Preparation and catalytic performance of superfine Ni/BaTiO3 catalyst

Superfine Ni/BaTiO₃ catalysts were prepared by impregnation method and used successfully for CO₂ reforming CH₄ to syngas. The effects of preparation method and the temperatures of calcination, reduction and reaction on the catalytic activity of the Ni/BaTiO₃ system were investigated. This revised version was published online in June 2006 with corrections to the Cover Date.     

螯合型二甘醇钛酸酯的合成及其催化性能研究

报导了两种新的螯合型二甘醇钛酸酯的合成方法，进行了ＩＲ和ＵＶ鉴定，并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系，探讨了催化剂结构与催化性能的关系。     

钙钛矿型复合氧化物Ca_xSr_（1－x）TiO_3催化剂上的甲烷氧化偶联反应

在固定床反应器上，评价了不同温度下钙钛矿型复合氧化物ＳｒＴｉＯ３和ＣａＴｉＯ３的组成变化对甲烷氧化偶联反应的影响．同时，利用ＸＰＳ和ＣＯ２－ＴＰＤ对催化剂的结构及其氧物种的反应特性进行了表征．结果表明：ＳｒＴｉＯ３和少量Ｃａ掺杂的ＣａｘＳｒｌ－ｘＴｉＯ３有利于在较低温度（９２３Ｋ）下催化反应的活性和选择性，而ＣａＴｉＯ３体系则在高温（１０７３Ｋ）下表现出较好的活性和选择性．钙钛矿型复合氧化物ＳｒＴｉＯ３和ＣａＴｉＯ３组成变化对不同温度下反应活性的影响与ＣＯ２－ＴＰＤ的脱附谱图有很好的平行关系．     

Sol-Gel Preparation and Photoelectrochemical Properties of Fe2TiO5 Thin Films

Polycrystalline Fe₂TiO₅ films were prepared on nesa silica glass substrates by the sol-gel method, and their photoanodic properties were measured in a three-electrode wet cell with an aqueous buffer solution of pH = 7. Gel films were crystallized into Fe₂TiO₅ when fired at 500°C. The photoanodic current significantly increased when the films were fired at 700°C, and then decreased with increasing firing temperature. Thicker films obtained by repeating the gel film deposition and firing showed smaller photocurrent, and the 50 nm thick film prepared via non-repetitive deposition exhibited the maximum photocurrent. Although the photoresponse was extended to wavelengths near 500 nm, the maximum quantum yield was as low as 0.12 at a wavelength of 340 nm.     

Heterometallic lead-titanium oxyalkoxide precursors to lead titanate thin films

Two lead titanium oxyalkoxides with composition Pb₂Ti₄O₂(O₂CCH₃)₂(OC₂H₅)₁₄ and Pb₂Ti₂O₂(O₂CCH₃)₂(OCH(CH₃)₂)₈ have been isolated and characterised by elemental analysis, IR, ²⁰⁷Pb NMR and molecular weight measurements. X-ray structural analysis of the 1:2 complex confirmed the presence of two Pb₂Ti₂O units which are linked by a common Pb···Pb edge and are held together by alkoxide and acetate bridges. The acetate groups have migrated from the Pb to the Ti centres during the reaction. Hydrolysis of the 1:1 Pb/Ti complex produced clear gels providing the H₂O/complex ratio was less than 4. Heat treatment of the gel results in loss of residual organics below 400°C. The XRD pattern indicates the presence of the pyrochlore and perovskite phases after heating at 500°C but the sample is poorly crystalline. Complete conversion to the perovskite phase of lead titanate occurs on heating to 600°C for 1 hour. Thin films of lead titanate were deposited by dip-coating a solution of this complex in isopropanol. Analyses of the films, carried out using electron microprobe, Scanning Auger Spectroscopy and Rutherford Backscattering, indicated that they were of excellent quality, crystalline after heating at 600°C and with relatively sharp substrate-coating interface.     

Microstructure and electrical properties of BaTiO<Subscript>3</Subscript> and (Ba,Sr)TiO<Subscript>3</Subscript> ferroelectric thin films on nickel electrodes

Nickel thin films have been sputtered on standard Si/SiO₂ substrates with TiO₂ as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates were used for deposition of BaTiO₃ and (Ba,Sr)TiO₃ dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates under identical conditions but crystallized in an oxygen atmosphere.     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

Single crystalline nanowires of lead titanate (PbTiO₃) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure and optical properties of PbTiO₃ nanowires were investigated. The PbTiO₃ nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO₃ with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies are responsible for the light emission of PbTiO₃ nanowires.     

Synthesis of zirconium titanate with an ordered M-fergusonite (beta) structure

We report a new zirconium titanate compound (Zr,Ti)O₂ with 27.5-35 mol% titania (TiO₂) formed from the oxides at 35-38 kbar, 1400-1500 °C. Crystal structure investigations at atmospheric conditions with powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed a monoclinic structure related to that of M-fergusonite (beta). Unit-cell dimensions (from 27.5 to 35 mol% TiO₂): a=7.267(20)-7.340(2) Å, b=10.435(3)-10.429(1) Å, c=5.023(11)-5.040(1) Å, β=136.45(12)-137.55(1)°, V=262.44(92)-260.40(12) Å³, Z=4. Rietveld refinement (R_F=1.55) of a sample with 32.8 mol% TiO₂ indicates that site A is 8-fold coordinated, mostly occupied by Zr, while site B has 6-fold average coordination, occupied by Ti and Zr. Site B is at least partly ordered, as indicated by superstructure reflections 0 0 1 and −2 0 1 detected with TEM, reducing the space group from C2/c to C2. Pronounced streaking of selected diffraction spots is linked to the boundaries of lamellar domains in twin orientation, with twin planes either (200) or (20−2). Adjacent lamellae differ slightly in composition, causing subtle asymmetry of the twin diffraction patterns.     

The effect of B2O3 addition on the crystallization of amorphous TiO2-ZrO2 mixed oxide

The effect of B₂O₃ addition on the crystallization of amorphous TiO₂-ZrO₂ mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO₂-ZrO₂ mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO₂-ZrO₂ into a crystalline ZrTiO₄ compound, while a larger amount of boria (?8 wt%) promotes the crystallization process. FT-IR spectroscopy and ¹¹B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO₄ units delay, while a build-up of trigonal BO₃ promote, the crystallization of amorphous TiO₂-ZrO₂ to form ZrTiO₄ crystals.     

聚苯乙烯—钛酸钡复合材料介电性能的研究

以聚苯乙烯与化学沉淀法钛酸钡陶瓷为基本组成，采用溶液共混，溶液聚合，表面处理后溶液聚合三种方法进行复合，发现后两种复合的钛酸钡颗粒表面发生界面变化，形成活性界面，使得溶液聚合法和表面处理后溶液聚合所得到的材料具有较低的介电损耗，在高频下能保持较高的介电系数。