Commensurate Nb2Zr5O15: Accessible Within the Field Nb2ZrxO2x+5 After All

Doped niobium zirconium oxides are applied in field-effect transistors and as special-purpose coatings. Whereas their material properties are sufficiently known, their crystal structures remain widely uncharacterized. Herein, we report on the comparably mild sol-gel synthesis of Nb₂Zr₅O₁₅ and the elucidation of its commensurately modulated structure via neutron diffraction. We describe the structure using the most appropriate superspace as well as the convenient supercell approach. It is part of an α-PbO₂-homeotypic field with the formula Nb₂Zr_xO_2x+5, which has previously been reported only for x≥5.1, and is closely related to the structure of Hf₃Ta₂O₁₁. The results, supported by X-ray diffraction and additional synthesis experiments, are contextualized within the existing literature. Via the sol-gel route, metastable Nb−Zr−O compounds and their heavier congeners are accessible that shed light on possible structures of these commercially utilized materials.     

Proposal of a New Hf(IV)/Zr(IV) Separation System by the Solvent Extraction Method

A liquid-liquid extraction study has been conducted to separate hafnium from zirconium, using Cyanex 301 in kerosene. Noticeably, it is the first time that Cyanex 301 is utilized to separate Hf(IV) from Zr(IV). In this series of experiments, several parameters influencing the separation have been investigated, such as the initial pH, the extractant concentration, the metal ion concentration, the temperature, the type of the diluents and the salt addition. Regarding the aging of the Zr(IV) and Hf(IV) solutions, the solutions with a maximum 3 d aging time could be used with no difficulties. It was observed that the initial pH increase caused an increase in the Zr(IV)/Hf(IV) separation factor. Moreover, the distribution decreased with the temperature increase, suggesting that the reaction is exothermic. In agreement with the resulting data, the optimum separation factor illustrates the value of 7 at a pH of 4.00 in the presence of NaCl as an added salt. The attractive characteristics of the presently designed method are the use of low acidic nitrate solutions, the lack of using thiocyanate and a higher extractability of hafnium-Cyanex 301 relative to zirconium-Cyanex 301 complexes.     

Standard rate constants of charge transfer of Nb(V)/Nb(IV) redox pair in equimolar NaCl-KCl melt

Standard rate constants of charge transfer (k _s) on platinum and glassy carbon electrodes for Nb(V)/Nb(IV) redox pair in the NaCl-KCl-K₂NbF₇ melt are determined using the method of cyclic voltammetry in the temperature range of 973 to 1123 K. It is found that k _s increases with increasing temperature and when we pass from glassy carbon to platinum electrode. The “apparent” activation energies of charge transfer are determined; it is shown that the charge transfer between the Nb(V) and Nb(IV) complexes is quasi-reversible and is controlled predominantly by the diffusion.     

Homoleptic organometallic anions of Ti, Zr, Hf, and Nb

Reactions of C(6)H(5)Li and 4-CH(3)C(6)H(4)Li with halides of Ti, Ir, Hf, and Nb lead to the formation of homoleptic organometallic anions of these metals. Owing to their thermal instability and their sensitivity towards H(2) O and O(2) , these compounds are characterized by single-crystal structure determinations at low temperature, whereas other physical data could only be obtained occasionally. Three pentacoordinate complex anions [Ti(C(6)H(5))(5)](-), [Ti(4-CH(3)C(6)H(4))(5)](-), and [Zr(C(6)H(5))(5)](-) have square-pyramidal structures that display only slight deviations from the ideal geometry, in contrast to the already known structures of [Ti(CH(5))(5)](-). The hexacoordinate complex anions [Zr(C(6)H(5))(6)](2-), [Zr(4-CH(3)C(6)H(4))(6)](2-), [Nb(C(6)H(5))(6)](2-), and [Nb(4-CH(3)C(6)H(4))(6)](2-) all have trigonal-prismatic structures, in accord with the known hexamethyl complex dianions. In contrast, the hexacoordinate complex anion [Hf(C(6)H(5))(6)](2)(-) has an octahedral or close to octahedral structure, in contrast to the known trigonal-prismatic structures of [Ta(C(6)H(5))(6)](-) and [Ta(4-CH(3)C(6)H(4))(6) (-). A qualitative explanation for this structural variability is given.     

Charge-transfer kinetics in the Nb(V)/Nb(IV) couple in alkali-metal molten chlorides

Charge-transfer standard rate constants k _s for Nb(V)/Nb(IV) redox couple in KCl-NbCl₅ and CsCl-NbCl₅ chloride melts at glassy carbon and platinum electrodes are determined. The Nb(V) electro-chemical reduction process in the NaCl-KCl (equimolar mixture)-NbCl₅ melt was shown being reversible even at high polarization scan rate (v = 2.0 V s^?1); hence, the determination of k _s appeared impossible. Values of k _s in KCl-NbCl₅ melts are higher than those in CsCl-NbCl₅ melts. Quantum-chemical calculations done in nM⁺[NbCl₆]—model systems by the Discrete Fourier Transformation method showed that the calculated ratio of charge-transfer activation energies in the K⁺-Cs⁺ series corresponds to changes in the experimental charge-transfer rate constants. The charge-transfer standard rate constants increase with the increasing of temperature and with the passing from glassy carbon electrode to platinum one.     

Standard charge transfer rate constants for Nb(V)/Nb(IV) redox pairs in fluoride melts

Standard charge transfer rate constants (k _s) were defined for Nb(V)/Nb(IV) redox couples in NaF-KF (eutectic)-K₂NbF₇, KF-K₂NbF₇, and CsF-K₂NbF₇ melts using the cyclic voltammetry technique. It was established that in fluoride melts, the k _s values change in the following order depending on the composition of the second coordination sphere: k _s (CsF) < k _s (KF) < k _s (NaF-KF).     

The Ion-exchange Capacity of Ti and Zr Lamellar Hydrogenphosphates. TG measurements

Thermogravimetric data were used to calculate the number of acidic Brönsted sites in lamellar α-titanium (α-TiP), γ-titanium (γ-TiP), α-zirconium (α-ZrP) and γ-zirconium (γ-ZrP) hydrogenphosphates. The numbers of acidic sites calculated for these lamellar compounds were 7.81, 5.67, 6.33 and 5.56 for α-TiP, γ-TiP, α-ZrP and γ-ZrP, respectively. These values are in good agreement with those found through potentiometric titration. The data obtained prove that thermogravimetric measurements can be used as a reliable analytical tool to follow the ion-exchange capacity of this kind of crystalline lamellar compounds.     

溶胶-凝胶法制备氧化铝光学薄膜

氧化铝薄膜性能优异,具有较高的介电常数、高热导率、抗辐照能力强、抗碱离子渗透能力强以及在很宽的波长范围内透明等性能。因此,氧化铝薄膜广泛地应用于微电子器件、电致发光器件、光波导器件以及抗腐蚀涂层等众多领域[1]。特别是氧化铝光学薄膜具有高的抗激光损伤阈值[2],用     

丙烷在负载型V2O5/Zr3(PO4)4催化剂上的氧化脱氢

制备了无定型的磷酸锆Ｚｒ３（ＰＯ４）４载体,采用浸渍法在载体上负载０６％～６０％的Ｖ２Ｏ５．所制备的催化剂在丙烷氧化脱氢反应中具有较好的催化性能,如３０％Ｖ２Ｏ５／Ｚｒ３（ＰＯ４）４催化剂在丙烷转化率为１７０％时,丙烯选择性可达５３８％,丙烯收率达９１％．考察了不同反应条件下催化剂的性能．ＸＲＤ、ＩＲ和Ｒａｍａｎ光谱表明,Ｖ２Ｏ５在Ｚｒ３（ＰＯ４）４载体上主要是以高度分散的钒氧物种存在;ＥＳＲ分析结果证明催化剂中存在Ｖ４＋物种,表明Ｖ５＋／Ｖ４＋参与了氧化还原反应．     

Complexes of Zr(IV) and Nb(V) with 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one

The complexing of Zr(IV) and Nb(V) by 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one (HPMBzP) in various mineral acids has been studied by solvent extraction. The pyrazolone tautomers have been isolated and characterised, and the composition and structure of zirconium and niobium complexes have been established using various chemical and spectroscopic techniques.     

Preparation of water and alkali durable porous glass membrane coated on porous alumina tubing by sol-gel method

Composite porous glass membranes were prepared by the sol-gel method. A thin porous glass layer, about 2 μm thick, was coated on the surface of the porous ceramic tubing (Al₂O₃:99.9 wt.%, pore diameter: 200 nm). The composition of the porous glass layer of the composite membrane was SiO₂-ZrO₂. Considering from the fact that the desalination ratio of the feed aqueous NaCl solution (NaCl 0.5 wt.%) was about 90% by use of these membranes, they were defect-free. The best composition of the porous glass layer was 70 SiO₂-30 ZrO₂ from the standpoint of preparing membranes. These membranes had a large water and alkali durability. These membranes can be expected to apply to recovering dyes and paints from organic solvents and to be used as a gas separation membrane.     

Investigation on Concentrated Ⅴ（Ⅳ）/Ⅴ（Ⅴ） Redox Reaction by Rotating Disc Voltammetry

The kinetic characteristics of the concentrated Ⅴ（Ⅳ）/Ⅴ（Ⅴ） couple have been studied at a glassy carbon electrode in sulfuric acid using rotating-disc electrode and cyclic voltammetry. The kinetics of the Ⅴ（Ⅳ）/Ⅴ（Ⅴ） redox couple reaction was found to be electrochemically quasi-reversible with the slower kinetics for the Ⅴ（Ⅴ） reduction than that for the Ⅴ（Ⅳ） oxidation. And, dependence of diffusion coefficients and kinetic parameters of Ⅴ（Ⅳ） species on the Ⅴ（Ⅳ） and H2SO4 concentration was investigated. It is shown that the concentration of active species Ⅴ（Ⅳ） should be over 1 mol·L^-1 for the redox flow battery application. Further, with increasing the Ⅴ（Ⅳ） and H2SO4 concentration, the diffusion coefficients of Ⅴ（Ⅳ） were gradually reduced whereas its kinetics was improved considerably, especially in the case of Ⅴ（Ⅳ） and H2SO4 up to 2 and 4 mol·L^-1.     

Glycol modified cis -diisopropoxy- bis ( N -phenylsalicylideneiminato)zirconium(IV): syntheses,characterization and low temperature transformation to nanocrystalline zirconia

Zr(OPrⁱ)₄·PrⁱOH reacts with N-phenylsalicylideneimine in anhydrous benzene in 1 : 2 molar ratio to afford [Zr{O(C₆H₄)CH=NPh}₂{OPrⁱ}₂] (1). Further reactions of 1 with various glycols yield heteroleptic complexes of the type [Zr{O(C₆H₄)CH=NPh}₂{O–G–O}] [where–G–= (CH₂)₂ (2), (CH₂CHCH₃) (3), (CH₃CHCHCH₃) (4), (CH₂CHC₂H₅) (5), (CH₂)₃ (6), (CH₂CH₂CHCH₃) (7), and (CH₂)₆ (8)]. All new derivatives have been characterized by elemental analyses, FTIR and NMR (¹H and ¹³C{¹H}) studies. FAB mass spectra of 1 and 7 revealed the monomeric nature of these complexes. Complete hydrolyses and low temperature transformations of 1 and 7 using Sol-Gel technique formed tetragonal phase of ZrO₂ at 700°C, whereas transformation of tetragonal to monoclinic phase occurred at 900°C. SEM observations of these samples indicate formation of agglomerates of nanocrystalline zirconia (Scherer analysis).     

Facing unexpected reactivity paths with Zr(IV)-pyridylamido polymerization catalysts

This work provides original insights to the better understanding of the complex structure-activity relationship of Zr(IV)-pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (Zr(NMe(2))(4) vs. Zr(Bn)(4)) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible σ-bond metathesis/protonolysis reaction is found to take place on the Zr(IV)-amido complexes in the 298-383 K temperature range, changing the metal coordination sphere dramatically (from a five-coordinated tris-amido species stabilized by bidentate monoanionic {N,N(-)} ligands to a six-coordinated bis-amido-mono-amino complexes featured by tridentate dianionic {N(-),N,C(-)} ligands). Well-defined neutral Zr(IV)-pyridylamido complexes have been prepared from Zr(Bn)(4) as metal source. Their cationic derivatives [Zr(IV) N(-),N,C(-)}Bn](+)[B(C(6)F(5))(4)](-) have been successfully applied to the room-temperature polymerization of 1-hexene with productivities up to one order of magnitude higher than those reported for the related Hf(IV) state-of-the-art systems. Most importantly, a linear increase of the poly(1-hexene) M(n) values (30-250 kg mol(-1)) has been observed upon catalyst aging. According to that, the major active species (responsible for the increased M(n) polymer values) in the aged catalyst solution, has been identified.