Formation of crystalline TiO2−xNx and its photocatalytic activity

Amorphous precursors to nitrogen-doped TiO₂ (NTP) and pure TiO₂ (ATP) powders were synthesized by hydrolytic synthesis and sol-gel method (SGM), respectively. Corresponding crystalline phases were obtained by thermally induced transformation of these amorphous powders. From FT-IR and XPS data, it was concluded that a complex containing titanium and ammonia was formed in the precipitate stage while calcination drove weakly adsorbed ammonium species off the surface, decomposed ammonia bound on surface of precipitated powder and led to substitution of nitrogen atom into the lattice of TiO₂ during the crystallization. The activation energies required for grain growth in amorphous TiO_2−xN_x and TiO₂ samples were determined to be 1.6 and 1.7 kJ/mol, respectively. Those required for the phase transformation from amorphous to crystalline TiO_2−xN_x and TiO₂ were determined to be 129 and 142 kJ/mol, respectively. A relatively low temperature was required for the phase transformation in NTP sample than in ATP sample. The fabricated N-doped TiO₂ photocatalyst absorbed the visible light showing two absorption edges; one in UV range due to titanium oxide as the main edge and the other due to nitrogen doping as a small shoulder. TiO_2−xN_x photocatalyst demonstrated its photoactivity for photocurrent generation and decomposition of 2-propanol (IPA) under visible light irradiation ().     

Alkynylation of N-tosylimines with aryl acetylenes promoted by ZnBr2 and N,N-diisopropylethylamine in acetonitrile

We found a suitable condition for the effective alkynylation of N-tosylimines with aryl acetylenes. The reaction of N-tosylimines and aryl acetylenes in the presence of ZnBr₂ and DIEA (N,N-diisopropylethylamine) in CH₃CN afforded the desired N-tosyl propargylamines in moderate to good yields.     

New synthesis of excellent visible-light TiO2−xNx photocatalyst using a very simple method

An excellent visible-light-responsive (from 400 to 550 nm) TiO_2−xN_x photocatalyst was prepared by a simple wet method. Hydrazine was used as a new nitrogen resource in this paper. Self-made amorphous titanium dioxide precursor powders were dipped into hydrazine hydrate, and calcined at low temperature (110 °C) in the air. The TiO_2−xN_x was successfully synthesized, following by spontaneous combustion. The photocatalyst was characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscope (TEM), UV-Vis diffuse reflectance spectrometer (DRS), and X-ray photoelectron spectroscopy (XPS). Analysis of XPS indicated that N atoms were incorporated into the lattice of the titania crystal during the combustion of hydrazine on the surface of TiO₂. Ethylene was selected as a target pollutant under visible-light excitation to evaluate the activity of this photocatalyst. The newly prepared TiO_2−xN_x photocatalyst with strong photocatalytic activity and high photochemical stability under visible-light irradiation was firstly demonstrated in the experiment.     

Preparation and photocatalytic degradability of TiO2/polyacrylamide composite

Based on the unique absorbent characters and three-dimensional network structure of polyacrylamide (PAM) superabsorbent polymer, a photocatalytic degradable TiO₂/PAM composite was synthesized by an aqueous solution polymerization method with N,N′-methylene bisacrylamide as crosslinker, potassium peroxydisulfate as initiator, acrylamide as monomer, and TiO₂ (P-25) as functional filler. The photocatalytic degradability of the composite was evaluated using methyl orange as photodegradation target, and the recovery and reproducibility of the composite was investigated. It was found that TiO₂/PAM composite had a good photocatalytic degradability, the composite also possessed a good reproducibility of photocatalytic degradability, which is possible to be used in practical process.     

石墨相氮化碳/二氧化锡复合材料的制备及光催化性能

采用热聚合法和水热法相结合的方法制备了g-C_3N_4/SnO_2复合光催化剂。利用XRD、SEM、TEM、FT-IR和UV-Vis DRS等多种测试手段对所得样品的物相结构、微观形貌和吸光特性等进行了表征。结果表明,异质结构复合光催化剂的最大光吸收边位置相对纯相SnO_2发生了明显的红移,并且SnO_2颗粒均匀分布于g-C_3N_4表面,其中最优组分(50%-g-C_3N_4/SnO_2)光催化降解染料罗丹明B(RhB)的效率达到了纯相g-C_3N_4的3.78倍。     

Study of NOx and CO2 production of cultivated soil in closed microcosm experimental system

The aim of present project was to develop a microcosm experimental method for estimation of NO_x and CO₂ emission of microbial origin from cultivated soil. The effect of different factors (such as temperature, water supply, mineral-N source and organic matter addition, role of soil organisms and heavy metal contamination) that controlling the accumulation of N₂O and CO₂ in soil atmosphere and release to air was studied in closed microcosm laboratory model experiments. The headspace gas composition of closed glass vessels of 800-1200 cm³ containing 100-200 g brown forest soil sample was analysed. The N₂O and CO₂ concentration of gas samples was analysed by gas chromatographic methods and NO-content by means of chemiluminescent detection. Concerning the results, it can be stated that the applied microcosm experimental model proved to be a suitable tool for detecting the effect of factors influencing the NO_x and CO₂ release from agricultural soil. The temporal changes of N₂O and CO₂ concentration demonstrated the impact of the coupled microbial processes resulting in these greenhouse gases. The gas production depended on the soil moisture level, temperature and C/N ratio significantly. The inhibitory effect of toxic heavy metals (e.g. Cd) could also be affected by the C/N ratio. The appearance of NO as an intermediate of microbial processes was observed as well.     

C/g-C3N4/MoS2复合材料的制备及光催化性能

首先以尿素和葡萄糖为前驱体,通过热缩合方法制备了C/g-C₃N₄,然后利用溶剂热法合成C/g-C₃N₄/MoS₂三元复合材料。通过不同的手段对其进行了表征,结果表明,与C/g-C₃N₄相比,该三元复合材料不仅具有更强的光吸收性能和更大的表面积,而且更有利于电子的转移。同时对其可见光催化降解甲基橙性能进行研究,结果发现,C/g-C₃N₄/MoS₂-2.0%复合材料(含有质量分数为2.0%的MoS₂)表现出最高的反应速率常数(0.0086 min^-1),分别为g-C₃N₄/MoS₂-2.0%(0.0015 min^-1)和C/g-C₃N₄(0.0036min^-1)的5.7倍和2.3倍。     

Crystal structures and magnetic properties of CeAu4Si2 and CeAu2Si2

Single crystals of CeAu₄Si₂ and CeAu₂Si₂ have been grown out of ternary fluxes rich in Au, and the former, also by sintering the stoichiometric composition at 750 °C. The single-crystal X-ray refinement result for CeAu₄Si₂ is orthorhombic, Cmmm (No. 65, Z=2), different from a tetragonal result found from an X-ray powder diffraction refinement [H. Nakashima, et al., J. Alloys Compds. 424 (2006) 7]. For CeAu₂Si₂, this is the first report of the stoichiometric crystalline phase, in the known tetragonal I4/mmm structure. The anisotropic field- and temperature-dependent magnetizations, as well as specific heat and resistivity data are compared. Although both compounds have related structural packing, they present unique magnetic features. CeAu₂Si₂ is a typical antiferromagnet with T_N=8.8(1) K and CeAu₄Si₂ features a ferromagnetic component below T_c=3.3(1) K. Both phases have effective moments close in value to that of free Ce³⁺.     

Bi2WO6/g-C3N4复合型催化剂的制备及其可见光光催化性能

利用溶剂热法, 把Bi₂WO₆纳米颗粒植入g-C₃N₄层间和表面成功地制备了Bi₂WO₆/g-C₃N₄复合型光催化剂。通过XRD、SEM、TEM、BET和UV-Vis分别对样品的结构、组成、形貌、比表面积、光学性能进行了表征。结果表明, g-C₃N₄层状结构被部分剥离成碎片且与Bi₂WO₆纳米颗粒形成了复合物。Bi₂WO₆/g-C₃N₄复合型光催化剂与单一Bi₂WO₆相比不仅扩展了可见光的响应范围、增大了比表面还加速了光生电子与空穴的分离。结果表明, Bi₂WO₆的最佳负载量为60wt%时, 复合型光催化剂具有最高的可见光催化活性且性能稳定、易回收。     

Bi2WO6/g-C3N4复合型催化剂的制备及其可见光光催化性能

利用溶剂热法,把Bi2WO6纳米颗粒植入g-C3N4层间和表面成功地制备了Bi2WO6/g-C3N4复合型光催化剂。通过XRD、SEM、TEM、BET和UV-Vis分别对样品的结构、组成、形貌、比表面积、光学性能进行了表征。结果表明,g-C3N4层状结构被部分剥离成碎片且与Bi2WO6纳米颗粒形成了复合物。Bi2WO6/g-C3N4复合型光催化剂与单一Bi2WO6相比不仅扩展了可见光的响应范围、增大了比表面还加速了光生电子与空穴的分离。结果表明,Bi2WO6的最佳负载量为60wt%时,复合型光催化剂具有最高的可见光催化活性且性能稳定、易回收。     

A comparison of the structure and localized magnetism in Ce2PdGa12 with the heavy fermion CePdGa6

Single crystals of Ce₂PdGa₁₂ have been synthesized in Ga flux and characterized by X-ray diffraction. This compound crystallizes in the tetragonal P4/nbm space group, Z=2 with lattice parameters of and . It shows strongly anisotropic magnetism and orders antiferromagnetically at T_N∼11 K. A field-induced metamagnetic transition to the ferromagnetic state is observed below T_N. Structure-property relationships with the related heavy-fermion antiferromagnet CePdGa₆ are discussed.     

EuZn2Si2 and EuZn2Ge2 Grown from Zn or Ga(ln)/Zn Flux

Single crystals of the novel ternary compounds EuZn₂Si₂ and EuZn₂Ge₂ were grown from pure gallium, indium, or zinc metal used as a flux solvent. Crystal properties were characterized using X-ray single-crystal analyses via Gandolfi and Weissenberg film techniques and by four-circle X-ray single-crystal diffractometry. The new compounds crystallize with ternary derivative structures of BaAl₄, i.e., EuZn₂Si₂ with ThCr₂Si₂-type (a=0.42607(2) nm, c=1.03956(5) nm, I4/mmm, R₁=0.038) and EuZn₂Ge₂ with CaBe₂Ge₂-type (a=0.43095(2) nm, c=1.07926(6) nm, P4/nmm, R₁=0.067). XAS and magnetic measurements on EuZn₂Si₂ and EuZn₂Ge₂ revealed in both compounds the presence of Eu²⁺ ions carrying large magnetic moments, which order magnetically at low temperatures. The magnetic phase transition occurs at T_N=16 and 7.5 K for the silicide and the germanide, respectively. In EuZn₂Si₂ there occurs a spin reorientation at 13 K and furthermore some canting of antiferromagnetically ordered moments below about 10 K. In EuZn₂Ge₂ a canted antiferromagnetic structure is formed just at T_N.     

Conversion of NO in NO/N2, NO/O2/N2, NO/C2H4/N2 and NO/C2H4/O2/N2 Systems by Dielectric Barrier Discharge Plasmas

An experimental study on the conversion of NO in the NO/N₂, NO/O₂/N₂, NO/C₂H₄/N₂ and NO/C₂H₄/O₂/N₂ systems has been carried out using dielectric barrier discharge (DBD) plasmas at atmospheric pressure. In the NO/N₂ system, NO decomposition to N₂ and O₂ is the dominating reaction; NO conversion to NO₂ is less significant. O₂ produced from NO decomposition was detected by an on-line mass spectrometer. With the increase of NO initial concentration, the concentration of O₂ produced decreases at 298 K, but slightly increases at 523 K. In the NO/O₂/N₂ system, NO is mainly oxidized to NO₂, but NO conversion becomes very low at 523 K and over 1.6% of O₂. In the NO/C₂H₄/N₂ system, NO is reduced to N₂ with about the same NO conversion as that in the NO/N₂ system but without NO₂ formation. In the NO/C₂H₄/O₂/N₂ system, the oxidation of NO to NO₂ is dramatically promoted. At 523 K, with the increase of the energy density, NO conversion increases rapidly first, and then almost stabilizes at 93–91% of NO conversion with 61–55% of NO₂ selectivity in the energy density range of 317–550 J L⁻¹. It finally decreases gradually at high energy density. A negligible amount of N₂O is formed in the above four systems. Of the four systems studied, NO conversion and NO₂ selectivity of the NO/C₂H₄/O₂/N₂ system are the highest, and NO/O₂/C₂H₄/N₂ system has the lowest electrical energy consumption per NO molecule converted.     

Stereoselective synthesis of anti-2-oxazolidinones by Ph3P-CCl4-Et3N mediated SN2 cyclization of N-Boc-β-amino alcohols

Ethyl anti-4-substituted phenyl-2-oxo-1,3-oxazolidine-5-carboxylates were synthesized stereoselectively in excellent yields using the Ph₃P-CCl₄-Et₃N system by S_N2 cyclization of N-Boc-β-amino alcohols. syn to anti conversion of ethyl 4-substituted phenyl-2-oxo-1,3-oxazolidine-5-carboxylates using DBU as base is also described.     

Nickel deficiency in RENi2-xP2 (RE=La, Ce, Pr). Combined crystallographic and physical property studies

Large single crystals from RENi_2-xP₂ (RE=La, Ce, Pr) were synthesized from the pure elements using Sn as a metal flux, and their structures were established by X-ray crystallography. The title compounds were confirmed to crystallize in the body-centered tetragonal ThCr₂Si₂ structure type (space group I4/mmm (No. 139); Pearson's symbol tI10), but with a significant homogeneity range with respect to the transition metal. Systematic synthetic work, coupled with accurate structure refinements indicated strong correlation between the degree of Ni-deficiency and the reaction conditions. According to the temperature dependent dc magnetization measurements, LaNi_2-xP₂ (x=0.30(1)), as expected, is Pauli-like paramagnetic in the studied temperature regime, while the Ce-analog CeNi_2-xP₂ (x=0.28(1)) shows the characteristics of a mixed valent Ce³⁺/Ce⁴⁺ system with a possible Kondo temperature scale on the order of 1000 K. For three different PrNi_2-xP₂ (x?0.5) samples, the temperature and field dependence of the magnetization indicated typical local moment 4f-magnetism and a stable Pr³⁺ ground state, with subtle variations of T_C as a function of the concentration of Ni defects. Field-dependent heat capacity data for CeNi_2-xP₂ (x=0.28(1)) and PrNi_2-xP₂ (x=0.53(1)) are discussed as well.     

Hydrothermal synthesis, characterization, and photocatalytic properties of Zn2SnO4

Nanosized Zn₂SnO₄ (ZTO) particles were successfully synthesized by a simple hydrothermal process in water/ethylene glycol mixed solution using amines (ethylamine, n-butylamine, n-hexylamine, and n-octylamine) as mineralizer. The products were characterized by X-ray diffractions (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ adsorption. The results indicated that the hydrothermal conditions, such as alkaline concentration (n-butylamine), reaction temperature, solvent composition, and the kind of amines, had an important influence on the composition, crystallinity, and morphology of the product. The as-synthesized ZTO samples exhibited high activities and durabilities for photodegradation of methyl orange and the activities were mainly affected by the crystallinities of the samples. A hexagonal-shaped ZTO (H-ZTO) sample was prepared in 0.53 M of n-butylamine solution at 180 °C for 20 h and its optical properties were characterized by UV-Vis diffuse reflectance and Photoluminescence (PL) spectra. Furthermore, the photocatalytic H₂ evolution reaction from ethanol aqueous solution over H-ZTO was also investigated.     

GO/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能

以水热法制备的20% g-C₃N₄/TiO₂（20%为质量分数）为基,将其与不同质量分数的氧化石墨烯（GO）复合制备出可见光催化性能优良的GO/TiO₂-g-C₃N₄三元复合材料。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis DRS）、光致荧光光谱（PL）、瞬态光电流响应等分析测试手段对样品的结构、形貌和光电性能进行表征。研究了不同质量分数GO的加入对GO/TiO₂-g-C₃N₄在可见光下降解亚甲基蓝（MB）溶液的影响。结果表明： g-C₃N₄/TiO₂与GO复合后,锐钛矿相TiO₂颗粒形成小团簇附着在g-C₃N₄和GO片层表面,且当GO含量为15%时,TiO₂形成的团簇最小,对可见光的吸收最多且光生电子-空穴对的复合率最低。可见光照射下,15% GO/TiO₂-g-C₃N₄复合材料对MB的降解率在3 h内可达98.4%,且其降解速率常数（0.022 4 min^-1）分别是纯TiO₂（0.001 5 min^-1）和g-C₃N₄/TiO₂（0.002 5 min^-1）的15倍和9倍。     

Cu2O/g-C3N4催化合成吲哚-2-羧酸酯

我们通过原位还原的方法将吸附在g-C3N4表面上Cu2+还原,制备出Cu2O/g-C3N4复合材料,并利用XRD、SEM、FT-IR、XPS等分析手段表征Cu2O/g-C3N4.表征结果显示:Cu元素主要以Cu2O的形式吸附在g-C3N4载体上.另外,还考察了Cu2O/g-C3 N4在“一锅法”合成吲哚-2-甲酸乙酯的反应中的催化性能.结果表明:即使在较低的催化担载量和温和的反应条件下,Cu2O/g-C3 N4仍能表现出良好的催化性能并获得44.1％的收率.     

Magnetic diphase nanostructure of ZnFe2O4/γ-Fe2O3

Magnetic diphase nanostructures of ZnFe₂O₄/γ-Fe₂O₃ were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe₂O₄/γ-Fe₂O₃ was formed, in which the presence of ZnFe₂O₄ enhanced the thermal stability of γ-Fe₂O₃. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe₂O₃. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe₂O₃ content.     

The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.