松散接触下 Au-Ce强相互作用对 Au/CeO2/3DOM Al2O3催化剂催化柴油炭烟燃烧活性的影响

与汽油发动机相比,柴油发动机具有热效率高、CO2排放低、寿命长、续航距离远和经济性好等优点,可大大缓解能源短缺,降低 CO2排放量.因此,机动车柴油化是当前发展趋势.然而,柴油发动机在使用过程中会排放大量炭烟颗粒物,对人体危害极大.因此,控制炭烟颗粒排放成为环境催化研究的重点之一.
　　炭烟颗粒物催化燃烧反应是典型的固(炭烟颗粒)-固(催化剂)-气(O2)多相催化反应.三维有序大孔氧化物(3DOM)具有大孔径和内部贯通的孔道结构,能有效提高炭烟颗粒与催化活性中心的接触性能.同时,纳米 Au颗粒在大孔氧化物表面的负载可有效提高催化剂本征活性,但纳米 Au颗粒催化剂热稳定性较差. CeO2具有较好的储放氧性能,可与贵金属活性组分发生相互作用,从而提高贵金属纳米颗粒的分散度和稳定性.因此,本文从柴油炭烟颗粒物催化燃烧反应本质出发,设计制备了高炭烟燃烧催化活性的3DOM氧化物担载 Au基催化剂,研究了 Au与 CeO2强相互作用对炭烟燃烧活性的影响.
　　采用胶体晶体模板法制备3DOM Al2O3载体,由微孔膜氨沉淀法制备 CeO2/3DOM Al2O3催化剂,以还原-沉积法制备 Au/3DOM Al2O3和 Au/CeO2/3DOM Al2O3催化剂,并利用扫描电镜、N2物理吸附-脱附、X射线衍射、透射电镜、紫外漫反射光谱、H2程序升温还原和 X射线光电子能谱等手段对催化剂形貌、比表面积、物理化学性质和氧化还原性进行了表征.结果表明,在 CeO2/3DOM Al2O3中, Al3+可进入到氧化铈晶格内,形成 Al-Ce-O固溶体,产生氧空位,这有利于氧物种转移.此外, Au/CeO2/3DOM Al2O3催化剂中 Au和 CeO2之间的强相互作用能增加 Au纳米颗粒表面活性氧物种数量,从而促进柴油炭烟燃烧反应.纳米颗粒 Au的担载使得催化柴油炭烟燃烧的起燃温度明显降低,其中 Au/CeO2/3DOM Al2O3催化剂表现出最高的催化活性,T10,T50和T90分别为273,364和412oC.     

纳米ZnO室温选择氧化H2S特性的研究

碱式碳酸锌在不同焙烧温度下制得的纳米ZnO具有六方晶系纤锌矿结构，平均粒径为15.4 nm、19.1 nm、22.9 nm和33 nm，以其为脱硫剂，对H2S室温脱硫性能进行了研究。利用XRD和XPS技术对脱硫反应前后的样品进行了表征。实验结果表明，纳米ZnO的脱硫性能随粒径的增大而降低，常温、常压下，260 ℃焙烧的纳米ZnO对H2S有高的去除率，并且H2S可选择性地被氧化为单质硫。     

Dawson结构(NH4)6P2Mo18O62·12H2O纳米粉体的室温固相合成及形成机理

以H₆P₂Mo₁₈O₆₂·23H₂O和(NH₄)₂C₂O₄·H₂O为原料，首次采用室温固相反应合成出(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体，并运用元素分析、FTIR、XRD、TEM、TG-DTA和BET等技术对其组成、结构和性能进行了表征。发现(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体平均粒径为40 nm，保留着杂多阴离子的Dawson结构，具有Dawson结构的特征衍射峰，比表面积为143.9 m²·g^-1，在445 ℃以下杂多阴离子有良好的热稳定性。在该固相反应中，研磨和放热反应热能可加速反应物分子的扩散速率和生成物分子的成核速率，使产物粒径减小；反应物含有结晶水和生成物H₂C₂O₄·2H₂O对形成小粒径的(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体起关键作用。     

硫代乙酰胺体系电沉积法制备CdS纳米膜

The film of surface active agents spread out on the surface of the electrolyte of Thioacetamide and cadmium chloride. CdS nanofilm was deposited at the interface of surface active agents and electrolyt by the method of electrodeposition. The optimal conditions on which the nanofilm was prepared of the least crystals and uniform particles could be attained via analytical results of L₁₆(4⁵) orthogonal experiments. The optimal conditions: castor oil/hexadecanoll 0.06 mL·cm^-2，CdCl₂/CH₃CSNH₂ 4 mmol·L^-1, cell voltage 5 V, electrodeposition temperature 15 ℃. The effects on the grain size of temperature, surface-active agent, electrodyte concentration, cell voltage and pH become smaller in the series. If the temperature was high, the movement of molecules of surface-active agent and electrodyte would be faster, thus the preparation of the film would be difficult. The grain size of thinfilm varied with the surface-active agents, however, when the amount of surface-active agents reached a certain value, the grain size would remain unchanged. The higher the electrodyte concentration, the larger the grain size of nanofilm. The surface forms were changed at the same time. If the pH of the electrodyte was higher or lower, nanofilm could not be prepared successfully, thus the pH range should be is 3～6. SEM image of the nanofilm shows the occurance of dendrite. The sucessful preparation of nanofilm is closely related to the nature of surface activre agent due to the nanofilm growth mechanism.     

纳米Zn-Co铁氧体的固相合成及电磁损耗特性研究

采用NH₄HCO₃与FeCl₃·6H₂O，Zn(NO₃)₂·6H₂O，Co(NO₃)₂·6H₂O进行室温固相反应制得前驱物，经微波加热处理后，进而热分解分别制得复合氧化物ZnFe₂O₄、CoFe₂O₄和Co_0.5Zn_0.5Fe₂O₄。由激光粒度分析仪、XRD和SEM表征：获得了颗粒分布比较均一、平均粒度为65 nm左右、立方晶系尖晶石结构的纳米铁氧体粉体。经测试样品的相对介电常数和相对磁导率后，研究了它们的电磁损耗特性。结果表明：Co_0.5Zn_0.5Fe₂O₄在100～1 800 MHz内比另外两种铁氧体具有更好的电磁损耗特性。     

高分散纳米二氧化钛混合晶体的合成、结构与光催化性能

Using TiCl₄ and urea as the raw materials and nanometric carbon black as plate, nanometric mix-crystals of rutile and anatase TiO₂ were prepared at 100 ℃ for 10～180 min by homogeneous precipitation method. The effects of pH on the ratio of nanometer TiO₂ mix-crystals were also discussed. TEM measurement indicates that the TiO₂ is spherical particles, and the average diameter of the particles is 20 nm. XRD and TG-DTA were also used to characterize the nanometer mix-crystal materials. The photocatalytic experiment show that the mix-crystal material has the best photocatalytic reactivity. After being irradiated under the sunlight for 40 min, the compound can completely degrade the acid-red 3R.     

纳米晶PbTiO3负载CuO催化NO分解

A large specific surface area perovskite-type mixed oxide PbTiO₃ supported cupric oxide was synthesized as a catalyst for NO decomposition and characterized by techniques such as XPS, XRD, H₂-TPR before and after NO decomposition reactions. The catalytic properties were tested with a fix-bed micro-reactor. The results showed that the PbTiO₃ was inactive for the reactions, but 1wt % Cu/PbTiO₃ catalyst gave fairly good activities for NO decomposition at temperature as low as 473 K. Copper species were found well-dispersed but weakly interacted with the support before NO decomposition, and the NO decomposition caused significant change in the environment of the copper species, which became Cu(Ⅰ) and most probably incorporated into surface crystal lattice of the nano-sized PbTiO₃. In NO reaction, a large amount of oxygen atoms from the decomposition of NO penetrated into the nano-sized PbTiO₃ support and caused small expansion of crystal lattice. The transport of oxygen between the copper species and the catalyst support may be helpful to speed up the kinetic regeneration of active metal sites from oxygen occupancy and resulted in good catalytic performance.     

新颖氧化镁纳米带共沉淀法合成与表征

氧化镁是一种具有重要工业用途的物质,在催化、陶瓷、塑料和橡胶等领域有着广泛的应用.当尺寸细化至纳米量级后,因纳米材料所特有的体积效应和表面效应,纳米氧化镁在低温烧结、微波吸收、催化性能等众多方面呈现出许多不同于本体材料的热、光、电、力学和化学特性,因而引起了人们广泛的研究兴趣[1,2].其中氧化镁纳米线、纳米带、纳米管等一维纳米结构材料以其新颖的结构形式及与之相关的性能,近年来更为引人关注.     

Fe3+掺杂TiO2光催化降解聚乙烯薄膜的研究

以快速溶胶-凝胶法制备了纳米TiO₂光催化剂，并用Fe³⁺对其掺杂改性，在室温条件下, 用于固相光催化降解聚乙烯(PE)包装薄膜的研究. 对催化剂和薄膜进行了X衍射分析(XRD)、傅立叶红外光谱分析(FT-IR)、扫描电子显微镜(SEM)形貌观察. 结果表明， 60 W紫外光辐射240 h后， PE失重为8.43%, 锐钛矿型纳米TiO₂光催化剂使PE失重30.66%；用Fe³⁺掺杂后，0.5%Fe₂O3/TiO₂、1.0%Fe₂O₃/TiO₂和2.0%Fe₂O3/TiO₂分别使PE失重35.91%、20.72%和13.30%. 光催化剂加速了PE的失重，碳链的断裂和光氧化腐蚀，在薄膜表面形成大量的坑洞，降解产物中的小分子量的石蜡含量明显增高. Fe³⁺掺杂有一个最佳量， 0.5%Fe₂O3/TiO₂光催化降解PE的活性最高.     

氧化锌薄膜的电化学沉积和表征

以透明导电玻璃(TCO)为衬底，用硝酸锌水溶液作为电解液，研究了阴极还原沉积ZnO薄膜的反应机理和电化学行为. 通过改变工艺条件来控制ZnO的生长速率， 得到了粒径为10～15 nm的纳米ZnO薄膜. XRD分析显示纳米ZnO薄膜纯度高， 呈纤锌矿结构. 光学测试结果表明，在可见光区其透光度高达90%，禁带宽度为3.37 eV.