Surface-modified MnS nanoparticles were synthesized in mixed solvent of water-ethanol by the reaction of MnCl2•2H2O, Na2S•9H2O and surface modification agent dialkyldithiophosphate(DDP). The structure of surface-modified MnS nanoparticles was investigated by XPS,FTIR,TGA, XRD, TEM and HREM. The results show that the DDP-capped MnS nanoparticle consists of a layer of DDP molecules and MnS nanoparticles core. The diameter of DDP-capped MnS nanoparticles is 510 nm. The crystalline structure of inorganic MnS nanoparticle core is γ-MnS. Meanwhile, Surface-modified MnS nanoparticles have better chemical stability and thermostability. They are also well dispersed in organic solvents such as trichloromethane, benzene and in liquid paraffin.

In this paper, based on ab initio methods, the intrinsic reaction coordinate (IRC)of the reaction HCN+Cl→HCl+CN is traced at the basis level of UHF/6-311G. Along the IRC, the dynamical properties of the reaction are investigated. The theoretical rate constants of the conventional transition-state theory and variational transition-state theory are calculated, and they are for experimental reference. The product vibrational state distribution of CN for the reaction HCN(004,302)+Cl→HCl+CN is also calculated by the subroutine which is compiled using vibration transtion probability formula based on SCP-IOS theory. The calculated results are in od agreement with experiments.

 A series of Cu-Ce-O catalysts, prepared by amorphous citric processor, have been investigated by XRD, ICP and micro-reaction techniques. The results showed that for low copper content Cu-Ce-O catalysts, fluorite structure formed at low calcining temperature, CuO doped into the CeO2 matrix; for high copper content, in addition to fluorite structure, crystalline monoclinic phase CuO formed as well at high calcining temperature. No other crystalline phase formed even calcined at temperatures as high as 1000 ℃.The catalytic activity of CO oxidation was greatly promoted for the synergistic effect between copper oxide and ceria. The optimum catalyst is that calcined at 700 ℃ for 4h with the relative composition of 15% of Cu/(Cu+Ce) (atomic ratio),while the formulation of the active complex oxide with fluorite structure is Cu0.06Ce0.94O1.94.

The formation and photodissociation of Pb/S cluster ions, produced by tow different ways of laser ablation, were studied with a tandem time-of-flight mass spectrometer. By laser direct ablation on a mixed Pb+S sample, the cluster ions with the compositions of PbnSn-1+ or PbnSn- were the most abundant species and can be identified as the stable components of Pb/S cluster ions. By laser double ablation on separated Pb sample and S sample, the products were PbnSm+(n=1-3, m=0-9) and PbnSm-(n=1-7, m=0-9) formed through reactions between Pb clusters and S clusters. Form the distributions of cluster compositions and the photodissociation of clusters, we can confirm two different formation mechanisms of Pb/S clusters according to the producing ways of clusters.

A copolymer containing hydrophobic monomers(styrene, methyl methacrylate and butyl acrylate)and hydrophilic momomer (acrylacrylic acid)was synthesized by solution polymerization, and then neutralized by N,N-diethylamino ethanol to form soap-free hydrosol. The hydrosol coating could be prepared by mixing this hydrosol with the crosslinking agent M(NH3)42+ (M2+ could be either Zn2+,Cu2+. Ni2+ or Co2+). It was supposed that in the soap-free acrylate hydrosol/M(NH3)42+ mixed system, before heating,M2+ in the form of M(NH3)42+could not react with the hydrosol(P-COO-)completely leaving some _COO-free to stabilize the hydrosol, and after heating(or curing),M2+ could be set free from NH3 ligand to join the coordination-crosslinking reaction with(P-COO-) forming network structure (P-COO-)n M2+.IR spectrographic analysis, fluorescence analysis and the linear sweep voltammetry plarogrphic analysis identified the existence of (P-COO-)nM2+ in the coating film. The crosslinking extent of the coating film was investigated by DSC and gravimetric analysis. All results indicated that the appropriate crosslinking agent was Zn(NH3)-2+ and the optimum curing condition was heating at 80℃ for 30 min. The crosslinking process of the hydrosol with Zu(NH3)42+ was examined by TEM. The kinetics of the crosslinking reaction has been studied preliminarily by DSC showing that the reaction activation energy was 34.0kJ•mol-1 and the order of reaction was 3.3, indicating that the crosslinking reaction may be a rather complex reaction. 

 Dimerization reactions of thioketene and bis(trifluoromethyl) thioketene have been studied by means of HF/6-31G* and semiempirical AMI. All the geometries of the stationary points on the reactions path have been optimized by energy gradient technique, and all the transition states were characterized by vibration frequency analysis. The results can be summed up as follows: three different dimerization processes of thioketene and bis(trifluoromethyl)thioketene are all concerted but nonsynchronous,taking place through twisted four-membered cyclic transition states. The activation enthalpies were calculated to be 122.53, 126.47 and 136.68 kJ•mol-1 respectively for three thioketene dimerization processes. Contrarily, for the three bis(trifluoromethyl)thioketene dimerization reactions, the activation enthalpies are 287.05,274.65 and 218.84kJ•mol-1 respectively, which are in consistence with experimental fact.

【Abstract】 In order to study the aldol condensation of 2.15-hexadecanedione on the surface of aluminium, the intermolecular condensation mechanism of acetone occurring on aluminum was simulated by using semi-empirical AM1 method embodied in MOPAC 6.0 program package. The optimized structures and geometry parameters of 5 transition complexes and 4 intermediates were given. First, 2 molecules of acetone coordinated with aluminum by electrostatic attraction. One atom of hydrogen of acetone migrated to aluminum because of the pulling of the negative oxygen of aluminum, and then aldol condensation occured. Some aluminum containing complex substances may be generated according to the energy variation of intermediates.

The microstructure and electric conduction variations in compounds Nd0.67Sr0.33-xBaxMnO3(x=0.27, 0.165, 0.06) and Nd0.67SrxBaxMnOz(x=0.27, 0.06) were studied. It was found that the conduction mechanism of Nd0.67Srx.Ba0.33-xMnO3 doped by mixed divalent ions differs from that of Nd0.67Sr0.33 MnO3 or Nd0.67Ba0.33MnO3 doped by single divalent ions. Due to the lattice contraction induced by nonstoichimetry, the resistivity reduces obviously and the resistivity transition (I-M) appears with decreasing temperature in Nd0.67SrxBaxMnOz. In addition, it was found that the lattice contraction induced by the nonstoichiometry on Mn site is larger than that on A site.

Catalysts with spinel structure derived from Hydrotalcite-like Compounds (HTLcs) containing cobalt have been investigated in NO catalytic reduction by CO. It was found that catalysts with spinel structures derived from HTLcs had obviously higher activity than that prepared from general methods. A two-step reaction was observed during the reaction curse: NO was first reduced to N2O by CO, and with the increase of temperature, the N2O was reduced to N2. The reactivity of the catalysts studied increased with the amount of cobalt-content in the catalyst, and decreased with the calcination temperature. The crystal defect would play and important role in the reaction.

The kind of lyotropic liquid crystal formed by Igepal CO series-H2O system is related to the number of EO group of the surfactants, but the concentration range is related to the minumin water content needed for the formation of lyotropic liquid crystal and the maximum water content solubilizated in lyotropic liquid crystal. n<10, lamellar liquid crystal forms and n>10, hexa nal liquid crystal forms. The minumin and maximum ratios of water to surfactant in amphiphtic bilayer of lamellar liquid crystal increase nonlinearly and linearly, respectively, with the EO group in lgepal CO series surfactant. There is no observable change for the formation of lamellar liquid crystal with addition of Igepal CO 710 in the Igepal CO 520 system. But the system shows the transformation of liquid crystal from hexa nal to lamellar when Igepal CO 520is added in the Igepal CO 710 system.

The variation of interfacial tension with temperature of two different systems, water-oil (liquid paraffin, C18H38, solution of solid paraffin)and silicone oil-vegetable oil was determined and the factors that influence the variation of the shape of the relation curves were examined. It is found that the presence of minute amount of surface active impurity was the main cause of the shape variation of the relation curves. The shape variation was eliminated by adsorptive agent. Therefore, it is important to insure purity of the experimental system in order to obtain reliable results on the study of thermocapillary flow caused by interfacial tension.

A novel material, uncoated polyamline/bentonite layered nanocomposits has been prepared successfully and characterized by XRD、FTIR、CV、TGA. Experiments suggest that it still has the layered structure of bentonite, but has larger interlayer space. The properties of both polyaniline and bentonite are reserved. This material has potential applications as electrode material for electrochemical battery and electrode modifyiny materials.

The microstructures of the middle-phase microemulsions were studied by using ESR and NMR techniques. The results from the two methods show that the microstructures of the middle-phase microemulsions under the change from O/W to bicontinuous(BC), and to W/O with the variation of NaCl concentration, and BC structure includes O/W and W/O. The models of the bicontinous structure were constructed on the base of the studies.

The mechanism of the cycloadditohn reaction of singlet difluorosilylene with formaldehyde have been studied by RHF/6-311G* gradient method. The electron correlation energy corrections of energies for all the structures were computed using second-order Moller-Plesset perturbation theory(MP2). The results show that this reaction proceeds via two steps:1)Difluorosilylene and formaldehyde form an intermediate complex, it is an exothermal reaction with no barrier.2) The intermediate complex isomerizes to form the product, after being corrected by zero-point energies, the barrier is 127.28 kJ•mol-1 (MP2/6-311G* 6-311G*).

The microstructural characteristics of P-25 TiO2 photocatalysts calcined at 600, 650,700, 750, 800, 900 and 1000℃ have been studied using XRD, TEM and BET. The photocatalytic activity of the samples were also examined using the degradation of phenol as a model reaction. The results indicate that the calcination significantly affects both microstructural characteristics and photoactivity, and there is an apparent relationship between photocatalytic activity and centain mocrostructural characteristics. Over the range of calcination temperatures and durations studied, the sample calcined at 650℃ for 3 h revealed the highest photoreactivity, which can be ascribed to an improvement in crystallinity on calcination. The increase in the rutile content and grain size caused by the calcination at higher temperatures were observed to decrease the photocatalytic activities of the TiO2 samples.

The flocculation of two kinds of silica particles with different surface properties have been studied on the addition of PAM. In certain pH range, PAM can flocculate suspensions of SiO2particles which have been calcined with a little water added. Although PAM doesn’t flocculate suspensions of SiO2 particles calcined with no water added, it produces od coordinate flocculating effect on mixing with PA.

研究了一些氧化物的H2－TPR及CO－TPR行为，结果发现，Co3O4／Al2O3，NiO／SiO2，NiO和Pd／NiO的H2－TPR温度要低于它们的CO－TPR温度，特别是Pd／NiO样品，它的H2－TPR温度为598K，而其CO－TPR温度高达949K，差别为351K，因此有可能利用Pd／NiO在一定温度下选择性地与CO中的H2反应而将其除去. 实验结果表明，Pd／NiO可在603K及4000h-1的条件下从H2（0.34％），CO（50％）和N2（余）的混合气中选择性地除去90％以上的H2，吸氢容量为每克样品55mL标准态H2.