钛酸盐功能材料的研究与应用

本文综述了钛酸盐功能材料的各种性质、合成方法及用途。指出关于新型钛酸盐产品的制备、新性能的发现及寻求新的应用领域是一项值得深入研究的课题。     

纳米结构钛酸盐电极快速测定水体COD

分析了纳米结构钛酸盐电极快速测定COD的基本原理及COD标准物质定值方法。通过对纳米结构钛酸盐表征分析,钠型钛酸盐电极具有较高的灵敏度,外加0.7 V工作电位,测定COD溶液标准物质的线性相关系数大于0.995,误差在±8%以内;与国标方法比较,测量同一水样的误差在±15%以内。纳米结构钛酸盐电极可用于测量水体COD。     

Variations on the theme of closest packing: The structural chemistry of barium titanate compounds

The crystal structures of most barium titanates can be described as hexagonal closest packings consisting of atoms of Ba and O and of vacancies between them. The pseudohexagonal cell constants of these compounds are close to the ideal hexagonal values. The most common stacking is the six-layer sequence (hcc)₂. The mean diameter of a closest packed particle in these packings is 2.85 Å, while the mean thickness of a layer is 2.33 Å. The recognition of this closest packing principle has been helpful in the solution of many of the crystal structures of this group. With the exception of BaTi₄O₉, all the barium titanates which are usually classified as tunnel structures or Wadsley-Andersson phases can be described as cubic closest packings. The deviations of the pseudocubic phases from the ideal cubic values are larger than in the pseudohexagonal cases. A few of the barium titanates are related to the so-called 3.0-Å phases based on the rutile-type octahedral chain. These structures are characterized by having two almost closest packed corrugated layers at right angles to each other. The structures of a number of compounds in which the Ti⁴⁺ atoms are replaced partly by Ti³⁺, Al, Pt⁴⁺, or Li are based on principles similar to those of the barium titanates proper. The mean TiO distances in the coordination octahedra of the barium titanates depend strongly on the distortions of the octahedra.     

Synthesis and ionic conduction of sodium titanate Na<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>7</Subscript>

Chemical and phase transformations in the course of synthesis of sodium titanate Na₂Ti₃O₇ have been studied. Prepared sodium titanates have been characterized by X-ray powder diffraction analysis, scaning electron microscopy, and impedance spectroscopy, their electrochemical testing has been conducted. Mechanochemical interaction of titanium dioxide and sodium carbonate at the grinding stage has been revealed. The utilization of mesoporous titanium dioxide have been shown to provide a considerable decrease of final annealing temperature. Thus obtained titanates exhibit high electrochemical capacity.     

氮磷配位的钛酸酯络合物的X射线光电子能谱研究

制备了单烷基羧酸型和磺酸型钛酸酯氮配位与磷配位的配合物.用XPS法证明有N→Ti或P→Ti配位键生成,并从化学位移量推测了键的强度,磺酸型较羧酸型易配位,羟基取代胺的氮配体配位较容易发生;磷配位由于存在Ti→P的反馈作用,使化学位移不如氮配位明显.此外,异丙基钛酸酯与乙醇胺的反应物,证明分子内有N→Ti配位键生成.     

Synthesis of classes of ternary metal oxide nanostructures

Nanoscale structures, such as nanoparticles, nanorods, nanowires, nanocubes, and nanotubes, have attracted extensive synthetic attention as a result of their novel size-dependent properties. Ideally, the net result of nanoscale synthesis is the production of structures that achieve monodispersity, stability, and crystallinity with a predictable morphology. Many of the synthetic methods used to attain these goals have been based on principles derived from semiconductor technology, solid state chemistry, and molecular inorganic cluster chemistry. We describe a number of advances that have been made in the reproducible synthesis of various ternary oxide nanomaterials, including alkaline earth metal titanates, alkali metal titanates, bismuth ferrites, ABO(4)-type oxides, as well as miscellaneous classes of ternary metal oxides.     

Synthesis and properties of chromium-containing bismuth titanates with the pyrochlore structure

Chromium-containing bismuth titanates with the pyrochlore-type structure Bi_1.6Cr _x Ti₂O_6.4+1.5x were synthesized by the ceramic method. The region of formation of solid solutions of pyrochlores (chromium-doped bismuth titanates) was determined. The picnometric and X-ray densities were compared, and the electrophysical and magnetic characteristics were studied.     

Synthesis and properties of Sc- and Mg-doped bismuth titanates with the pyrochlore structure

Scandium(Magnesium)-containing bismuth titanates with the pyrochlore structure have been synthesized for the first time. Their homogeneity range has been determined by means of X-ray diffraction analysis and scanning electronic microscopy. Scandium and magnesium distribution over the cationic positions has been studied. Electrophysical properties of single-phase compounds have been studied. The total conductivity of the compounds is a function of magnesium (scandium) and bismuth concentrations.     

1,4 polymerization of isoprene by titanate catalyst systems

Titanates are versatile in the 1,4 polymerization of isoprene. The (R′O)₄Ti/RAlCl₂ catalyst gives either cis- or trans-1,4-polyisoprene, depending on the nature of both the titanate and the solvent. Primary titanates give cis-1,4-polyisoprene in both aliphatic and aromatic solvents. Secondary titanates give cis-polyisoprene in aliphatic solvents, and trans-1,4-polyisoprene in aromatic solvents. Tertiary titanates give trans-polyisoprene in both aliphatic and aromatic solvents. A mechanism is postulated which takes into consideration the role of the solvent. ESR studies of the various titanate–RAlCl₂ catalysts were made; the paramagnetic structures are related to polymerization mechanisms.     

Adsorption of 137Cs on titanium ferrocyanide and transformation of the sorbent to lithium titanate: a new method for long term immobilization of 137Cs

Dynamic adsorption of radiocesium on titanium ferrocyanide grains from reactor coolant simulating solution containing salts at moderate concentrations has been investigated. Effective decontamination of the neutral solutions has been achieved, in the amounts of a more than 20 thousand bed volumes. After adsorption the titanium ferrocyanide was transferred to titanates and calcined at 900 °C. The leaching test of the obtained lithium titanates indicates that the loaded adsorbent can serve as an effective primary barrier in nuclear waste repositories.     

Organic–Inorganic Hybrids Based on Ultrathin Oxide Layers: Designed Nanostructures for Molecular Recognition

The application of layered solids for molecular recognition is summarized. By using layered solids (silicates, aluminosilicates, titanates, hydroxides, and so on), ions and molecules can be concentrated from aqueous and vapor phases. The large surface area and tunable surface properties derived from the layered structures contribute to molecular recognition. The choice of materials and modification of the nanostructure were carefully investigated to optimize the performance based on molecular recognition (selective adsorption, substrate selective reaction, detection, etc.). The progress made in materials syntheses (variation of layered materials, sophisticated modification, controlled morphology, and processing) has made the design of materials more attractive and realistic.     

Synthesis, structure, and impedance spectra of iron-containing bismuth titanates

Iron-containing bismuth titanates with a cubic pyrochlore Bi_1.6Fe _x Ti₂O_{7 ? δ} structure were synthesized by the ceramic method. The region in which iron-containing pyrochlores are formed was determined. The pycnometric specific gravity of the samples was measured. Based on XRD and pycnometric specific gravity data, it was concluded that iron atoms lie in the bismuth sublattice. The electric properties of the materials were studied by high-temperature impedance spectroscopy. A strong effect of polarization on the impedance spectra was found.     

Catalytic combustion of diesel soot over perovskite-type catalyst: Potassium titanates

Potassium titanates with a high crystallinity were successfully prepared by the sol-gel method and characterized by XRD, SEM, and BET surface area measurements. K₆Ti₄O₁₁, K₂Ti₂O₅, K₂Ti₄O₉ were found to have better soot oxidation performance compared with Pt/TiO₂ and CeO₂ based catalysts. K₂Ti₂O₅ may be an excellent candidate for soot oxidation due to its high oxidation activity, water-stability, resistance to sulfur poisoning and economical advantages. Certain amount of NO _x can contribute to the catalytic combustion of diesel over potassium titanates, implying that K₂TiO₅ may be a kind of catalyst for simultaneous removal of NO _x and soot.     

Polymers Based on Epoxy Resins and Functional Derivatives of Polychlorobiphenyls

A new way to utilize polychlorobiphenyls was suggested: transformation of Sovol base hydrolysis products into glycidyl ethers and titanates. The resulting products were tested as components of epoxy compounds which are subsequently cured to obtain three-dimensional polymer networks.     

纳米碱土金属钛酸盐对MnO_2电极电化学行为的影响

采用溶胶-凝胶法制得钙钛矿型MTiO_3(M=Mg,Ca,Sr,Ba)纳米粉体，并将所得纳 米MTiO_3用于40%KOH电解液中MnO_2电极的物理改性。恒流放电测试结果表明，掺 杂5%的纳米MTiO_3能部分抑制MnO_2电极第二步放电过程中电化学惰性物质 Mn_3O_4的生成，可使MnO_2电极放电提高40%以上；改性电极的可充性能也得到一 定的改善。循环伏安测试表明，在充放电过程中，纳米MTiO_3只是填充到MnO_2空 隙中，并未参与电极反应；纳米MTiO_3的掺入改善了电极的传质和传荷环境，增大 了改性电极的氧化还原电流，提高了电活性物质的利用率；但经多次循环充放，纳 米MTiO_3不能有效地阻止MnO_2的结构崩溃，只能有限地延缓其容量的衰减速度。     

Electrophysical properties of bismuth titanates with the pyrochlore structure Bi<Subscript>1.6</Subscript>M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript>2</Subscript>O<Subscript>7–δ</Subscript> (M = In,Li)

Lithium-containing bismuth titanates with the pyrochlore-type structure Bi_1.6Li_xTi₂O_7–δ were obtained for the first time. The formation of the pyrochlore phase was confirmed by X-ray diffraction analysis, scanning electron microscopy and local microanalysis. In Bi_1.6M_xTi₂O_7–δ, the lithium and indium are occupied the bismuth sites, primarily. The electrophysical properties of doped bismuth titanates were studied by impedance spectroscopy in the frequency range 1–10⁶ Hz. In the low-temperature range (of up to ~400°C), electron conductivity predominates; above 400°C, the oxygen-ion type of conductivity is revealed. In the range p(O₂) = 0.21–1 atm, the average value of the sum of ion transport numbers is 0.5 at 500–550°C. The relaxation process was found from the frequency dependences of the dielectric parameters (ε', tan δ, M''), which was of the same type for systems with different dopants (In, Li) probably due to the hopping mechanism of oxygen conductivity.     

Layered hydrazinium titanate: advanced reductive adsorbent and chemical toolkit for design of titanium dioxide nanomaterials

LHT-9, a layered hydrazinium titanate with an interlayer spacing of ~9 ?, is a new nanohybrid compound combining the redox functionality of hydrazine, the ion-exchange properties of layered titanate, the large surface area of quasi-two-dimensional crystallites, surface Br?nsted acidity, and the occurrence of surface titanyl bonds. LHT-9, ideally formulated as (N(2)H(5))(1/2)Ti(1.87)O(4), relates to a family of lepidocrocite-type titanates. It possesses a high uptake capacity of ~50 elements of the periodic table. Irreversibility of reductive adsorption allows LHT-9 to be used for cumulative extraction of reducible moieties (noble metals, chromate, mercury, etc.) from industrial solutions and wastewaters. Unlike sodium titanates that do not tolerate an acidic environment, LHT-9 is capable of uptake of transition metals and lanthanides at pH > 3. Adsorption products loaded with the desired elements retain their layered structures and can be used as precursors for tailored titanium dioxide nanomaterials. In this respect, the uptake of metal ions by LHT-9 can be considered as a method complementary to electrostatic self-assembly deposition (ESD) and layer-by-layer self-assembly (LBL) techniques. LHT-9 is readily synthesized in one step by a mild fluoride route involving hydrazine-induced hydrolysis of hexafluorotitanic acid under near-ambient conditions.     

ChemInform Abstract: On the Crystal Energy and Structure of A2TinO2n+1 (A: Li,Na, K) Titanates by DFT Calculations and Neutron Diffraction.

The formation energies of the title alkali layered titanates (n = 3, 4, 6) are determined by DFT calculations for different monoclinic structure configurations.     

From titanates to TiO2 nanostructures: Controllable synthesis, growth mechanism, and applications

The design and fabrication of nanostructures based on titanium dioxide (TiO 2 ) have attracted much attention because of their low cost, non-toxicity, stability, and potential applications in industry and technology. Recently, one-dimensional (1D) structured titanates have been used as titanium source to prepare TiO 2 nanostructures with various crystalline phases, shapes, sizes, exposed facets, and hierarchical structures. Among the synthetic strategies, hydrothermal method is a facile route to controllable preparation of well-crystalline TiO 2 in one step. Herein, we review our recent progress in transferring 1D titanates into TiO 2 nanostructures through hydrothermal method, including the transformation mechanism and applications.