介孔SnO_2的制备及气敏性能研究

采用CTAB模板法制备了具有介孔结构的SnO2。通过小角X射线衍射,BET法对其进行了表征。采用静态配气法对介孔SnO2的气敏性能进行了研究。结果表明:随着煅烧温度的升高,介孔SnO2的比表面积从105.54m2/g降到38.11m2/g。通过延长陈化时间和进一步水热处理可以增加介孔SnO2材料的比表面积。气敏测试表明:在4.5V加热电压下,气敏元件对体积分数为50×10-6酒精蒸气有较好的气敏性能,灵敏度为9.4,响应-恢复时间均为8s。     

In2O3基气敏材料的催化性能及敏感机理研究

采用微反应器–气相色谱联用装置和气敏性能测试设备,评价了不同掺杂的In2O3材料对异丁烷的催化及气敏性能。研究表明:掺杂贵金属(Pd、Pt、Au等)可大幅度提高材料对异丁烷的催化活性,灵敏度也由2.99提高到4以上;而掺杂碱性金属氧化物则降低了材料的催化活性和灵敏度。材料的气敏性能和催化性能存在密切的关系。并浅析了材料的敏感机理。     

碳酸镍沉淀过程的研究以及介孔氧化镍的制备

Nickel carbonate and nickel oxide are important inorganic fine chemicals, widely used in chemical, metallurgical, electronic and energy sources industries. The research was beginning with studying the effects of anions on precipitation process of nickel carbonate. Activity coefficient shows the effect size of the microcosmic effects between ions and solvent. Meissner's semi empirical model was applied to calculate the average activity coefficients of nickel carbonate in different electrolyte solutions at different conditions. And the conditional solubility of nickel carbonate was also calculated. The calculated results show that activity coefficients of NiCO3 in sodium sulphate solutions are less than that in sodium chloride solutions, and the solubilities in sodium sulphate solutions are larger. To improve the confidence of the calculations, Bromley's and Pitzer's models were also applied to calculate activity coefficients. The calculation results of Bromley's and Pitzer's models are very close to Meissner's results. And then experiments were carried out to measure the surface tensions, and contact angles of solutions on NiCO3 surface. According to the experiment results, the solid-liquid interface tension between NiCO3 and sodium sulphate solution is larger than that between NiCO3 and sodium chloride solution. And the tiny crystal NiCO3 has larger solubility in sodium sulphate solutions, which indicates that crystallization of NiCO3 in sodium sulphate solution is more difficult than in sodium chloride solution. The influence of SO 42- and Cl- on precipitation and crystallization process of NiCO3 was also studied based on crystal dynamics. The supersaturations at different initial concentration of reaction system were compared. Diffusion coefficients of ions were described by Glasstone's model. The diffusion coefficients of Ni2+ and CO 32- in chloride solutions are larger than those in sulphate solutions. In sulphate solutions, the diffusion coefficients and supersaturation are both less, therefore nucleation and growth rates are more slowly. Furthermore, the experiments of crystallization dynamics show that the reaction of nickel carbonate precipitation is a first order reaction while the reaction rate constant is about 0.02 min-1. Based on the theoretical analysis above, technology process of nickel carbonate precipitation was studied subsequently. The effects of nickel salt, feeding mode, controlling pH, reaction temperature and aging condition on purity, particle size, appearance of product and recovery ratio of nickel were investigated. Then using industrial nickel electrolyte solution and sodium carbonate as the raw materials, nickel carbonate product with nickel content of about 51%,average particle size of 17 μm was prepared at optimal conditions, and the recovery ratio of nickel is around 99.5%. Nickel carbonate with high purity was obtained via an innovative impurity removal process, called wash-dry-rewash-redry process. The sodium and chlorine qualitative contents of the nickel carbonate purified by the innovative method are both less than 0.01% and the sulphate content is no more than 0.1%. The mechanism of sodium and chlorine adsorption onto nickel carbonate's surface was discussed, using Stern's model of electric double layer. Moreover computational simulation technology was applied to investigate on how anions affect the crystallization of NiCO3 at atom scale. The lattice structure was relaxed before establishing crystal surfaces. The computational unit cell parameters are very close to the experimental data. Five main surfaces were studied, i.e. the (104), (100), (110), (001) and (101) surfaces. SO 42- substitutes the CO 32- on the outmost layer. Cl- adsorbs onto the surfaces and has relative weaker interaction with the surfaces. Compared with only hydrated surfaces, the growth rates of defected hydrated surfaces significantly decrease, especially for SO 24- defected ones. The (104) surface is the most stable surface and is mainly expressed in the equilibrium morphology of the resulting crystal. Finally, based on the study of nickel carbonate synthesis, nickel oxide with mesoporous structure was prepared by adding template into the nickel source and calcination. The effects of types of surfactant, dosage of surfactant, calcination temperature and calcination time on pore structure and specific surface area of nickel oxide were investigated. The results show that the surface area of the nickel oxide prepared by sodium dodecyl sulphate (SDS, anion surfactant) is much larger than those of which prepared by CTAB and octadecylamine. It is suggested that the inorganic species, basic nickel carbonate, is interacted with the template, SDS, by electrostatic attraction force. The precursor hardly has any surfactant residue after calcination. Nickel oxide with high specific surface area (>200 m2· g-1) is synthesized by adding low amount of template at the mole ratio of SDS:Ni less than 0.1:1.0. The nickel oxide has H3 type hysteresis and the pore size distribution mainly ranges from 2 nm to 10 nm. And it has good thermal stability.