电感耦合等离子体原子发射光谱法测定化学合成反应液中铑含量

为了更加快速准确的测定化学合成反应液中铑含量,建立微波消解前处理与电感耦合等离子体原子发射光谱的组合监测方法。采用硝酸-硫酸混合酸体系对样品进行微波消解前处理,将有机铑络合物体系转化为无机酸体系。在相同的条件下分别选用铑元素233.477 nm、249.077 nm、343.489 nm三个波长进行样品的测定,铑元素的质量浓度在(0~1.0)mg·L^(-1)线性良好,线性相关系数r≥0.9997,方法检出限分别为0.01 mg·L^(-1)、0.03 mg·L^(-1)、0.10 mg·L^(-1)。波长343.489 nm具有更好的灵敏度,更适合铑元素的检测,样品回收率98.0%~102.5%,相对误差为2.8%~3.4%,相对标准偏差为0.2%~1.1%。该方法是在密闭空间进行样品前处理,避免了元素的损失,操作简便,耗时短,精密度高,适用于化学合成反应液中铑含量检测。

电解水阳极析氧替代反应及高效催化剂研究进展

开发先进的电解水制氢技术,推动制氢产业规模化发展,是缓解当前能源危机和环境污染的有效途径.当前发展的电解水制氢技术存在析氧反应(OER)动力学缓慢、能耗高、O2附加值低、活性氧物种降解隔膜等问题,限制了电解水制氢的大规模应用.对电解水系统进行反应设计,以热力学上更易发生的阳极反应替代能垒较高的OER,降低过程能耗的同时,得到高附加值的氧化产品,具有显著的经济效益和发展潜力.本文系统综述了牺牲剂氧化反应(Sacrificial agent oxidation reaction,SAOR)和电化学合成反应(Electrochemical synthesis reaction,ESR)在OER替代研究中的最新进展,对这两大类替代反应进行了分类,重点讨论了它们的氧化机制、适用的非贵金属基催化剂及相应的调制策略.此外,对开发高性能催化剂助力低能耗混合电解水制氢系统可能面临的挑战和未来的发展方向进行了展望.

高分子材料的催化合成

介绍了常见的与高分子合成化学反应有关的化学催化、物理催化和生物催化的类型、特点和应用.

Electrochemical synthesis of catalytic materials for energy catalysis

Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy‐related electrocatalytic reactions.Compared with conventional wet‐chemical,solid‐state and vapor deposition synthesis,electrochemical synthesis is a simple,fast,cost‐effective and precisely controllable method for the preparation of highly efficient catalytic materials.In this review,we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms,spherical and shaped nanoparticles,nanosheets,nanowires,core‐shell nanostructures,layered nanomaterials,dendritic nanostructures,hierarchically porous nanostructures as well as composite nanostructures.Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed.Structure‐performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples.We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods,and we propose some research challenges and future opportunities in this field.

Ultrasonication solid state chemical reaction synthesis and characterization of nanocrystalline Zn(Oxin)_2·2H_2O (zinc 8-quinolinolate)

Under near ambient temperature and ultrasonication, nanocrystalline Zn(Oxin)2·2H2O (zinc 8-quinolinolate) was synthesized by solid state chemical reaction. The particle size distribution was relatively uniform, the morphology of the mare was ball like particle. The phase, particle size and morphology of the prepared nanocrystalline were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction (ED). The results show that the crystallite product has an average size of about 30 nm. The effects of a series of reaction conditions on the synthesis of Zn(Oxin)2·2H2O by solid state reaction were studied. During the synthesis of nanocrystalline Zn(Oxin)2·2H2O, the solid state reaction conditions such as changing reactant, matching proportion of reactant, adding inert substance, joining a little solvent or surface active solvent and grinding at different times may influence morphology, particle size and the size distribution of final products.

Sonochemical Synthesis of Maleated Rosin

The cycloaddition reaction of rosin and maleic anhydride under ultrasonic irradiation has been investigated. The results show that both isomerization and Diels-Alder cycloaddition reactions were accelerated remarkably. The sonochemical reaction reached equilibrium in 5-10 min at 110℃, comparing with regular synthesis of 4-5 h over 180℃.

Investigation into Syngas Generation from Solid Fuel Using CaSO4-based Chemical Looping Gasification Process

Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal oxide and calcium sulfate） to transfer heat and oxygen to the fuel. In this paper, the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor. Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process, showing some different features from the CLC. The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios. It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance. The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and ex- perimental results. It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.

The Search for New Methods of Synthesis Possible of Organometallic Compounds of P, As, Sb, Bi

The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N （nitrogen） atoms have been replaced on atoms of P （phosphorus）, As （arsenic）, Sb （antimony） and Bi （bismuth）. The authors have proposed a new mechanism for the possible reactions.

Mechanism of Clay Mineral Affect on Strength of Solidification Sludge

To solve the problem of vast cement and low strength in the treated sludge, clay mineral used for accessorial solidification material was applied to advance strength. The principle of solidification sludge strength because of clay mineral is not clear and has not supported the choice of clay mineral. The mineral and pore water is analyzed in order to contrast clay mineral added or not based on the XRD and pore water chemical character. The result shows that the absorbed quantity of Ca2~ was reduced by sludge because of clay mineral added, the hydrated reaction was advanced and integrated solidified materials was formed.

Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

The acid-functionalized ionic liquid([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance(NMR) and Fourier transform infrared spectroscopy(FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a homogeneous kinetic model was established. The results show that the reaction heat ΔH is 10.94 × 103J·mol-1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea-are 60.38 × 103 and 49.44 × 103J·mol-1,respectively.

Preparation and properties of nano-composite ceramic coating by thermo chemical reaction method

Nano-composite ceramic coating was fabricated on Q235 steel through thermo chemical reaction method. Structure of the coating was analyzed and the properties were tested. The results show that a few of new ceramic phases, such as MgAI2O4, ZnAI2O4, AI2SiO5, Ni3Fe and Fe3AI, are formed on the coating during the process of solidifying at 600 ℃. The ceramic coating is dense and the high bonding strength is obtained. The average bonding strength between the coating and matrix could be 14.22 MPa. The acid resistance of the coating increase by 8.8 times, the alkali resistance by 4.1 times, the salt resistance bv 10.3 times, and the wear resistance bv 2.39 times.

Enzyme-catalyzed Synthesis of Vitamin E Succinate Using a Chemically Modified Novozym-435

Vitamin E succinate was synthesized in organic solvents using a modified Novozym-435 as catalyst.In order to improve the catalytic performance of Novozym-435,the enzyme was modified using acetic anhydride, propionic anhydride and succinic anhydride separately.We found that both the hydrolytic activity and the thermal stability of the modified Novozym-435 were enhanced compared with the unmodified enzyme.The modified Novozym-435 catalysts were used to synthesize the succinate derivative of vitamin E.Compared with the native Novozym-435,the catalytic activity of the modified novozym-435 in promoting the synthesis of vitamin E succinate was dramatically increased,with the novozym-435 modified with succinic anhydride（N435-S）as the most active catalyst.Conditions for the synthesis of vitamin E succinate were also optimized.A mixture of tert-butanol and DMSO（volume ratio of 2︰3）was the most suitable medium for the reaction,whereas the appropriate molar ratio of vitamin E to succinic anhydride and reaction temperature were 1︰5 and 40°C,respectively.Under these reaction conditions,the yield of vitamin E succinate reached 94.4%.N435-S could be reused for five batches.

Electrode properties and phase composition of Ti_(0.5)Ni_(0.25)Al_(0.25) hydrogen storage alloys and theoretical simulation

Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.

Influence of Dispersion of Nano-ZnO Particles in Polymer Matrices on Properties of Relevant Nano Composite Fibers

The surface-passivated and non-surface-passivated zinc oxide nano-particles （marked as s-nanoZnO and ns-nanoZnO respectively） were evenly dispersed in polymer solutions with the aid of ultrasonic vibration to prepare nanocomposite film by free casting and to prepare nanocomposite fibers by wet spinning and to prepare nancomposites coating by surface smearing. The dispersion of s-nanoZnO and nsnanoZnO in PAN matrix were observed by transmittance electron microscopy, the mechanical properties of the relevant compesite samples were studied by INSRTON tensile strength tester. It was found that s-nanoZnO behaves a well-dispersed morphology in PAN films and fibers when its concentration was 2 wt% but ns-nanoZnO nano particles agglomerate into larger congeries in PAN films. It means that the surface-passivated process oft zinc oxide nano. particles was effective to disperse. The relative intensity and elonsation at break of s-nanoZnO-PAN composite fibers show maximum values with the increase of nano particle content in compesites （from 0 wt% to 2 wt% of s- nanoZnO）. The elasticity of the composite fibers increases whereas their modulus declines. Balanced the changes of the properties mentioned above, 2 wt% s-nanoZnO in PAN matrix is a proper content for the composite fibers spun by wet spinning. The result of surface smearing test means that the reactim between s-nanoZnO and polymer can be indicated by the color of nanocomposite surface coat on fibers.

SYNTHESIS OF FUNCTIONAL MACROMOLECULE INTERMEDIATE THROUGH COUPLING REACTION CATALYZED BY [bmim]Cl/FeCl_3 IONIC LIQUID

To obtain new functional aromatic polymer materiul. 3,3＇-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid （[bmim]CI/FeCl3） at mild reaction condition. Pure 3,3＇-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3＇-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following： the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3＇-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.

Synthesis and electrochemical performance of Li_3V_2(PO_4)_3 by optimized sol-gel synthesis routine

Li3V2（PO4）3 samples were synthesized by sol-gel route and high temperature solid-state reaction. The influence of Li3V2（PO4）3 as cathode materials for lithium-ion batteries on electrochemical performances was investigated. The structure of Li3Va（PO4）3 as cathode materials for lithium-ion batteries and morphology of Li3V2（PO4）3 were characterized by X-ray diffractometry （XRD） and scanning electron microscopy （SEM）. Electrochemical performances were characterized by charge/discharge and AC impedance measurements. Li3V2（PO4）3 with smaller grain size shows better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of Li3V2（PO4）3 are attributed to the refined grains and enhanced electrical conductivity. AC impedance measurements also show that the Li3V2（PO4）3 synthesized by sol-gel route exhibits significantly decreased charge-transfer resistance and shortened migration distance of lithium ions.

A Novel Efficient Method for Synthesis of β-Organoseleno Substituted Allyl Sulfoxides

Hydroselenation of 1, 2-allenyl sulfoxides give 2-organoseleno substituted allyl sulfoxides in high yields and the reaction is absolute regioselective.

A Simplified Green Chemistry Approach to the Synthesis of Carbon-Carbon Double Bonds Via Knoevenagel Condensation Catalyzed with ZrOCl2.8H2O

A green and simplified room-temperature procedure was reported for the synthesis of carbon-carbon double bonds by Knoevenagel condensation of various aldehydes with malononitrile and ethyl cyanoacetate in the presence of catalytic amount of ZrOCl2·8H2O in aqueous media.

Theoretical Considerations of Laminar Flame Speed as a Function of Initial Conditions and Basic Kinetic Properties with Respect to the Safety Problem

The Zeldovich-Frank-Kamenetskii solution for the flame velocity of a planar front with one-step overall chemical reaction was enhanced. The assumption that the consumption rate depends exclusively on a chemical component was removed. Instead, the reaction rate was considered to be dependent on all reactants of an overall reaction. The new formulation was applied to obtain the activation energy and the pre-exponential factor of a set of hydrogen-air mixtures.