Nanomechanical characterization of one-step combustion-synthesized Al(4)B(2)O(9) and Al(18)B(4)O(33) nanowires

Two kinds of aluminum borate nanowires, Al(4)B(2)O(9) and Al(18)B(4)O(33), were successfully synthesized by a one-step combustion method through control of the Al:B atomic ratio and synthesis temperature. Both nanowires are single crystalline but have distinguishing growth habits. Nanoindentation tests were performed directly on individual nanowires to reveal their mechanical properties. A 70% reduction in elastic modulus was found in Al(18)B(4)O(33) nanowires compared with their bulk counterpart. Al(18)B(4)O(33) nanowires exhibited higher hardness and elastic modulus than Al(4)B(2)O(9) nanowires.     

Preparation and characterization of Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film as electrode material for the degradation of phenol

In this work, a novel electrode of titanium substrate coated with mixed metal oxides of SnO(2), Sb(2)O(3), Nb(2)O(5) and PbO(2) was successfully prepared using thermal decomposition and electrodeposition. The surface morphology and the structure of the prepared thin film were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. Experimental results showed that the structure of the prepared electrode might be described as a Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film and its surface was mainly comprised pyramidal-shape beta-PbO(2) crystals. The modified electrode had higher oxygen evolution potential than that of other PbO(2) modified electrodes. Electrocatalytic oxidation of phenol in aqueous solution was studied to evaluate the potential applications of this electrode in environmental science. The phenol removal efficiency in an artificial wastewater containing 0.50g/L phenol could reach 78.6% at 20 degrees C and pH 7.0 with an applied electricity density of 20mA/cm(2) and treatment time of 120min. When 21.3g/L chloride was added to this wastewater, the removal efficiency could reach to 97.2%.     

Generation of H(2), O(2), and H(2)O(2) from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization

An intense femtosecond Ti-sapphire laser pulse was focused into water, leading to self-focusing. Apart from generating a white light (supercontinuum), the intense laser field in the self-focusing regions of the laser pulse dissociated the water molecules, giving rise to hydrogen and oxygen gas as well as hydrogen peroxide. Our analysis shows that the formation of free radicals O, H, and OH preceded the formation of the stable products of H(2), O(2), and H(2)O(2). Because O radicals and H(2)O(2) are strong oxydizing agents, one can take advantage of this phenomenon to design a laser scheme for sterilization in medical and biological applications.     

Analysis of isotopic CO(2) mixtures by laser photoacoustic spectroscopy

Photoacoustic spectroscopic studies on a mixture of six CO(2) isotopes ((12) C(16) O(2), (12) C(18) O(2), (13) C (16) O(2), (13) C(18) O(2), (16) O(12) C(18) O, and (16) O(13) C(18) O) in the wavelength range of 9-11 mum by use of a home-built high-pressure continuously tunable CO(2) laser with a bandwidth of 0.017 cm(-1) are discussed. The concentrations of all CO(2) isotopes present in the mixture could be determined with good accuracy. Furthermore, the previously unknown absorption cross sections of some important lines of the(12) C(18) O(2), (13) C(18) O(2), and (16)O (13) C(18) O isotopes in the 9-11-mum range are reported.     

Low-Temperature Thermal Decomposition of Sulfates to SO(2) for On-Line (34)S/(32)S Analysis

We describe a fast, inexpensive, and safe method of direct SO(2) extraction from BaSO(4) for sulfur isotopic analysis by mass spectrometry. Only two reagents are used: (1) pure NaPO(3), which is mixed with BaSO(4) sample, and (2) Cu foil, from which reaction boats are manufactured. The extraction precedes in the Cu boat placed into a quartz tube connected to a vacuum line. The boat is heated to 650-700 °C while pure SO(2) produced is collected in a "cold finger". Reaction is complete in 7-10 min. We have proven by means of (18)O-enriched BaSO(4) specimens that the oxygen isotopic composition of the SO(2) is totally controlled by (18)O content in NaPO(3), when the weight ratio of the reagent to sample exceeds 6:1. The method described can be used for "on-line" SO(2) preparation for isotopic analysis.     

Ni(2+) and H(2)PO(4)(-) uptake properties of compounds in the CaTiO(3)-CaFeO(2.5) system

A batch method was used to investigate the uptake of heavy metal cations and anions by the compounds in the CaTiO(3)-CaFeO(2.5) system, in which a series of oxygen vacancies was systematically introduced into a perovskite structure as the x-value of Ca(Fe(x)Ti(1-x))O(3-x/2) was increased. Samples of CaTiO(3), CaFe(0.1)Ti(0.9)O(2.95), CaFe(0.5)Ti(0.5)O(2.75), CaFe(0.67)Ti(0.33)O(2.67) and CaFeO(2.5) were prepared by solid mixing (SM), co-precipitation (CP) and gel evaporation (GE) methods. The resulting samples were calcined at temperatures between 400 and 1000 °C. The target crystalline phases differed according to the preparation method, but in most cases were formed at 700-800 °C. The Ni(2+) sorption isotherms of all the samples were fitted better by the Langmuir model than by the Freundlich model, while in the case of H(2)PO(4)(-) sorption isotherms, these were better fitted by the latter model. The uptake ability increased with increasing x value of the samples. The maximum values for the saturated sorption of Ni(2+) (Q(0)(Ni(2+)) = 2.83 mmol/g) and H(2)PO(4)(-) (K(F)(H(2)PO(4)(-)) = 2.95 mmol/g) were achieved for x = 1 (i.e. CaFeO(2.5)) sample.     

Degradation and by-product formation of diazinon in water during UV and UV/H(2)O(2) treatment

Kinetics and degradation products resulting from the application of UV and UV/H(2)O(2) to the US EPA Contaminant Candidate List pesticide diazinon were studied. Batch experiments were conducted with both monochromatic (low pressure [LP] UV 253.7 nm) and polychromatic (medium pressure [MP] UV 200-300 nm) UV sources alone or in the presence of up to 50 mg l(-1) H(2)O(2), in a quasi-collimated beam apparatus. Degradation of diazinon by both UV and UV/H(2)O(2) exhibited pseudo first order reaction kinetics, and quantum yield of 8.6 x 10(-2) and 5.8 x 10(-2) mol E(-1) for LP and MP lamps respectively. Photolysis studies under MP UV lamp showed 2-isopropyl-6-methyl-pyrimidin-4-ol (IMP) to be the main degradation product of diazinon at aqueous solution pH values of 4, 7 and 10. Trace levels up to 1.8 x 10(-3) microM of diazinon oxygen analogue diethyl 2-isopropyl-6-methylpyrimidin-4-yl phosphate (diazoxon) were detected only during the UV/H(2)O(2) reaction. Decay of both products was observed, as the UV/H(2)O(2) reaction prolonged, yet no mineralization was achieved over the UV fluence levels examined. Photolysis kinetics, quantum yield and UV/H(2)O(2) degradation of the reaction product IMP was determined using MP UV lamp at pH values of 4, 7 and 10.     

Generation of O2 from BaSO4 using a CO2-laser fluorination system for simultaneous analysis of delta18O and delta17O

With the observation of mass-independent isotopic anomalies in numerous atmospheric molecules, the ability to measure both delta17O and delta18O in a range of samples is needed. Sulfate oxygen isotopic studies conventionally report only delta18O values. Recent findings indicate that sulfate delta17O and delta18O values, particularly the delta17O value (= delta17O - (0.52)(delta18O)), can provide independent information on the origin, mixing, and transformation of sulfate in the atmospheric and surface environments, which is not resolvable by only delta18O measurements. Existing methods for analyzing sulfate delta17O and delta18O are extremely laborious and demand high-purity BrF5. Here we report a novel method of generating O2 directly from Barite (BaSO4) for simultaneous analysis of delta18O and delta17O by isotope ratio mass spectrometry (IRMS). The method utilizes a CO2-laser fluorination system that can also be used to quantitatively generate O2 from silicates and oxides. Partial but consistent oxygen yields from BaSO4 are obtained for samples >4 mg. Correction factors of +9.4% for delta18O and 4.89% for delta17O are obtained, and there is no deviation in the delta17O value due to the nonquantitative O2 generation. The system may process more than a dozen samples per working day, with analytical error of +/-0.05% and +/-0.8% for delta17O and delta18O, respectively. This new method is ideal for studies emphasizing an accurate sulfate delta17O value.     

Optimization of Zn(O,S)/(Zn,Mg)O buffer layer in Cu(In,Ga)Se<Subscript>2</Subscript> based photovoltaic cells

Device modeling of CIGS based thin film solar cell with Zn(O,S)/(Zn,Mg)O buffer layer was simulated in order to find the optimum ratios of magnesium in (Zn_1?x,Mg_x)O and oxygen in Zn(O_y,S_1?y) which led to the optimized values of x = 0.1?0.25 and y = 0.5?0.6. When the oxygen content of Zn(O,S) was lower than 30 %, the recombination at Zn(O,S)/CIGS interface became prominent and J_SC was severely limited. It was found that the V_OC is approximately independent of magnesium content in (Zn,Mg)O and oxygen content in Zn(O,S) layers, and the efficiency is highly affected by the fill factor. Also studied were the effect of thicknesses of (Zn,Mg)O and Zn(O,S) layers while the x and y were set at x = 0.2 and y = 0.6. Our simulations show that the optimum range for thickness of the (Zn,Mg)O layer is from 70 to 100 nm, while it is 20–30 nm for the Zn(O,S) layer.     

Enrichment of H(2)(17)O from tap water, characterization of the enriched water, and properties of several (17)O-labeled compounds

A low-abundance form of water, H(2)(17)O, was enriched from 0.04% to ～90% by slow evaporation and fractional distillation of tap water. The density and refractive index for H(2)(17)O are reported. Gas chromatography-mass spectrometry (GC-MS) of (16)O- and (17)O-1-hexanols and their trimethyl silyl ethers and of (16)O- and (17)O-hexamethyl disiloxanes was used to determine the percentage of (17)O enrichment in the H(2)(17)O. Furthermore, the chemical shifts of labeled and nonlabeled water dissolved in CDCl(3) differed sufficiently that we could verify the enrichment of H(2)(17)O. (17)O hexanol was synthesized by the reaction of iodohexane with Na(17)OH. (17)O-Labeled trimethylsilanol and (17)O-labeled hexamethyldisiloxane were prepared by the reaction of H(2)(17)O with bis(trimethylsilyl)trifluoroacetamide (BSTFA). To generate standards for (17)O NMR, H(2)(17)O(2), and (17)O camphor were prepared. H(2)(17)O was electrolyzed to form (17)O-labeled hydrogen peroxide which was quantified using two colorimetric assays. (17)O-Labeled camphor was prepared by exchanging the ketone oxygen of camphor using H(2)(17)O. The (17)O-labeled compounds were characterized using (17)O, (1)H, and (13)C NMR and GC-MS. While we were characterizing the labeled camphor, we also detected an unexpected oxygen exchange reaction of primary alcohols, catalyzed by electrophilic ketones such as camphor. The reaction is a displacement of the alcohol OH group by water. This is an example of the usefulness of (17)O NMR in the study of a reaction mechanism that has not been noticed previously.     

First-Principle Investigation of O2 Adsorption on the NiTi Alloy (110) Surface

The discrete-variational method within the framework of density functional theory was used to investigate the process of O2 adsorption occurring on the surface of NiTi alloy. The calculated results showed that O2 exhibits the adsorption state of O2δ-(0.36<δ <0.70). O2 only interact with one nearest surface Ti atom, and the Ti atom only adsorbs one oxygen atom of the O2 molecule.Other cluster atoms would not be influenced in the adsorption process. The density of state analysis showed that the interaction between Ti and O atom is mainly contributed to 2p (O) and 4s (Ti) orbitals.     

Observation of short-range oxygen migration and oxygen exchange during low temperature plasma anodization of silicon through thin ZrO2 films

Low temperature ¹⁶O plasma anodization of silicon through thin ¹⁸O-enriched ZrO₂ layers has been studied. Measurements of the overall oxygen (¹⁶O and ¹⁸O) and cation contents as well as their distribution in the films were carriedout using combined Rutherford backscattering and nuclear microanalysis techniques. The data show (1) the conservation of the order of oxygen atoms during SiO₂ growth and (2) a partial exchange of ¹⁸O present in the Zr¹⁸O₂ with the ¹⁶O in the plasma. These results show that the microscopic mechanism of oxygen transport during low temperature plasma anodization involves a short-range oxygen migration, in contrast with the case of high temperature thermal oxidation. Analysis of the ¹⁸O depth profiles in the Zr¹⁸O₂ shows that the exchange phenomenon is not only at the plasma-oxide interface but that it extends to a depth of about 200 Å. This strongly suggests that the formation of positive oxygen ions in the Zr¹⁸O₂ is due to high energy (about 30 eV) plasma electron bombardment. A possible mechanism for this process is discussed.     

Simultaneous determination of the (2)h/(1)h, (17)o/(16)o, and (18)o/(16)o isotope abundance ratios in water by means of laser spectrometry

We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative (2)H/(1)H, (17)O/(16)O, and (18)O/(16)O isotope abundance ratios in water. The method uses a narrow line width color center laser to record the direct absorption spectrum of low-pressure gas-phase water samples (presently 10 μL of liquid) in the 3-μm spectral region. It thus avoids the laborious chemical preparations of the sample that are required in the case of the conventional isotope ratio mass spectrometer measurement. The precision of the spectroscopic technique is shown to be 0.7‰ for δ(2)H and 0.5‰ for δ(17)O and δ(18)O (δ represents the relative deviation of a sample's isotope abundance ratio with respect to that of a calibration material), while the calibrated accuracy amounts to about 3 and 1‰, respectively, for water with an isotopic composition in the range of the Standard Light Antarctic Precipitation and Vienna Standard Mean Ocean Water international standards.     

A neutron powder diffraction study of short range order in ferroelectric Pb(Mg(1/3)Nb(2/3))O(3)

The structure of Pb(Mg(1/3)Nb(2/3))O(3) (PMN) was investigated using pulsed neutron powder diffraction. Rietveld analysis suggests small displacements of Pb and O atoms, with anomalously large thermal factors. The pair-distribution function (PDF) derived from experiment indicates the presence of short range order. Modeling in real space by fitting to the experimental PDF suggests displacements of lead and oxygen atoms of much larger magnitude than those indicated by the Rietveld analysis. Correlation of these displacements may be related to the onset of bulk ferroelectricity in this material.     

Isotope (18)O/(16)O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

We applied a photoacoustic spectroscopy technique to isotope ratio measurements of (16)O and (18)O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4nu(OH)) of water molecules near 720 nm were investigated. We identified the absorption lines of H(2)(16)O and H(2)(18)O in the photoacoustic spectra that we measured by using an (18)O-enriched water sample and the HITRAN database. We measured the difference in the (18)O/(16)O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is delta(18)O = -32 ? 16 per thousand, where the indicated deviation was a 1varsigma value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was delta(18)O = -28 ? 2 per thousand. This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H(2)(18)O/H(2)(16)O ratio in the environment.     

Dumbbell-like PtPd-Fe(3)O(4) Nanoparticles for Enhanced Electrochemical Detection of H(2)O(2)

Dumbbell-like Pt(x)Pd(100-x)-Fe(3)O(4) nanoparticles (NPs) were synthesized and studied for electrocatalytic reduction and sensing of H(2)O(2). In 0.1 M phosphate buffered saline (PBS) solution, the 4-10 nm Pt(x)Pd(100-x)-Fe(3)O(4) NPs showed the Pt/Pd composition-dependent catalysis with Pt(48)Pd(52)-Fe(3)O(4) NPs having the best activity. The Pt(48)Pd(52)-Fe(3)O(4) NPs were tested for H(2)O(2) detection, and their H(2)O(2) detection limit reached 5 nM, which was suitable for monitoring H(2)O(2) generated from Raw 264.7 cells. These dumbbell-like PtPd-Fe(3)O(4) NPs are the most sensitive probe ever reported and can be used to achieve real-time quantitative detection of H(2)O(2) in biological environment for biological and biomedical applications.     

Microwave dielectric properties of (A2+(1/3)B5+(2/3))0.5Ti0(0.5)O2 (A2+ = Zn, Mg, B5+ = Nb, Ta) ceramics

Dielectric properties of (A(2+)(1/3)B(5+)(2/3))(0.5)Ti0(0.5)O(2) (A(2+) = Zn, Mg, B(5+) = Nb, Ta) ceramics were investigated at microwave frequencies. A single phase with tetragonal rutile structure was obtained through the entire compositions. Dielectric properties were strongly dependent on the structural characteristics. The specimens with B(5+) = Nb showed a larger dielectric constant than those with B(5+) = Ta due to the decrease of bond valence. Quality factors (Qf) of the specimens with B(5+) = Ta were larger than those with B(5+) = Nb. Temperature coefficient of the resonant frequencies (TCF) of (Zn(1/3)Nb(2/3) )0(0.5)Ti0(0.5)O(2) was larger than that of (Mg(1/3)Ta(2/3))0(0.5)Ti0(0.5)O(2). These results could be attributed to the changes of the temperature coefficient of dielectric constant and the degree of oxygen octahedral distortion.     

Amorphous TiO(2) nanotube arrays for low-temperature oxygen sensors

Titania nanotube arrays (TNTA) were synthesized on a titanium substrate using anodic oxidation in an electrolyte containing ammonium fluoride and evaluated for low-temperature oxygen sensing. Their sensing properties were tested at different temperatures (50, 100, 150, 200, 250 and 300?°C) when exposed to various oxygen concentrations. The as-prepared TNTA are amorphous and exhibit much higher carrier concentration than that of annealed TNTA. Such amorphous TNTA show much higher sensitivity than that of annealed TNTA, SrTiO(3) and Ga(2)O(3) sensors. This sample demonstrates the lowest detectable oxygen concentration of 200 ppm, excellent recovery and good linear correlation at 100?°C. These results indicate that TNTA are indeed very attractive oxygen-sensing materials.     

In-situ X-ray absorption study of evolution of oxidation states and structure of cobalt in Co and CoPt bimetallic nanoparticles (4 nm) under reducing (H2) and oxidizing (O2) environments

In-situ near edge X-ray absorption fine structure spectroscopy was performed to monitor the oxidation states of Co and CoPt nanoparticles (NPs) of 4 nm size in the presence of H(2) and O(2) in the pressure range of 1 bar and 36 Torr respectively. Platinum helps the rapid reduction of cobalt oxides in hydrogen at a rather low temperature (38 °C). In addition, reversible changes of the oxidation states of cobalt in the Co and CoPt NPs as a function of cycling oxygen pressure (in the range of millitorr to 36 Torr) are quantified and compared. The role of Pt in the process of Co reducing and oxidizing was explored. Our findings permit the prediction of the cobalt oxidation states as the reaction conditions are altered. The experimental results also suggest the presence of tetrahedral structure of Cobalt oxide that differs from the Co(3)O(4) spinel structure.     

Oxidative degradation of dimethyl phthalate (DMP) by UV/H(2)O(2) process

The photochemical degradation of dimethyl phthalate (DMP) in UV/H(2)O(2) advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H(2)O(2) alone. In contrast, the combined UV/H(2)O(2) process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H(2)O(2) concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H(2)O(2) advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10(9) M(-1)s(-1) through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H(2)O(2) advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal.