Effect of 1,1,2,2-Tetrachloroethane on the IR Spectra of Molecular and Ionic Complexes of Methanesulfonic Acid with Aprotic Bases

The method of multiple attenuated total internal reflection (MATIR) infrared spectroscopy is used to study the effect of 1,1,2,2-tetrachloroethane (TCE) on the spectra of the BH⁺ · (AHA)^– ionic pairs formed by methanesulfonic acid (MSA) with DMF or 2-pyrrolidone and the spectra of molecular complexes of MSA with ethyl acetate. In TCE solutions, the structure with a strong symmetric hydrogen bond in the (AHA)^– anions is preserved and the strength of the hydrogen bond practically does not change in molecular complexes. Changes in the absorption coefficients in the spectra are observed in the region of skeletal vibrations at frequencies below 1800 cm^–1 up to a onefold excess of TCE for the ionic pairs BH⁺ · (AHA)^– and up to a fourfold excess of TCE for molecular complexes.     

Functionalization of single-walled carbon nanotubes with (R-)oxycarbonyl nitrenes

Sidewall functionalization of single-walled carbon nanotubes (SWCNTs) via the addition of (R-)oxycarbonyl nitrenes allows for the covalent binding of a variety of different groups such as alkyl chains, aromatic groups, dendrimers, crown ethers, and oligoethylene glycol units. Such additions lead to a considerable increase in the solubility in organic solvents such as 1,1,2,2-tetrachloroethane (TCE), dimethyl sulfoxide (DMSO), and 1,2-dichlorobenzene (ODCB). The highest solubilities of 1.2 mg/mL were found for SWCNT adducts with nitrenes containing crown ether of oligoethylene glycol moieties in DMSO and TCE, respectively. The presence of chelating donor groups within the addends allowed for the complexation of Cu(2+) and Cd(2+). Atomic force microscopy (AFM) and transmission electron microscopy (TEM) revealed that the functionalized tubes form thin bundles with typical diameters of 10 nm. The presence of thin bundles in solution is supported by (1)H NMR spectroscopy. The elemental composition of the functionalized SWCNT was determined by X-ray photoelectron spectroscopy (XPS). The use of Raman and electron absorption spectroscopy (UV/Vis-nIR) showed that the electronic properties of the SWCNTs are mostly retained after functionalization, indicating a low degree of addition within this series of SWCNT derivatives.     

Ameliorating the sensitivities,thermal and combustion properties of RDX by in situ self-assembly TA-Pb/Cu shells to RDX surface

In order to ameliorate the sensitivities, thermal and combustion properties of cyclotrimethylenetrinitramine (RDX), tannic acid (TA) is used to react with lead and copper via in situ self-assembly to coat RDX for preparing RDX@TA-Pb/Cu microcapsules. The structures of RDX@TA-Pb/Cu microcapsules are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Fourier-transform infrared spectra (FT-IR). The surface topography of RDX@TA-Pb/Cu microcapsules are characterized by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The mechanical sensitivities and explosion points of RDX@TA-Pb/Cu microcapsules are measured to study the influence of TA-Pb/Cu shells on mechanical and thermal safeties of RDX. The non-isothermal properties of RDX@TA-Pb/Cu microcapsules are characterized by differential scanning calorimetry (DSC). The catalytic effects of TA-Pb/Cu shells on RDX are characterized by accelerating rate calorimeter (ARC). The residues of RDX@TA-Pb/Cu microcapsules after combustion in air are collected and characterized by SEM and XRD to further study the catalytic effect of TA-Pb/Cu shells. The study results show that a 150 nm TA-Pb/Cu shells are uniformly coated on RDX surfaces. The chemical structure of RDX maintains constant during in situ self-assembly coating process. The mechanical and thermal safeties of RDX are enhanced after coating with TA-Pb/Cu shells. The decomposition and combustion property of RDX can be catalyzed by TA-Pb/Cu, and the catalytic effects of in situ self-assembly coating are better than that of physical mixing. The RDX@TA-Pb/Cu microcapsules can be used in RDX based composite modified double base (CMDB) propellants.     

乙醇/水体系负载型纳米Cu/Fe二元合金的合成、改性及其还原三氯乙烯的性能

在乙醇/水体系中采用KBH4液相还原法, 以石墨微粉为载体, Cu为复合金属, 通过两步法合成了具有球状团簇结构的负载型纳米Cu/Fe二元合金. 与单纯负载型纳米Fe0相比, 该复合材料对三氯乙烯(TCE)具有更高的还原脱氯性能, 纳米Fe0的质量浓度为10 g/L时, 5 h内能将10 mg/L的TCE完全去除. 将十六烷基三甲基溴化铵(CTAB)用于负载型纳米二元合金的表面改性, 改性后的材料对TCE的还原脱氯性能提高. 改性材料连续降解TCE 36 d, 10.2 mg/L TCE在7 h内即完全去除, 材料改性后不易氧化失活, 还原性能保持长期稳定.     

Oxygen, carbon, and sulfur segregation in annealed and unannealed zerovalent iron substrates

Finely ground and pretreated iron substrates known as "zerovalent iron" or "Fe0" are used as reductants in the environmental remediation of halogenated hydrocarbons, and the composition of their surfaces significantly affects their reactivity. Samples of unannealed and annealed (heat-treated under H2/N2) zerovalent iron were analyzed using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). Surface concentration of the iron and of the impurities observed by XPS and AES, carbon, chlorine, sulfur, and oxygen, were measured before and after soaking in trichloroethylene (TCE) and in water saturated with TCE (H2O/TCE) to simulate chlorocarbon remediation conditions. Samples pretreated by annealing at high temperature under H2 contained less iron carbide. The carbide contaminant was evident in both iron and carbon XPS spectra, with binding energies of 709.0 and 283.3 eV for the Fe 2p3/2 and C 1s, respectively. The annealed Fe0 surface also contained more sulfur. The carbide concentration was essentially unchanged by TCE and H2O/TCE exposure, whereas the sulfur decreased in proportion to chlorine adsorption following the dechlorination reaction. While oxygen concentration is initially lower on the annealed substrate surface, it rapidly increased during the model TCE remediative treatment process and thus does not represent a significant effect of the annealing process on surface reactivity.     

Metal-insulator transition of charge-transfer salts based on unsymmetrical donor DMET and metal halide anions (DMET)4(MCl4)(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane)

New charge-transfer salts based on an unsymmetrical donor DMET [dimethyl(ethylenedithio)diselenadithiafulvalene] and metal halide anions (DMET)4MIICl4(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane) have been synthesized and characterized by transport and magnetic measurements. The crystal structures of the DMET salts are isostructural, consisting of a quasi-one-dimensional stack of DMET and insulating layers containing metal halide anions and TCE. Semimetallic band structures are calculated by the tight-binding approximation. Metal-insulator transitions are observed at TMI = 25, 15, 5-20, and 13 K for M = Mn, Co, Cu, and Zn, respectively. The M = Cu salt exhibits anisotropic conduction at ambient pressure, being semiconducting in the intralayer current direction but metallic for the interplane current direction, down to T(MI). The metal-insulator transitions are suppressed under pressure. In the M = Co and Zn salts, large magnetoresistances with hysteresis are observed at low temperatures, on which Shubnikov-de Haas oscillations are superposed above 30 T. In the M = Cu salt, no hysteresis is observed but clear Shubnikov-de Haas oscillations are observed. The magnetoresistance is small and monotonic in the M = Mn salt. Paramagnetic susceptibilities of the spins of the magnetic ions are observed for the M = Mn, Co, and Cu salts with small negative Weiss temperatures of approximately 1 K. In the nonmagnetic M = Zn salt, Pauli-like pi-electron susceptibility that vanishes at TMI is observed. The ground state of the pi-electron system is understood as being a spin density wave state caused by imperfect nesting of the Fermi surfaces. In this pi-electron system, the magnetic ions of the M = Mn, Co, and Cu salts interact differently, exhibiting a variety of transport behaviors.     

Quantitative analysis of precious metals in automotive shredder residue/combustion residue via EDX fluorescence spectrometry

The recovery of precious metals from automotive shredder residue (ASR) dust/combustion residue is an option that is not usually considered due to the lack of available information. Therefore, before any disposal or recovery application can be considered, it is necessary to determine the significance of the levels and distribution of precious metal in ASR dust/ASR combustion residue. In the present study, quantitative analysis of precious metals (Pt, Pd, Au, Ag and Cu) in the ASR residue samples was performed using energy dispersive X-ray (EDX) fluorescence spectrometer. With the fundamental parameter (FP) method, the X-ray intensity is obtained and the quantitative analysis is performed using theoretical calculation. This method is very effective for quantitative analysis of unknown samples without standard samples. Further, in order to analyse the precious metal distribution within the ASR combustion residues, the microstructural characterisation and elemental mapping were also carried out with the aid of field emission scanning election microscopy combined with electron dispersive spectroscopy (FE-SEM EDS). Significant amount of Pt, Pd, Au, Ag and Cu element concentrations in the ASR residue were identified. Total precious (Pt, Pd, Au, Ag and Cu) metals obtainable values are representing about 12.23 wt% from its initial ASR dust/combustion residues. Considering their relevant concentrations, these metals should be properly recovered for recycling purposes before to dispose or landfill.     

Effect of 1,1,2,2-tetrachloroethane on IR spectra of HCl complexes withN,N-dimethylformamide and 1-methyl-2-pyrrolidone formed by a strong quasi-symmetric hydrogen bond

The effect of 1,1,2,2-tetrachloroethane (TCE) on the IR spectra of HCl complexes withN,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (N-MP) with strong quasisymmetric hydrogen bonds was studied using Multiple Attenuated Total Reflection (MATR) IR spectroscopy. The addition of TCE does not change the background absorption spectra, but results in a change in the extinction coefficients of some bands of these complexes. The analysis of the spectra shows that the HCl−DMF complexes interact only with one molecule of TCE, and the HCl−N-MP complexes interact with two molecules of TCE. It is shown that the neutral component of the system (TCE) has no effect on the parameters of the strong quasi-symmetric H-bond in the complexes studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 956–960, May, 1997.     

Preparation, characterization and catalytic behavior of Pt-Cu nanoparticles in methane combustion

Fine and well dispersed Pt-Cu bimetallic nanoparticles stabilized by polyvinyl pyrrolidone (PVP) were synthesized by alkaline polyol method. The molar ratio of Pt to Cu was 1 : 1. Further, the Pt-Cu bimetallic nanoparticles were supported on alumina and their catalytic behavior in methane combustion was investigated. The as-prepared as well as the supported Pt-Cu nanoparticles were characterized by transmission elec-tron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), fractal analysis and X-ray diffraction (XRD). The dependence of methane combustion on the morphology and surface composition of Pt-Cu nanoparticles was analyzed based on the experimental results.     

短孔道Cu-Mn/Zr-Ce-SBA-15催化剂的制备及其催化甲苯燃烧性能

采用水热法制备了Zr-Ce-SBA-15(ZCS)介孔材料,并以它为载体,通过浸渍法制备了不同Cu/Mn比和Cu-Mn含量的Cu-Mn/ZCS催化剂.采用N2吸附-脱附、透射电镜、扫描电镜、X射线衍射和X射线光电子能谱(XPS)等手段对催化剂进行了表征,并在微型固定床反应器上评价了催化剂催化甲苯燃烧性能.结果表明,Cu...     

UV-spectroscopic study of complex formation by certain cycloolefins with tetracyanoethylene and molecular iodine

UV spectroscopy of charge-transfer complexes (CTCs) with tetracyanoethylene (TCE) and iodine has been used to study the relative donor ability of mono- and bicycloolefins and the stability of the CTCs. The donor ability of bicycloolefins, characterized by _CT(TCE), increases with increase in ring strain. The equilibrium constants for complex formation of bicycloolefins with TCE are linearly related to the rate constants of the reaction of epoxidation by tert-butyl hydroperoxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1314–1318, June, 1990.     

庚酸甲酯高温燃烧化学动力学机理的系统简化和分析

采用详细化学反应动力学机理的系统简化方法, 对庚酸甲酯高温燃烧化学动力学机理进行了系统简化. 首先采用两步直接关系图法(Directed relation graph method, DRG)和主成分分析(Principle component analysis, PCA)方法对由1087个物种、4592步可逆反应组成的庚酸甲酯燃烧的详细机理进行框架简化, 得到了包含108个物种, 547步基元反应的框架机理. 在此框架机理基础上, 进一步采用计算奇异值摄动法(Computational singular perturbation, CSP)对框架机理进行时间尺度分析, 再选取30个准稳态物种, 采用准稳态近似(Quasi steady state approximation, QSSA)方法构建了包含78个物种、74步总包反应的全局简化机理. 模拟结果表明, 在较宽的参数范围内, 框架机理和全局简化机理均能重现庚酸甲酯高温燃烧时的点火延迟、物种浓度分布和熄火等燃烧特性. 此外, 基于框架机理阐明了庚酸甲酯高温燃烧的反应路径和对点火有重要影响的基元反应. 与详细机理相比, 框架机理保留了良好的精确性和全局性, 可以很好地反映庚酸甲酯的燃烧特性, 有助于对生物柴油的燃烧过程的理解.     

15N and 13C NMR study of protonated monoaminopyridines in CDCl3-DMSO

The 2-, 3- and 4-amino-pyridine and their protonated forms, obtained by reaction with pyridinium chloride, were investigated by 15N NMR spectroscopy. Exhaustive evidence has been found that the protonation occurs mainly on the annular nitrogen. Protonation of 4-aminopyridine by dehydrohalogenation of 1,1,2,2-tetrachloroethane (TCE) was also studied by 13C NMR spectroscopy, which indicated that the protonation occurs via the formation of adducts.     

Composition-dependent sintering behaviour of chemically synthesised CuNi nanoparticles and their application in aerosol printing for preparation of conductive microstructures

Copper, nickel and copper–nickel nanoparticles were prepared by solution combustion method for use in direct write printing. Structural (X-ray diffraction) and morphological (transmission electron microscope) investigations showed that pure metal (Cu and Ni) and CuNi alloy particles with face-centred cubic crystal structure were formed. Atomic absorption spectrometer studies confirmed that the nanoparticle compositions corresponded to the initial Cu/Ni molar ratios selected for synthesis. Particle size and morphology were significantly influenced by composition, with high Cu content coinciding with small, spherical particles as opposed to larger, irregular shapes observed at high Ni concentrations. X-ray photoelectron spectroscopy measurements revealed that after the reduction process the surface of the alloy nanoparticles was partially oxidised in air and the amount of metallic surface species decreased, while the concentration of oxidic surface species and hydroxides increased with increasing Cu concentration (i.e. decreasing particle size). Dispersions of CuNi nanoparticles have been deposited by use of AerosolJet? and sintered under reducing atmosphere at 300–800?°C in order to prepare conductive structures. Resistivity measurements and microscopical studies (SEM-FIB) of printed and sintered CuNi structures showed that the sintering properties of nanoparticles were dependent on their chemical composition.     

Absolute surface coverage measurement using a vibrational overtone

Determination of absolute surface coverage with sub-monolayer sensitivity is demonstrated using evanescent-wave cavity ring-down spectroscopy (EW-CRDS) and conventional CRDS by employing conservation of the absolute integrated absorption intensity between gas and adsorbed phases. The first C-H stretching overtones of trichloroethylene (TCE), cis-dichloroethylene, and trans-dichloroethylene are probed using the idler of a seeded optical parametric amplifier having a 0.075 cm(-1) line width. Polarized absolute adsorbate spectra are obtained by EW-CRDS using a fused-silica monolithic folded resonator having a finesse of 28 500 at 6050 cm(-1), while absolute absorption cross sections for the gas-phase species are determined by conventional CRDS. A measure of the average transition moment orientation on the surface, which is utilized for the coverage determination, is derived from the polarization anisotropy of the surface spectra. Coverage measurement by EW-CRDS is compared to a mass-spectrometer-based surface-uptake technique, which we also employ for coverage measurements of TCE on thermally grown SiO(2) surfaces. To assess the potential for environmental sensing, we also compare EW-CRDS to optical waveguide techniques developed previously for TCE detection.     

Photocatalytic reactivity of surface platinized TiO2: substrate specificity and the effect of Pt oxidation state

Surface platinized TiO(2) (Pt/TiO(2)) has been frequently studied, but its photocatalytic reactivities reported in the literature are not consistent in some cases. To understand the discrepancies, the effects of Pt speciation on TiO(2) on the photocatalytic degradation (PCD) of a few chlorinated organic compounds (trichloroethylene (TCE), perchloroethylene (PCE), dichloroacetate, etc.) were investigated with several Pt/TiO(2) samples that were prepared differently. The oxidation state of Pt deposits was analyzed by X-ray photoelectron spectroscopy and was found to be the most important factor in determining the initial PCD rates of chlorinated organic compounds. TiO(2) with oxidized Pt species (Pt(ox)/TiO(2)) was less reactive than TiO(2) with metallic Pt (Pt(0)/TiO(2)) for all substrates tested. In particular, Pt(ox)/TiO(2) strongly inhibited the PCD of TCE and PCE whereas it was more reactive than pure TiO(2) for the PCD of other compounds. The photocurrents obtained with the Pt(ox)/TiO(2) electrode were lower than those with the Pt(0)/TiO(2) electrode, which was ascribed to the role of Pt(ox) species as a recombination center. It is proposed that TCE adsorbed on Pt(ox) chemically mediates the charge recombination through the redox cycle of TCE. The Pt effects in photocatalysis are highly substrate-specific and depend on the Pt-substrate interaction as well as the properties of Pt deposits.     

Cu-Co/SBA-15催化剂的结构特征及其催化甲苯燃烧性能

 以介孔 SBA-15 分子筛为载体, 用等体积共浸渍法制备了不同 Cu/Co 比和不同 Cu-Co 含量的 Cu-Co/SBA-15 催化剂, 采用 N2 吸附-脱附、高分辨透射电镜、X 射线衍射、X 射线光电子能谱和程序升温还原等手段对催化剂进行了表征, 并在微型固定床反应器上评价了催化剂催化甲苯燃烧性能. 结果表明, 所有催化剂仍具有 SBA-15 分子筛的介孔结构, Cu 含量较低时催化剂中存在 Cu-Co-O 固溶体, Cu 含量较高时会形成 CuO. 催化剂表面的 Co 对甲苯催化燃烧有重要的作用, 催化剂中的 Cu 可以降低 Co 的还原温度, 从而有利于催化剂活性的提高. 40%(Cu0.25Co0.75)/SBA-15 催化剂具有最高的活性, 在 285 oC 时可完全催化燃烧消除甲苯.     

基于直接关系图方法的丁酸甲酯燃烧反应机理的框架简化

由于直接关系图(DRG)方法的概念简单和计算量较小,使得DRG方法目前已经成为详细燃烧反应机理框架简化的主流方法。DRG方法中评价物种之间依赖关系的相互作用系数和关系图连接权重的计算方法控制着DRG方法的简化效果。采用四种不同形式的相互作用系数的定义方法,分别与标准的DRG搜索算法和基于误差传播的搜索算法结合,构建了丁酸甲酯的框架燃烧反应机理。通过系统的误差分析比较了不同简化方法构建的框架机理的模拟可靠性。重点采用基于元素流量分析的反应路径分析方法研究了框架机理的化学动力学。最后,通过交集的思想构建了一个只包含96个物种的丁酸甲酯框架燃烧反应机理,并且反应路径分析结果表明丙烯的燃烧化学动力学在丁酸甲酯燃烧过程中占有重要地位。本文通过对不同DRG方法的系统比较研究表明了反应路径分析在框架机理可靠性验证中的重要性,对进一步发展更为有效的框架简化方法提供重要依据。     

Visible-light-induced photocatalytic performances of ZnO-CuO nanocomposites for degradation of 2,4-dichlorophenol

Nanostructured ZnO and CuO, and coupled oxides, i.e., ZnCu, Zn2Cu, and ZnCu2, with ZnO:CuO molar ratios of 1:1, 2:1, and 1:2, respectively, were successfully prepared through a simple, one-step, mi-crowave-assisted urea–nitrate combustion synthesis, without the use of organic solvents or surfac-tants. The prepared samples were characterized using X-ray diffraction, X-ray photoelectron spec-troscopy, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, Fourier-transform infrared spectroscopy, diffuse reflectance spectroscopy, and photo-luminescence spectroscopy. The optical absorption of ZnO extended into the visible region after CuO loading. The photocatalytic activities of ZnO, CuO, and the coupled oxides were evaluated based on photodegradation of 2,4-dichlorophenol under visible-light irradiation. The coupled metal oxide Zn2Cu showed the best photocatalytic activity;this was mainly attributed to the extended photore-sponsive range and the increased charge separation rate in the nanocomposite. The photocatalytic degradation process obeyed pseudo-first-order kinetics. The results suggest that the coupled metal oxide Zn2Cu has potential applications as an efficient catalytic material with high efficiency and recyclability for the photocatalytic degradation of organic pollutants in aqueous solution under visible-light irradiation.     

Methanol Suppression of Trichloroethylene Degradation byMethylosinus trichosporium (OB3b) and Methane-Oxidizing Mixed Cultures

The effect of methanol on trichloroethylene (TCE) degradation by mixed and pure methylotrophic cultures was examined in batch culture experiments. Methanol was found to relieve growth inhibition ofMethylosinus trichosporium (OB3b) at high (14 mg/L) TCE concentrations. Degradation of TCE was determined by both radiolabeling and gas chromatography techniques. When cultures were grown on methanol over 10 to 14 d with 0.3 mg/L TCE, OB3b degraded 16.89 ±0.82% (mean± SD) of the TCE, and a mixed culture (DT type II) degraded 4.55±0.11%. Mixed culture (JS type I) degraded 4.34±0.06% of the TCE. When grown on methane with 0.3 mg/L TCE, 32.93±2.01% of the TCE was degraded by OB3b, whereas the JS culture degraded 24.3 ±1.38% of the TCE, and the DT culture degraded 34.3 ±2.97% of the TCE. The addition of methanol to cultures grown on methane reduced TCE degradation to 16.21 ±1.17% for OB3b and to 5.08±0.56% for JS. Although methanol reduces the toxicity of TCE to the cultures, biodegradation of TCE cannot be sustained in methanol-grown cultures. Since high TCE concentrations appear to inhibit methane uptake and growth, we suggest the primary toxicity of TCE is directed towards the methane monooxygenase.