Solvent extraction of Hf(IV) and Zr(IV) with some 1-phenyl-3-methyl-4-acylpyrazolones-5

The distribution of Hf, Zr and Nb between aqueous solutions of mineral acids and solutions of 1-phenyl-3-methyl-4-acylpyrazolones-5 (acyl=acetyl, ethoxycarbonyl, butyryl, capronyl, capryl and benzoyl) in various organic solvents has been studied. The dependence of the distribution ratio of metal on the acidity of the aqueous phase, the analytical concentrations of reagents and metals, and on the organic solvent was investigated. The composition of the complex extracted is MeP₄ for Hf and Zr. The conditions for the separation of Zr, Hf and Nb are defined, and a comparison is made with extractions by means of thenoyltrifluoroacetone.     

Influence of alloying elements on the mechanical and thermodynamic properties of ZrB12 ceramics from first-principles calculations

Although ZrB₁₂ is a promising advanced material because of the boron cuboctahedron cages, the hardness of ZrB₁₂ remains controversy. Here, we apply first-principles calculations to study the influence of transition metals (4d- and 5d-) on the hardness and thermodynamic properties of ZrB₁₂. The calculated hardness of ZrB₁₂ is 32.9 GPa, which is in good agreement with the previous theoretical result. Importantly, the calculated hardness of Re-doped ZrB₁₂ is up to 40.0 GPa, which is a potential superhard material. The essential reason is that the alloying element of Re enhances the localized hybridization of B B and Zr B atoms, and then forms the strong B B covalent bond and Zr B bond. The result is well demonstrated by the chemical bonding and lattice parameter. Here, our work shows that the alloying elements of Nb, Mo, and Re enhance the thermodynamic properties of ZrB₁₂. The Debye temperature of Re-doped ZrB₁₂ is 1225.2 K, which is larger than that of the parent ZrB₁₂ (1213.5 K).     

Study of molecular size in ethylene-propene copolymerization with zirconocene and hafnocene catalysts

Ethylene-propene copolymerization was carried out with Cp₂MCl₂ (Cp = cyclopentadienyl), rac-Et(Ind)₂MCl₂, rac-Me₂Si(Ind)₂MCl₂ (Et = ethylene, Me₂Si = dimethylsilyl, Ind = indenyl, M = Zr or Hf)/methylaluminoxane. In the case of using ansa-hafnocenes, the minimum molecular size (extended chain length) of ethylene-propene copolymer was obtained at about 50 mol-% of propene content in the copolymer. The polymerization activity decreased with increase of propene feed ratio in non-bridged non-specific metallocenes. Higher polymerization activities were observed for the copolymerization compared to ethylene and propene homo-polymerization with ansa-isospecific metallocenes. The factor of molecular size lowering was studied by the chain propagation and chain transfer reaction.     

Triazene-N-oxides as new type of fluorimetric reagents. part i. trace determination of zirconium at the nanogram level

Summary Triazene-N-oxides are being reported for the first time as a new type of metallofluorescers. Among eleven triazene-N-oxides studied, 3-(2-hydroxyphenyl)-l-phenyl triazene-N-oxide(R₁₁) gives fluorescence with Zr, Hf, Nb(V) and Ta(V). A method has been developed for trace determination of Zr with R₁₁, excitation and emission maxima of the system being 435 nm and 570 nm respectively.In the pH range between 1.65 and 1.95 the fluorescence intensity of Zr-R₁₁ system is linear over the range 5 ppb to 1.5 ppm of zirconium. Some thirty ions show no interference or can be removed by the use of masking agents. Only Hf, W and Mo cause interference. The method is simple and very rapid.

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Triazen-N-Oxide als neuartige fluorimetrische Reagenzien. I. Bestimmung von Zirkon im Nanogrammbereich

Zusammenfassung Triazen-N-oxide wurden erstmalig als fluoreszenzanregende Reagenzien für Metalle vorgeschlagen. 3-(2-Hydroxyphenyl)-1-phenyltriazen-N-oxid (R₁₁) gibt mit Zr, Hf, Nb(V) and Ta(V) Fluoreszenz. Ein Verfahren für die Bestimmung von Zr-Spuren mit R₁₁ durch Anregung bei 435 nm und Messung beim Fluoreszenz-Maximum (570 nm) wurde ausgearbeitet. Im pH-Bereich 1,65–1,95 ist die Fluoreszenz-Intensität von Zr-R₁₁ zwischen 5 ppb und 1,5 ppm Zr linear. Einige dreißig Ionen stören nicht bzw. können maskiert werden. Nur Hf, Mo und W stören.

     

Selective separation and reversed phase extraction of zirconium and hafnium from a multitracer solution

The solvent extraction of Zr and Hf was studied using 444-trifluoro-1-(2-thienyl)-1,3-butanedione (TTA) from a multitracer solution containing carrier-free radioisotopes of Zr, Hf, and other elements. The multitracer was prepared from Au foil irradiated with high-energy heavy-ion beams. Effects of HCl and HNO₃ concentrations and organic solvent on the extraction and coextraction of other radionuclides have been studied. It was found that decalin (decahydronaphthalene) was the best solvent among 14 solvents studied and the optimum aqueous phase was 2 mol·dm^–3 HCl or HNO₃. About 2–10% of Sr, Rb, Sc and Nb were coextracted with Zr and Hf. The reversed phase extraction of Zr and Hf was also developed by using ethylenediaminetetraacetic acid (EDTA) solution at pH range of 8.5–10.     

A cyclopentadienyl ring exchange method for the attachment of early transition metal metallocene dichlorides to a polymer support

PMR and mass spectral analysis have been used to study the interchange of π-bonded cyclopentadienyl rings with σ-bonded cyclopentadienyl rings in the compounds (C₅H₅)₄M (M = Ti, Zr, Hf, Nb, Ta, Mo and W) and (C₅H₅)₃V or a-bonded benzylcyclopentadienyl rings in the compounds (C₆H₅CH₂C₅H₄) (C₅H₅)₂MC1 (M = Ti, Zr, Hf, Nb, Ta, Mo and W). As soon as the Cp₄M species are generated (indicated by a color change), the interchange occurs and the equilibrium is established. As reported, no such interchange was observed in (C₅H₅) ₄Mo in the PMR time scale; however, it does occur after a longer time. By using this interchange behavior of the cyclopentadienyl ring, metallocene dichlorides of Ti, Zr, Hf, V, Nb, Ta, Mo and W have been attached to polystyrene-divinylbenzene beads.     

Extraction and separation of Zr,Nb and Hf by Aliquat 336 and its mixtures with TOPO from acidic thiocyanate media

Presence of thiocyanate ions results in appreciable extraction of Zr(IV) by Aliquat 336 from low aqueous HCl acidities, i.e., 0.1 to 4.5M. The variation of concentrations of HCl, thiocyanate and Aliquat 336 greatly influences the extent of extraction. Mixtures of Aliquat 336 and TOPO result in synergistic extraction of Zr and Hf from acidic thiocyanate media, the extracted species being the disolvate with TOPO. By controlled adjustment of HCl, SCN^– and Aliquat 336 concentrations, separation of Zr, Nb and Hf is possible. A maximum separation factor (D_Nb/D_Zr) of 3675 has been achieved under certain conditions.     

Untersuchungen in den Systemen Titan (Zirkonium,Hafnium)-Niob-Kohlenstoff

Zusammenfassung Die Aufteilung der Phasenfelder in den Dreistoffen: Titan (Zirkonium, Hafnium)-Niob-Kohlenstoff wird mit Hilfe gesinterter Proben bei je einer Temperatur ermittelt. Alle drei Systeme sind durch das Auftreten großer homogener Bereiche der Mischcarbide (Ti, Nb) C_1-x , (Zr, Nb) C_1-x und (Hf, Nb) C_1-x charakterisiert. Nb₂C löst wenig von dem Zweitcarbid. Eine thermodynamische Betrachtung führt zu einer Abschätzung der Stabilitätsdifferenz zwischen NbC_1-x und Nb₂C.

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The ternary systems: Ti(Zr, Hf)–Nb–C have been examined by means of sintered specimens. The equilibria of the above mentioned systems are characterized by the occurrence of a large domain of the respective solid solutions (Ti, Nb) C_1-x , (Zr, Nb)C_1-x and (Hf, Nb)C_1-x . Nb₂C dissolves very little of the second carbide. Thermodynamic considerations lead to an evaluation of the difference of stability between NbC_1-x and Nb₂C.

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Mit 6 Abbildungen     

Catenated polysulfur ligands: the pentasulfides of di-η5-cyclopentadienyl-zirconium(IV) and -hafnium(IV)

The thiols Cp₂M(SH)₂, where M = Ti and Zr, react to form the complexes Cp₂MS₅ when treated with mono- and di-sulfur transfer reagents. Treatment of Cp₂MCl₂ with Li₂S₂ and sulfur gave Cp₂MS₅, M = Ti, Zr and Hf, in better yield. The new Zr and Hf complexes have a six-membered MS₅ ring in a chair conformation similar to the previously observed for M = Ti. Variable temperature NMR studies show that the barriers to MS₅ ring inversion decrease in the order Ti > Hf > Zr.     

A chelating resin containing 1-(2-thiazolylazo)-2-naphthol as the functional group; synthesis and sorption behavior for trace metal ions

A new polystyrene-divinylbenzene resin containing 1-(2-thiazolylazo)-2-naphthol (TAN) functional group was synthesized and its sorption behavior for 19 metal ions including Zr(IV), Hf(IV) and U(VI) was investigated by batch and column experiments. The chelating resin showed a high sorption affinity for Zr(IV) and Hf(IV) at pH 2. Some parameters affecting the sorption of the metal ions are detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(IV) and Hf(IV) that were higher than those of the other metal ions were 0.92 and 0.87 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as: Zr(IV)>Hf(IV)>Th(IV)>V(V)>Nb(V)>Cu(II)>U(VI)>Ta(V)>Mo(VI)>Cr(III)>Sn(IV)>W(VI). Quantitative recovery of most metal ions except Zr(IV) was achieved using 2 M HNO₃. Desorption and recovery of Zr(IV) was successfully performed with 2 M HClO₄ and 2 M HCl.     

Theoretical exploration on the vibrational and mechanical properties of M3C2/M3C2T2 MXenes

MXenes have attracted intensive attention in chemistry and material science for their special structures and properties. In order to understand the basic physical properties of the M₃C₂/M₃C₂T₂ (MSc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W; TF, O, OH) MXenes, first-principles calculations are carried out to investigate the structural, vibrational, and mechanical properties in this work. Both the metal atoms and surface groups can significantly influence the configurations or mechanical behaviors of the MXenes. The dehydrogenation tendency is calculated to evaluate the possible forms of the M₃C₂(OH)₂ toward M₃C₂O₂. The work functions of MXenes functionalized by different groups are compared, and the lower work functions for the  OH functionalized ones, which can be as low as 1.358 eV for the Sc₃C₂(OH)₂, suggest potential good performance in electron emission. In addition, the stability, mechanical properties, and the Raman and infrared (IR) activity modes of the MXenes are reported. Generally, functionalized MXenes would present smaller lattice parameters, lower free energies, and stronger mechanical strength compared to their counterparts. The data obtained may provide important theoretical ground for the investigations of the applications of MXenes.     

Study of the Cycloaddition of CO2 with Styrene Oxide Over Six-Connected spn Topology MOFs (Zr,Hf) at Room Temperature

A series of MOFs with a 6-connected spn topology were synthesized (MOF-808-(Zr, Hf), PCN-777-(Zr, Hf), MOF-818-(Zr, Hf)). Through the in situ DRIFTS of NH₃ adsorption-desorption, we found that the activated catalyst mainly contains Lewis acid sites. The effects of different organic ligands on the Lewis acid of the Zr₆ cluster were analyzed by XPS and NH₃-TPD, and the relative Lewis acidity of the same metal was obtained: PCN-777>MOF-808>MOF-818. In the Py-FTIR results, we confirmed that MOF-818 has a higher acid site density. In the activity test, MOFs with mesoporous structure showed better catalytic activity under normal temperature and pressure. Among them, MOF-818 can still maintain a high degree of crystallinity after catalysis. Finally, we use density functional theory to propose the mechanism of the cycloaddition reaction of carbon dioxide and styrene oxide. The results show that the metal is coordinated with styrene oxide and halogens attack the β carbon of the epoxide.     

A density‐functional theory approach to the separation of K2ZrF6 and K2HfF6 via fractional crystallization

Because of the low absorption cross‐section for thermal neutrons of zirconium (Zr) as opposed to hafnium (Hf), Zr‐metal must essentially be Hf‐free (<100 ppm Hf) to be suitable for use in nuclear reactors. However, Zr and Hf always occur together in nature, and due to very similar chemical and physical properties, their separation is particularly difficult. Separation can be achieved by traditional liquid–liquid extraction or extractive distillation processes, using Zr(Hf)Cl₄ as feedstock. However, the production of K₂Zr(Hf)F₆ via the plasma dissociation route, developed by the South African Nuclear Energy Corporation Limited (Necsa), could facilitate the development of an alternative separation process. In this theoretical study, the results of density‐functional theory (DFT) simulations of K₂Zr_(1‐z)Hf_zF₆ solid solutions [using Cambridge Serial Total Energy Package (CASTEP)] are presented, for which the supercell approach was applied in an attempt to determine whether solid solution formation during crystallization from aqueous solutions (fractional crystallization) is thermodynamically possible, which would hinder the separation efficiency of this method. Consequently, the calculated thermodynamic properties of mixing were used to evaluate the separation efficiency of Zr and Hf by fractional crystallization using a thermodynamic model to calculate the relative distribution coefficients. The small mixing enthalpies that were calculated from the DFT results, indicates that lattice substitution of Zr(IV) by Hf(IV) in K₂ZrF₆ could occur with relative ease. This is not surprising, considering the close similarities between Zr and Hf, and it was therefore concluded that K₂Zr_(1‐z)Hf_zF₆ solid solution formation might well restrict the separation efficiency of Zr and Hf by fractional crystallization of K₂Zr(Hf)F₆. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Mechanistic aspects of the olefin polymerization with metallocene catalysts

With C₁-, C₂- or C_s-symmetric metallocenes, different intermediates and types of copolymers can be obtained from randomly distributed to alternating structures. Substitution of the Cp-ring in [Me₂C-(tert-Bu Cp)(Flu)]ZrCl₂ yields ethene/norbornene copolymers with an alternating structure, because the rigid norbornene can only be inserted from the open side of the metallocene. By variation of the polymerization parameters, copolymers with glass transition temperatures above 180°C and molecular weights > 100 000 are synthesized. By supporting different metallocenes on a silica/methylaluminoxane (MAO) carrier the deactivation reaction under electron and hydrogen transfer can be suppressed. This is proved for different Al/Zr ratios when trimethylaluminum (TMA) is used as cocatalyst by the lack of methane evolution by metallocenes and by near independence of the polymerization activity on the prereaction time, after reaching maximum activity. Aluminumalkyls and MAO leach Cp₂ZrCl₂ from the carrier, the leached metallocene is only active in polymerization by adding MAO.     

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph₂P‐N‐PPh₂ at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp₂TiCl)₂] (Cp=η⁵‐cyclopentadienyl) generated [Cp₂Ti(Cl)P(Ph₂)N(H)PPh₂] ( 2 ). The heterometallacyclic complex [Cp₂Ti(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp₂Ti(η²‐Me₃SiC₂SiMe₃)] with the amine 1 . Reactions of the lithium amide [(thf)₃Li{N(PPh₂)₂}] with [Cp₂MCl₂] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp₂M(Cl){κ²‐N,P‐N(PPh₂)₂}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp₂Zr(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.     

Effect of the coordination sphere of d<Superscript>0</Superscript> metallocene on triplet-triplet energy transfer

The triplet nature of rare long-lived states of d⁰ metallocenes formed upon ligand-to-metal energy transfer was confirmed by studies of triplet-triplet charge transfer in biscyclopentadienyl complexes Cp₂MCl₂ (M = Zr (1), Hf (2)). The interaction between precatalysts and substrates of catalytic polymerization systems, viz., complexes 1 and 2 and unsaturated hydrocarbons (alkenes and dienes), was studied in the region of concentrations close to catalytic values. For organometallic π-complexes, it has been shown for the first time that, in the case of the unsaturated hydrocarbons, the efficiency of energy transfer obeys the Perrin equation. The process occurs at distances R ₀ close to the diameter of the interacting molecules and is well described by the exchange-resonant mechanism of interaction. In the case of the cyclopentadiene-Cp₂MCl₂ (M = Zr, Hf) systems, R ₀ = 14.6 Å. A linear relationship between the critical radius of the quenching sphere R ₀ and the number of carbon atoms in a linear α-olefin has been revealed for the first time and evidences the formation of a π-complex between the precatalyst and substrate molecules. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–39, January, 2007.     

Properties of boron,boride, and indium nanomaterials: The melting temperatures of spherical nanoparticles,nanowires, and nanofilms

High-temperature synthesis of boron nanowires with a fixed structure, spherical nanoparticles, cylindrical nanowires, and nanofilms of indium created a basis for theoretical studies of the nanochemistry of the boron family. The melting temperatures of these nanomaterials were studied as depending on their structural properties and electronic structure, as well as T _m trends in M _x B _y nanoborides, where M = Ti, Zr, or Hf; V, Nb, or Ta; Cr, Mo, or W; Fe, Co, or Ni.     

Über das Mischungsverhalten von Nb3Sn mit Ti3Sn,Mo3Al und verwandten Phasen

Zusammenfassung Nb₃Sn und Mo₃Al bilden eine lückenlose Mischreihe. Nb₃Sn löst bei 1600°C rd. 60 Mol% Ti₃Sn, 30 Mol% Zr(3)Sn, 40 Mol% Hf(3)Sn bzw. 50 Mol% Nb(3)Si.Mit 5 Abbildungen     

Effect of Nb alloying additions on the characteristics of anodic oxide films on zirconium and their stability in NaOH solution

The characteristics of oxide films on Zr and Zr–Nb alloys (with Nb content of 2.5, 5, and 10 at.%) galvanostatically formed (at a current density of 100 μA cm^?2) in 0.5 M H₂SO₄ solution were investigated by means of electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy spectra were interpreted in terms of an “equivalent circuit” with the circuit elements representing the electrochemical properties of a single layer oxide. The resistance of the oxide films was found to increase with increased Nb content in the alloy while the capacitance showed an opposite trend. The stability of the anodic oxide films grown in the sulfuric acid solution on Zr and Zr–Nb alloys was investigated by simultaneously measuring the electrode capacitance and resistance at a working frequency of 1 kHz as a function of exposure time to naturally aerated 3 M NaOH solution. Analyses of the electrode capacitance and resistance values indicated a decrease in chemical dissolution rate of the oxide films with the increase of Nb content in the alloy.     

Synthesis of zirconocene-acetylene and zirconocene-diacetylene polymer

A new class of organometallic polymer having a backbone of conjugated Poly-yne and Zr-metal atoms has been prepared. Trichloroethylene (TCE) and Hexachlorobutadiene (HCB) are quantitatively converted by n-butyllithium to dilithioacetylene (LiCCLi) and dilithiodiacetylene (Li CC CC Li) respectively. Quenching with Cp₂*ZrCl₂ affords high yields of the polymers Zr(Cp₂*)CC_n and Zr(Cp₂*)CC CC_n where Cp* = C₅(CH₃)₅ = pentamethyl cyclopentadienyl. The Cp₂*ZrCl₂ and the polymers were characterized by viscosity, molecular weight, elemental analysis, FTIR, NMR spectra, and TGA. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3899–3902, 1999