BC matrix were examined by transmission electron microscope and scanning electron microscope with inbuilt energy dispersive X-ray analysis. The mechanism of the formation of the nanocrystalline ZnO particles onto the BC nanofibrils was discussed. Moreover, the antibacterial activity of the nanocrystalline ZnO particle-incorporated BC sheet against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) was also evaluated.     

Zn-containing porphyrin as a biomimetic light-harvesting molecule for biocatalyzed artificial photosynthesis

Among the porphyrin molecules with different metal insertion sites and functional ligands, Zn-porphyrin most efficiently regenerates NADH through photo-induced electron transfer in the presence of [Cp*Rh(bpy)H(2)O](2+), a rhodium-based electron mediator. Photochemical regeneration of NADH by Zn-porphyrin is successfully coupled with redox enzymatic synthesis under dark state conditions.     

Template-free polyoxometalate-assisted synthesis for ZnO hollow spheres

ZnO hollow spheres with diameters ranging from 400 to 600 nm and the thickness of shell approximate 80 nm were synthesized by a simple polyoxometalate-assisted solvothermal route without using any templates. The effect of polyoxometalate concentration, reaction time and temperature on the formation of the hollow spheres was investigated. The results indicated that the hollow spheres were composed of porous shells with nanoparticles and polyoxometalate play a key role in controlling morphology of ZnO. A possible growth mechanism based on polyoxometalate-assisted assembly and slow Ostwald ripening dissolution in ethanol solution is tentatively proposed. In addition, the room temperature photoluminescence spectrum showed that the ZnO hollow spheres exhibit exciting emission features with wide band covering nearly all the visible region.     

RF magnetron sputtering of ZnO and Al-doped ZnO films from ceramic and nanopowder targets: a comparative study

Undoped zinc oxide (ZnO) and aluminium-doped zinc oxide (ZAO) thin films have been prepared on glass substrates by RF magnetron sputtering from ceramic and nanopowder targets at room temperature (RT). The effects of target nature on the properties of the films have been studied. The X-ray diffraction (XRD) patterns show that ZnO and Al-doped ZnO thin films are highly textured along the c-axis perpendicular to the surface of the substrate from either nanopowder or ceramic targets. From the SEM images, it appears that the surface morphologies of ZAO films exhibit difference from that of undoped ZnO films. All films exhibit a transmittance higher than 80% in the visible region. The optical band gap (E_g) of ZnO and ZAO films obtained from nanopowder target is higher than those prepared using ceramic target. In two cases, Al-doping leads to a larger optical band gap (E_g) of the films.