Synthesis and Study of Acid-Basic Properties of Ti(IV) and Zr(IV) Phosphates Immobylized in the Matrix of Clinoptilolite

Abstract

By combination of the ionexchange and ionic-molecular layering methods [1], the synthesis of natural zeolite derivatives (clinoptilolite) containing in its composition nano-size fragments of Ti(IV) and Zr(IV) phosphates was performed. It was determined by the X-Ray method, that the phosphates of Ti(IV) and Zr(IV) replicate crystal lattice of zeolite, manifesting in enhancing the line's intensity on X-Ray patterns. The Brensted's and Lewis's spectra of acidic centers distributions were obtained by Hammett's indicator spectrophotometric method [2] in the interval of pK, values from -4.4 to 14.2, which have shown that P(V) of the derivatives is represented mainly by HPO₄- and H₂PO₄-groups, with predomination of these latter. It is shown that the force of Brensted's acidic centers, influenced by H₂PO₄-groups. remains at the level of H₂PO_(aq)-anion, and the force of the centers due to HPO₄-groups shifts into alkaline region, about 0,5 unit of pK. The strong acidic Lewis's centers were detected at the levels of pK, from 0 to -4.0. The spectra of Ti(IV) and Zr(IV) phosphates is presented in (1) and (2) respectively. A set of the acquired results makes possible a suggestion about using P(V)-containing derivatives in processes which are catalyzed both with Brensted's and Lewis's centers participation.     

Constitution and Thermodynamic Properties of Phosphates of Group IV Elements (Si,Ge, Ti,Zr, Hf)

Abstract

The regularities of phase formation in the systems MO₂ -P₂O₅ (M = Si, Ge, Ti, Zr, Hf) are established and the phase diagrams for them are constructed. In the systems Mo₂ -P 0, (M = Si, Ge) the following compounds are obtained: M₅0(PO₄)₆ and Mp₂O₇ (for Si-cubic, tetragonal and two monoclinic modifications; for Ge-cubic and monoclinic modifications). At low temperatures (up to 500° C) the hexagonal forms SiP₂0₇-0,8 H₂0 and GeP₂0₇·1,6 H₂0 are stable. Two phases are determined in the TiO₂-PO system: the phase of tne variable composition based on 5TiO₂ ^·3P₂0₅ with 40,2 to 54,2 mass % P₂O₅ and another phase TiP₂0₇ (cubic and water-stabilized pseudohexagonal TiP₂0₇ * 3H₂0). Four Compounds are found in the systems MO₂-P₂0₅ (M = Zr, Hf): (MO)₂P₂0 (β- and α-forms for Zr and β-form for Hf), M₃(PO₄)₄, MP₂0₇ and M(PO3)₄. The crystal-chemical analogy is considered between silicium and germanium phosphates, and accordingly between those of zirconium and hafnium. The isolation of titanium phosphates is discussed. The crystallographic, refractometric and thermal characteristics of the compounds and their forms are given as well as the values of electrical and thermal conductivities for cubic modifications of Mp₂O₇. High-temperature mass spectrometry was used to determined the vapour composition and partial pressures as well as the activities of the components and Gibbs free energy in the system GeO₂-P₂O₅ at 1000–1200°C. negative deviations from the ideal are obtained and compared with the results of investigation of the phase diagram for the Geo₂-P₂0₅ system.     

Analytical applications of Zr(IV) and Ti(IV) arsenophosphates as ion-exchangers

The distribution of 27 metal ions between zirconium and titanium arsenophosphate and demineralized water, perchloric acid and nitric acid has been studied. On the basis of the results, several binary and ternary separations can be designed. The data have been used in application of these materials to the analysis of certain alloys and rocks.     

Crystalline phase effects on esca valence bands of Zr(IV) and Ti(IV) acid phosphates

The valence bands (V.B.) of ESCA spectra of Zr(IV) and Ti(IV) acid phosphates in different crystalline phases are reported. The various bands are assigned by comparison with Li₃PO₄. Variations on changing the crystalline phase for compounds having the same M(IV) ion are found. Two types of molecular orbitals are mainly involved. One related to PO bonds is affected by the crystalline phase. The other, related to M(IV)O bonds and confined into the layers of the compounds, are less sensitive to crystalline environment. Variation in the symmetry of the tetrahedral type PO^3?₄ anion are proposed to be mainly responsible of the observed effects.     

Synthesis and Physicochemical Study of Solid Complexes of Ti(IV), Zr(IV), and Zn(II) with Chrysin

Previously unknown solid complexes of Ti(IV), Zr(IV), and Zn(II) with chrysin were isolated, identified, and studied by thermogravimetric analysis and by UV-Vis, IR, and NMR spectroscopy.     

A chromogenic calixarene hydroxamic acid for the sequential separation of Ti(IV) and Zr(IV)

A new chromogenic calixarene with hydroxamic acid as chelating agent was synthesized by partial reduction of nitrocalixarene which was subsequently coupled with coumarin chloride. The reagent showed selective and quantitative extraction of Ti(IV) into chloroform at 6 M HCl and that of Zr(IV) at 0.5 M HCl. A facile liquid-liquid extraction method for the separation and spectrophotometric determination of Ti(IV) and Zr(IV) has been proposed. The validity of the method was checked by separating several synthetic mixtures. The method was successfully applied to the analysis of piezoelectric lead-zirconium-titanate (PZT) samples. The method shows remarkable simplicity and selectivity. The method can also be used for the determination of Ti(IV) and Zr(IV) in various environmental samples. The article is published in the original.     

Synthesis and characterization of semicarbazone metal complexes of Sn(IV) and Zr(IV)

Three semicarbazonyl ligands were synthesized and used to form six novel organometallic complexes with Ph2SnCl2 and Cp2ZrCl2. All these complexes were characterized by IR,1H NMR,MS and elemental analysis.     

Layered Group(IV) Metal Phosphates as Catalysts for MTBE Synthesis

Layered group(IV) metal phosphates and their phenylsulfonic acid derivatives were used as catalysts for the synthesis of methyl tert-butyl ether (MTBE) from methanol and isobutene. Because zirconium and titanium phosphates have only moderate acidic strength, relatively high temperatures are required to activate their Brønsted acidic sites. The optimal activity was obtained at ca. 443 K. Their phenylsulfonic acid derivatives, however, demonstrated higher acidic strength by giving much higher activity toward MTBE formation at relatively low temperaures. The catalysts were characterized in terms of their structure, thermal stability, surface area and acidic strength.     

Preparation and Optical Characterization of Sol-Gel Deposited Pb(Zr0.45Ti0.55)O3 Films

Homogeneous crack-free lead zirconate titanate (Pb(Zr_0.45Ti_0.55)O₃: PZT 45/55) films were prepared by a chemically modified sol-gel process using lead acetate trihydrate, zirconium n-propoxide, and titanium isopropoxide precursors. The coating solutions were modified by the addition of diethanolamine. Single and multilayer films were deposited with a 2000 rpm spin rate on fused silica and MgO(100) substrates. Multiple spin coating with an intermediate heat treatment in air at 400°C for 3 min between coatings was performed to obtain films up to 2 m in thickness. The formation of the tetragonal perovskite structure was found to depend on the intermediate firing temperature, final annealing temperature, and annealing time. A 650°C rapid thermal annealing treatment in oxygen was required to crystallize the PZT film into the perovskite structure. The films were characterized using optical spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and thermo-gravimetry and differential scanning calorimetry (TG-DSC). The optical constants of the PZT films were evaluated from spectral transmittance and reflectance measurements. Optical constants are presented over the visible and near infrared region.     

Optically detected magnetic resonance in the photoexcited triplet states of Ti(IV) and Zr(IV) cylopentadienyl complexes

The class of compounds (RCp)2MX2, where M is a group IV metal, Cp is cyclopentadienyl, R is an alkyl, and X is a halide, has been of continuing interest as precursors for olefin coordination polymerization catalysts. In this communication, we demonstrate that the technique of optically detected magnetic resonance (ODMR) reveals subtle differences in the composition of the frontier molecular orbitals associated with the nature of the alkyl substituents on the Cp rings.     

Steric and electronic consequences of flexibility in a tetradentate redox-active ligand: Ti(IV) and Zr(IV) complexes

A redox-active, tetradentate ligand, N,N'-bis-(3-dimethylamino-propyl)-4,5-dimethoxy-benzene-1,2-diamide ([N(2)N(2)(cat)](2-)), was developed, and the six-coordinate metal complexes [N(2)N(2)(cat)]TiCl(2) (3) and [N(2)N(2)(cat)]ZrCl(2) (4) were synthesized. The tetradentate ligand was determined to be fluxional in 3 and 4, enabled by reversible dissociation of the neutral amine groups of the [N(2)N(2)(cat)](2-) ligand. Both amine arms of 3 could be replaced by N,N-dimethylaminopyridine with an overall free energy change of -4.64(3) kcal mol(-1) at 298 K. Cyclic voltammetry experiments were used to probe the redox capabilities of the [N(2)N(2)(cat)](2-) ligand: complex 3 exhibited two one-electron oxidations at -0.19 and -0.52 V versus [Cp(2)Fe](+/0) while 4 exhibited a single two-electron oxidation at -0.55 V. Substitution of the chlorides in 3 for an imide afforded the dimer {[N(2)N(2)(cat)]Ti(μ-p-NC(6)H(4)Me)}(2), in which the metal centers are five-coordinate because of dissociation of one amine arm of the [N(2)N(2)(cat)](2-) ligand. While the bis-azide complex [N(2)N(2)(cat)]Ti(N(3))(2) was stable toward elimination of N(2), the bis-phenylacetylide complex [N(2)N(2)(cat)]Ti(C≡CPh)(2) could be oxidized by PhICl(2), resulting in subsequent reductive elimination of 1,4-diphenylbutadiyne.     

Thermal BEHAVIOR of the Ti(IV), Zr(IV) and Pb(II) Complexes with 5-nitro-8-hydroxyquinoline

Ti(IV), Zr(IV) and Pb(II) complexes with 5-nitro-8-hydroxyquinoline (5-NQ) were obtained by precipitation in acetone/ammonium solution medium. The compounds TiO(C₉H₅N₂O₃)2·;0.5H₂O, ZrO(C₉H₅N₂O₃)₂·₂H₂O and Pb(C₉H₅N₂O₃)₂ were characterized by Elemental Analysis, X-ray Diffratometry and Infrared Absorption Spectrometry and their thermal behavior followed by TG/DTA. This present study intends to show the variations in the thermal behavior of the compounds and in the composition and/or structure of final oxide residues, in different atmospheres and heating rates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and Applications of Poly(Acrylphenylamidrazone-Phenyl-Hydrazide-Acylphenylhydrazine) Chelating Fiber for Preconcentration and Separation of Trae In(III), Zr(IV), Tl(I), V(V), Ga(III) and Ti(IV) from Solution Samples

 An ICP-OES method using a new poly (acrylphenylamidrazone-phenylhydrazide-acylphenylhydrazine) chelating fiber to preconcentrate and separate trace In(III), Zr(IV), Tl(I), V(V), Ga(III) and Ti(IV) ions from solution samples has been established. The new chelating fiber was synthesized using polyacrylonitrile fiber as a starting material and the structure of the chelating fiber was determined by FT infrared spectrometry. The acidity, adsorption rate, re-use, capacity and interference on the adsorption of ions on the chelating fiber as well as the conditions of desorption of these ions from the chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES). The results show that the relative standard deviations for the determination of 10 ng/ml In, Tl, Ga and 1 ng/ml Zr, V, Ti were lower than 2.5%. The results obtained for these ions in real solution samples by this method were basically in agreement with the given values with average errors of less than 4%. Received November 29, 2000. Revision May 22, 2001.     

Synthesis of carbamates and ureas using Zr(IV)-catalyzed exchange processes

[reaction: see text] Zirconium(IV)-catalyzed exchange processes have been developed to prepare both carbamates and ureas from dialkyl carbonates and carbamates employing 2-hydroxypyridine (HYP) and 4-methyl-2-hydroxyquinoline (MeHYQ) as catalytic additives, respectively. A microwave acceleration effect was observed in Zr(IV)-catalyzed carbamate-urea exchange.     

Synthesis of C3-symmetric tris(beta-hydroxy amide) ligands and their Ti(IV) complex-catalyzed enantioselective alkynylation of aldehydes

[reaction: see text]. A series of new chiral C3-symmetric tris(beta-hydroxy amide) ligands have been synthesized via the reaction of 1,3,5-benzenetricarboxylic chloride and optically pure amino alcohols (up to 96% yield). The asymmetric catalytic alkynylation of aldehydes with these new C3-symmetric chiral tris(beta-hydroxy amide) ligands and Ti (O(i)'Pr)4 was investigated. Ligand 4c synthesized from (1R,2S)-(-)-2-amino-1,2-diphenylethanol is effective for the enantioselective alkynylation of various aldehydes, and high enantioselectivity was obtained with aromatic aldehydes and alpha,beta-unsaturated aldehyde (up to 92% ee).     

Stereochemically rigid hepta-coordinate,tris (N,N-diisopropyldithiocarbamato)- complexes of Ti(VI) and Zr(IV)

Tris (N,N-diisopropyldithiocarbamato)- complexes of the type CpM(S₂CN i-pr₂)₃ and (MeC₅H₄)M(S₂CN i-pr₂)₃ (where M = Ti, Zr), have been prepared by the reaction of Cp₂MCl₂ or (MeC₅H₄)₂MCl₂ with anhydrous Na(S₂CN i-pr₂) in refluxing CH₂Cl₂ or THF. Conductivity measurements and molecular weight determinations indicate that these complexes are monomeric and nonelectrolytic. On the basis of the IR spectra coordination number of “Seven” is assigned to Ti(IV) or Zr(IV) in these complexes. Whilst ¹H NMR spectra indicate that these are stereochemically rigid complexes. A monocapped trigonal prism structure, a rare configuration is suggested for these complexes.     

Synthesis,characterization and soft transformation of some bis(cyclopentadienyl) Ti(IV) and Zr(IV) complexes of Schiff's base ligands to nano‐sized titania or zirconia materials

Some bis(cyclopentadienyl) complexes of Ti(IV)and Zr(IV) have been synthesized by the metathetical reactions of Cp₂MCl₂ with the sodium salt of monofunctional bidentate Schiff's base ligands in 1:1 and 1:2 stoichiometry in anhydrous THF. All the derivatives of the types Cp₂MCl_2?n{O(C₆H₄)CH₆H₅}_n and Cp₂MCl_2?n{OC(CH₃)(R)₆H₅}_n (where R = CH₃ or C₆H₅ and n = 1 or 2) have been characterized by elemental analyses, molecular weight measurements, FT‐IR and ‐NMR [¹H and ¹³C{¹H}] studies. The FAB mass spectra of a few representative complexes and the molecular weight measurements in freezing benzene indicate their monomeric nature in solution. Spectral studies appear to indicate mono‐ and bi‐dentate mode of attachment of the ligand in solution and in the solid state, respectively. Thermogravimetric analyses (TGA) of Cp₂TiCl{O(C₆H₄)CH} ( 1 ) and Cp₂ZrCl{O(C₆H₄)CH} ( 7 ) indicate their low thermal stability. Transformations of some of these complexes to pure titania (TiO₂)/zirconia (ZrO₂) have been observed at relatively low sintering temperatures. Powder X‐ray diffraction (XRD) and scanning electron micrograph (SEM) studies suggest the nanocrystalline nature of these materials. Copyright © 2007 John Wiley & Sons, Ltd.     

Zr(IV) and Hf(IV) based metal-organic frameworks with reo-topology

Zr and Hf based MOFs with enhanced pore accessibility for large molecules and good hydrothermal stability were obtained using a bent dithienothiophene dicarboxylate and Zr(4+) or Hf(4+) source. A modulator (benzoic acid) facilitates formation of an eight-connecting cluster leading to a new framework which adopts reo topology.