Microstructural and compositional aspects of ZnO-based varistor ceramics prepared by direct mixing of the constituent phases and high-energy milling

ZnO-based varistor samples were prepared by the direct mixing of the constituent phases (DMCP) and sintering at 1100 °C for 2 h. The influence of the starting powder mixture's composition – the amounts of the pre-reacted varistor compounds and their composition – and its preparation, either with or without mechano-chemical activation (MCA), on the microstructure, phase composition and electrical characteristics of the varistor samples was studied. It showed that MCA improved the density and microstructural homogeneity of the varistor samples. MCA strongly affected the grain growth: it enhanced the nucleation of inversion boundaries (IBs) in the ZnO grains and the IBs-induced grain-growth mechanism resulted in uniform grain growth and hence a microstructure with smaller ZnO grains and a narrower grain size distribution. The final phase composition of the samples prepared by the DMCP method mainly depended on the presence of varistor dopants that can prevent the formation of the pyrochlore phase, especially Cr₂O₃, while MCA can affect it mostly by providing a homogeneous distribution of those dopants. The DMCP varistor samples prepared with MCA had much better current–voltage characteristics than the samples of the same composition prepared from unactivated powders.     

不同预处理工艺对磷石膏性能的影响

为研究不同预处理工艺对磷石膏性能的影响,通过X射线衍射、X射线荧光光谱、扫描电子显微镜、热重分析等手段表征磷石膏化学组分、微观形貌、晶型等特征,然后分别用普通煅烧法、微波煅烧法、水洗法、球磨法工艺对原状磷石膏进行力学性能、工作性能、凝结时间及需水量等指标的对比研究。结果表明：普通煅烧法、水洗法对可溶性五氧化二磷、氟类和有机质等杂质去除效果明显;微波煅烧法时间短,只需20 min左右;球磨法能细化颗粒,处理时间在20 min左右最佳。通过预处理制备的磷石膏物理化学特性都得到很大改善,抗压、抗折强度均优于GB/T 9776—2008《建筑石膏》指标,具有巨大的应用前景。     

Catalytic conversion of trichloroethylene on nickel containing beta zeolites into value added products

Nickel containing BEA zeolites, NiSiBEA and NiHAlBEA, with 2 wt% of Ni were prepared by a two-step postsynthesis method and conventional wet impregnation. The calcination of NiSiBEA and NiHAlBEA at 773 K for 3 h in air led to the formation of C-NiSiBEA and C-NiHAlBEA. After reduction at 873 K for 3 h in flowing 10% H₂/Ar, red-C-NiSiBEA and red-C-NiHAlBEA were obtained and investigated as the catalysts in hydrodechlorination of trichloroethylene at 503 K. Comparative study performed on red-C-NiSiBEA and red-C-NiHAlBEA showed very high stability of the catalyst prepared by a two-step postsynthesis method and strong deactivation of the catalyst prepared by conventional wet impregnation during ~ 17 h of reaction. Application of both catalysts resulted in high selectivity to unsaturated hydrocarbons that are the most desired products in HDC processes. TPH of the catalysts after kinetic run have shown that the main cause of deactivation of NiHAlBEA is the formation of carbonaceous species during hydrodechlorination of trichloroethylene.     

Preparation of Thermally Stable Mesostructured Nano-sized TiO2 Particles by Modified Sol–Gel Method Using Ionic Liquid

The mesoporous anatase form of TiO₂ was prepared by modified sol–gel method using ionic liquid as a template agent. The prepared nanosize TiO₂ particle was characterized by N₂-physisorption, XRD, TEM, and SEM. The physical properties of prepared TiO₂ particles were compared with that prepared by conventional sol–gel method without template. It has been proved that the anatase phase prepared by modified sol–gel process using ionic liquid was preserved well even if the TiO₂ samples were treated at high temperatures up to 800 °C while those prepared by conventional sol–gel method were transformed from anatase to rutile phase gradually during calcinations at 600 °C. Moreover, there was no phase transition in the sample obtained by sol–gel method with ionic liquid in spite of prolonged calcination for 60 h at 600 °C. However, in case of those samples prepared by conventional sol–gel method, the portion of rutile form was continuously increased with the increase in the calcination period.     

制备方法对Ce_(0.67)Zr_(0.33)O_2固溶体性能的影响

用氧化共沉淀法、均匀共沉淀法和柠檬酸溶胶-凝胶法制备了Ce_(0.67)Zr_(0.33)O_2固溶体,并将经和900℃焙烧后的固溶体进行了XRD、BET、Raman、H_2-TPR和储氧量(OSC)表征。结果表明,氧化共沉淀法和柠檬酸溶胶-凝胶法制备的Ce_(0.67)Zr_(0.33)O_2固溶体的储氧量、比表面积均高于均匀共沉淀法,且制备的固溶体经900℃焙烧4 h后未出现相分离,具有良好的热稳定性。     

Synthesis and Thermal Treatment of Pd-Cr@Carbon for Efficient Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

A nanostructured Pd-Cr catalyst was deposited on a supported carbon surface using the modified borohydride reduction method for the oxygen reduction reaction (ORR) to be utilized as an efficient catalyst in the proton-exchange membrane fuel cell. The crystal structure and feature nanostructure of the Pd-Cr@carbon were established through the use of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Meanwhile, its catalytic activity was studied using the cyclic voltammetry and electrochemical polarization techniques. Based on the XRD analysis, it was observed that the Pd phase with the fcc crystal structure was dominant, while the Pd-Cr phase with tetragonal crystal structure was detected only for the as-prepared sample and samples calcined at 573 K. The estimated average crystallite size of the Pd phase increased from 9.66 to 37.54 nm as the calcination temperature increased to 973 K, and the calcination time had a slight effect on the crystallite size. On the other side, the average crystallite size for the formed Pd-Cr phase slightly increased from 43.74 nm for the as-prepared sample to 44.90 nm for the sample calcined at 573 K for 3 h. The TEM examination revealed the uniform distribution of the Pd and Pd-Cr nanoparticles upon the carbon surface. The calcination temperature and time played an important role in controlling the structural and morphology parameters of Pd-Cr@carbon. The adsorption/desorption potentials were found to be dependent on the calcination temperature and time and hence the particle and crystallite sizes. The optimum ORR activity and chemical stability were observed for samples calcined at 773 K for 3 h.

     

Mechanochemical Synthesis of Visible-light Induced Photocatalyst with Nitrogen and Carbon Doping

Nitrogen and/or carbon doped titania photocatalysts were prepared by a novel mechanochemical method. The prepared powders possessed two absorption edges around 400 and 540 nm wavelengths and showed excellent photocatalytic ability for nitrogen monoxide oxidation under visible light irradiation. Under the irradiation of visible light of wavelength >510 nm, 37% of nitrogen monoxide could be continuously removed by the carbon and nitrogen co-doped titania prepared by planetary ball milling of P-25 titania-10% hexamethylenetetramine mixture followed by calcination in air at 400?C.     

Novel preparation method of highly active Co/SiO2 catalyst for Fischer-Tropsch synthesis with chelating agents

Co/SiO₂ catalysts were prepared by the incipient wetness method using the aqueous Co nitrate solution modified with various organic acids and/or chelating agents followed by drying and calcination. After H₂ reduction at 773 K, the catalyst prepared with nitrilotriacetic acid (NTA) showed Fischer-Tropsch synthesis (FTS) activity ca. 3 times higher than the catalyst without additives under mild reaction conditions (503 K, 1.1 MPa).     

TiO2薄膜光催化剂的性能研究

采用溶胶-凝胶法在玻璃管上制备了透明的TiO₂薄膜，并利用XRD、Raman、UV-Vis和XPS技术对薄膜进行了表征。结果表明,在773 K焙烧的TiO₂样品在290～330 nm处的吸收明显强于573 K焙烧的样品。在573 K焙烧的情况下，薄膜基本为非晶态，但却表现出良好的光催化活性，并随着负载层数的增加，薄膜的光催化活性逐渐增加。在573 K以上，随焙烧温度的升高，TiO₂薄膜的光催化活性逐渐降低。     

Preparation of Phase‐Pure K0.5Na0.5NbO3 Fine Powders by a Solid‐State Reaction at 625°C from a Precursor Comprising Nb2O5 and K,Na Acetates

Phase‐pure K_0.5Na_0.5NbO₃ (KNN) fine powders were synthesized via a solid‐state route from a homogeneous solid mixture. A colloidal dispersion comprising a mixed ethanol solution of potassium and sodium acetates and Nb₂O₅ fine particles was attrition milled and dried carefully to avoid water absorption. Two‐step calcination in air at 450°C and 625°C, each for 3 h, resulted in the phase‐pure KNN powders. The volume‐based median diameter of the final product was ca. 0.8 μm. Starting from the same precursors without dissolving the acetates, the phase‐pure KNN was never achieved even when the two calcination temperatures were increased to 550°C and 700°C, in spite of the same milling conditions. Key issues of eliminating second phases were (i) starting from a wet‐milled mixture with a single solution containing both of the A‐site species, and (ii) repeated wet milling of the reaction mixture to disintegrate reaction‐induced agglomerates. These enabled rapid nuclei growth from chemically interacted precursor prior to calcination, and short diffusion path due to repeated deagglomeration, excluding formation of off‐stoichiometric second phases. All these items were confirmed by different analytical tools, among others, thermo‐gravimetry and differential thermal analysis (TG‐DTA), particle size analyses, and XPS at various reaction stages. On the heating stage microscope, a shrinkage onset was observed at 850°C, that is, 150 K lower than that of conventionally prepared KNN, that is, via a solid‐state synthesis from carbonates by a two‐step calcination at 800°C and 750°C, for 4 h each. No second phase was observed after sintering up to 1100°C.     

微乳液结合Sol-Gel法制备纳米ZnTiO3及其表征

将溶胶-凝胶法与微乳液化学剪裁法相结合,以钛酸丁酯和氯化锌制备凝胶,在OP-10-SDS/正丁醇/环己烷/水复配微乳体系中进行化学剪裁制备前驱物,再经煅烧制备了组成单一的球状纳米ZnTiO3粉体,通过XRD、TEM、SEM、TG-DSC等方法对产物进行了表征,并讨论了凝胶的陈化时间、煅烧温度和煅烧时间对纳米ZnTiO3的组成、粒径和形貌的影响,提出了纳米ZnTiO3可能的形成机理。结果表明,在700℃煅烧2h制备的纳米ZnTiO3平均粒径为35nm,粒径分布比较均匀,基本呈单分散;适当延长陈化时间会减少ZnO及TiO2杂质;随着煅烧时间的延长,ZnTiO3晶体粒径开始增大;煅烧温度过高会使六方相ZnTiO3分解为立方相的Zn2TiO4和金红石型TiO2。     

微乳液结合Sol-Gel法制备纳米ZnTiO_3及其表征

将溶胶-凝胶法与微乳液化学剪裁法相结合,以钛酸丁酯和氯化锌制备凝胶,在OP-10-SDS/正丁醇/环己烷/水复配微乳体系中进行化学剪裁制备前驱物,再经煅烧制备了组成单一的球状纳米ZnTiO3粉体,通过XRD、TEM、SEM、TG-DSC等方法对产物进行了表征,并讨论了凝胶的陈化时间、煅烧温度和煅烧时间对纳米ZnTiO3的组成、粒径和形貌的影响,提出了纳米ZnTiO3可能的形成机理。结果表明,在700℃煅烧2h制备的纳米ZnTiO3平均粒径为35nm,粒径分布比较均匀,基本呈单分散;适当延长陈化时间会减少ZnO及TiO2杂质;随着煅烧时间的延长,ZnTiO3晶体粒径开始增大;煅烧温度过高会使六方相ZnTiO3分解为立方相的Zn2TiO4和金红石型TiO2。     

Preparation and characterization of LaFe1−xMgxO3/Al2O3/FeCrAl: Catalytic properties in methane combustion

MnO_x–CeO₂ mixed oxides prepared by sol–gel method, coprecipitation method and modified coprecipitation method were investigated for the complete oxidation of formaldehyde. Structure analysis by H₂-TPR and XPS revealed that there were more Mn⁴⁺ species and richer lattice oxygen on the surface of the catalyst prepared by the modified coprecipitation method than those of the catalysts prepared by sol–gel and coprecipitation methods, resulting in much higher catalytic activity toward complete oxidation of formaldehyde. The effect of calcination temperature on the structural features and catalytic behavior of the MnO_x–CeO₂ mixed oxides prepared by the modified coprecipitation was further examined, and the catalyst calcined at 773 K showed 100% formaldehyde conversion at a temperature as low as 373 K. For the samples calcined below 773 K, no any diffraction peak corresponding to manganese oxides could be detected by XRD measurement due to the formation of MnO_x–CeO₂ solid solution. While the diffraction peaks corresponding to MnO₂ phase in the samples calcined above 773 K were clearly observed, indicating the occurrence of phase segregation between MnO₂ and CeO₂. Accordingly, it was supposed that the strong interaction between MnO_x and CeO₂, which depends on the preparation route and the calcination temperature, played a crucial role in determining the catalytic activity toward the complete oxidation of formaldehyde.     

Photocatalytic degradation of 4-nitrophenol with ZnO supported nano-clinoptilolite zeolite

Photocatalytic degradation of 4-nitrophenol aqueous solution was investigated using ZnO/nano-clinoptilolite zeolite under UV irradiation. Nano-powders of clinoptilolite were prepared using a planetary ball mill mechanically method. The photocatalyst was prepared by ion exchanging of nano-clinoptilolite in a 0.1 M zinc nitrate aqueous solution for 24 h followed by calcination at 450 °C for 12 h. Samples were characterized by XRD, FT-IR, DRS, AAS, TG/DTG, SEM, TEM and BET. Effects of various key operating parameters on the degradation rate were studied. The COD and HPLC tests were also used to confirm the degradation extent of the pollutant.     

纳米石墨包覆球形LiFePO_4正极材料的制备及其性能研究

采用湿球研磨-喷雾干燥法合成了纳米石墨包覆的球形LiFePO_4材料。该材料呈现了大小较为均匀的球形颗粒,颗粒度较小。性能测试表明该材料具有优异的电化学性能,最佳样品C在0.1 C时的放电比容量为160.9 m A·h·g~(-1),在高倍率5 C下的比容量仍为120.5 m A·h·g~(-1),显示了良好的比容量维持率。该法制备细小而致密的球形颗粒,并通过纳米石墨包覆增强导电性,大大提高了LiFePO_4材料的电化学性能,此方法简便、高效,有工业化应用的前景。     

焙烧温度对Co-Ru-ZrO2/γ-Al2O3F-T合成催化剂性能的影响

采用浸渍法制备钴基催化剂,考察了催化剂焙烧温度对其F-T合成反应性能和产物分布的影响。制备催化剂时,不对催化剂进行焙烧,Co物种容易还原,并可较好分散,催化剂具有较高的催化活性和重质烃选择性。较高温度下焙烧,Co物种和载体间的相互作用增强,形成难还原的铝酸钴化合物,同时氧化钴晶粒聚集或烧结,Co物种的还原程度下降,催化剂CO加氢活性降低,重质烃选择性下降。在原料气n(H₂)∶n(CO)=2.0、483 K、1.5 MPa和800 h^-1条件下,未焙烧、673 K和923 K焙烧的催化剂上进行F-T合成反应,CO的转化率分别为80.27%、78.41%和61.14%,重质烃的选择性C₅⁺分别为88.54%、88.57%和77.95%。较低焙烧温度有利于反应速率的提高和重质烃的合成,较高焙烧温度使CO加氢活性下降,有利于低碳烃的生成。     

Influence of the preparation of organic coal–water fuel on its ignition

The integral ignition characteristics of a single droplet (initial radius 0.3–1.0 mm) of various organic coal–water fuels (prepared by means of a homogenizer or a ball mill) in an oxidant flux at 800–1100 K are compared. The fuel samples are based on spent motor, turbine, and transformer oils, filter cake from K coal, water, and plasticizer. The influence of the drop radius, the fuel composition, and the method and duration of sample preparation on the properties of the fuel (in particular, its structural stability and viscosity in the initial state) and on its ignition characteristics (the ignition delay, the time for total combustion, and the duration of the initiation stage) is determined. The limiting duration of structural stability is compared for samples of organic coal–water fuel prepared by means of a homogenizer and by means of a ball mill.     

Effect of synthesis process on the densification,microstructure, and electrical properties of Ca0.9Yb0.1MnO3 ceramics

Ca_0.9Yb_0.1MnO₃ thermoelectric materials have been prepared, through a classical solid‐state sintering method, from attrition‐ and ball‐milled precursors. After calcination step, microstructural observations have shown that attrition‐milled precursors possess much smaller particle sizes than the obtained by ball milling. Smaller precursors sizes lead to higher reactivity, producing higher density, hardness, and thermoelectric phase content in the sintered materials. The thermoelectric properties reflect the microstructural features, decreasing electrical resistivity in the attrition milling prepared samples without a drastic decrease in the Seebeck coefficient. As a consequence, power factor values are higher than the obtained in the classical solid‐state method samples. Moreover, the highest power factor values at 800°C are much higher than the best results obtained in this CaMnO₃ family. As a result, it has been found that it is possible to tailor the thermoelectric properties of Ca_0.9Yb_0.1MnO₃ ceramics by designing the appropriate preparation procedure while keeping in mind its industrial scalability.     

Structural and acidic properties of aerogels of niobia, niobia/selica, and niobiattania

Aerogel synthesis is an effective way to stabilize niobia, either by itself or in combination with another oxide, from crystallization induced by thermal treatment. Aerogels of niobia, niobia/silica, and niobia/titania prepared from the respective metal alkoxides were X-ray amorphous after calcination at 773 K for two hours and had surface areas that were higher than samples prepared by precipitation. These materials were also acidic as determined by n-butylamine titrauon. Thermal treatment at higher temperatures led to the crystallization of niobia or compound formation and a concomitant loss in acidity.     

高能球磨高温固相法制备尖晶石型铜铬黑颜料

以Cr2O3与CuO为原料,采用高能球磨高温固相法制备尖晶石型铜铬黑颜料;利用XRD、SEM和激光粒度仪等方法对制备颜料的结构、形貌及粒度进行了表征。系统研究了前体混料方式、球磨时间、煅烧温度、煅烧时间等条件对铜铬黑颜料晶型、粒度的影响;探讨了掺杂对铜铬黑颜料着色力的影响。研究表明,通过高能球磨可有效地控制颗粒大小及均匀性,NiO与CoO的掺入可显著提高其着色力。高能球磨10 min,煅烧温度900 ℃,保温时间3 h下制备出了粒径分布均匀着色力较好的铜铬黑颜料。