Separation of scandium(III) from lanthanides(III) with room temperature ionic liquid based extraction containing Cyanex 925

The separation of Sc(III) from Y(III), La(III) and Yb(III) in [C(8)mim][PF6] containing Cyanex 925 has been investigated, and is reported in this paper. A cation exchange mechanism of Sc(III) in [C(8)mim][PF6] and Cyanex 925 is proposed by study of the influence of anionic and cationic species on the extraction. The coefficient of the equilibrium equation of Sc(III) was confirmed by slope analysis of log D-Sc vs log [Cyanex 925], and the loading capacity also confirmed the stoichiometry of Cyanex 925 to Sc(III) was close to 3:1. Infrared data for Cyanex 925 saturated with Sc(III) in [C(8)mim][PF6] indicated strong interaction between P=O of Cyanex 925 and Sc(III). In addition, the relationship between log D-Sc and temperature showed that temperature had little influence on the extraction process, and the resulting thermodynamic parameters indicated that an exothermic process was involved.

Solvent extraction of scandium(III), yttrium(III), lanthanum(III) and gadolinium(III) using Cyanex 302 in heptane from hydrochloric acid solutions

The extractions of the selected rare earths (Sc, Y, La and Gd) from hydrochloric acid solutions have been investigated using bis(2,4,4-trimethylpentyl)-mono thiophosphinic acid (Cyanex 302, HL) in heptane as an extractant. The results demonstrate that the extractions of rare earths occur via the following reaction: Sc(OH)(2+) + 2[(HL)(2)]((O)) double left right arrow [Sc(OH)L-2 (.) 2(HL)]((O)) + 2H(+) Y3+ + 3[(HL)(2)]((O)) double left right arrow [Y(HL2)(3)]((O)) + 3H(+) La(OH)(2)(+) + 3[(HL)(2)](O) double left right arrow [La(OH)(2)L (.) 5(HL)]((O)) + H+ Gd(OH)(2+) + 3[(HL)(2)]((O)) double left right arrow [Gd(OH)L-2 (.) 4(HL)]((O)) + 2H(+) The pH(1/2) values and equilibrium constants of the extracted complexes have been deduced by taking into account the aqueous phase complexation of the metal ion with hydroxyl ligands and plausible complexes extracted into the organic phase. According to the pH(1/2) values, it is possible to realize mutual separation among Sc(III), Y(III), La(III) and Gd(III) with Cyanex 302 by controlling aqueous acidity.

Separation of scandium, yttrium and lanthanum in high-performance centrifugal partition chromatography with S-octyl phenyloxy acetic acid

Separation of scandium(III), yttrium(III) and lanthanum(III) was performed by high-performance centrifugal partition chromatography (HPCPC) employing the stationary phase of S-octyl phenyloxy acetic acid (CA-12). The liquid-liquid extraction behavior of CA-12 for Sc(III), Y(III) and La(III), the acidity of aqueous phase, and the operation conditions of HPCPC were examined. The retention volume (V-R) increased with the order of Y(III), La(III) and Sc(III) accompanied with the elution of the mobile phase in different pH, which is lowered from 4.6 to 2.1.

Solvent extraction of scandium(III), yttrium(III), lanthanides(III), and divalent metal ions with sec-nonylphenoxy acetic acid

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA100 has been studied and correlated with the dielectric constant.

Solvent extraction of scandium(III) by Cyanex 923 and Cyanex 925

The extraction equilibria of Sc(III), Zr(IV), Ti(IV), Th(IV), Fe(III) and Lu(III) from sulphuric or hydrochloric acid media by Cyanex 923 (mixture of straight chain alkylated phosphine oxides) and Cyanex 925 (mixture of branched chain alkylated phosphine oxides) were studied at various aqueous acidities. The extractant Cyanex 923 demonstrated better scandium loading and selectivity for TI(IV). Fe(III) and Lu(III) than Cyanex 925. The effects of extractant concentration on the extractions of sulphuric acid and Sc(III) by Cyanex 923 were examined. The stoichiometries of the extraction reactions were postulated based on slope analysis. The experimental results indicate that Cyanex 923 can be employed to recover scandium directly from the hydrolytic mother solution arising from TiO2 production via the sulphate process. The parameters studied were scandium loading capacity, phase ratio, concentrations of Ti(IV) scrubbing and Sc(III) stripping agents. A new solvent extraction technology of scandium recovery was developed. The purity of the final Sc(III) product is above 95% with a yield > 94%. (C) 1998 Elsevier Science B.V.

STRUCTURE OF AQUABIS-(PICOLINATO)SCANDIUM HYDROXIDE DIHYDRATE

The crystal structure of the title complex was established by X-ray diffraction analysis. Each scandium ion is seven-coordinated by two oxygen atoms and two nitrogen atoms from the picolinato ions, one water oxygen atom and two hydroxide ions. The nitrogen atom and one carboxyl oxygen atom of each picolinato ion are coordinated to the same scandium ion to form a five-membered chelating ring. Each hydroxide ion is coordinated to two scandium ions to form hydroxide bridges and a dimeric molecule unit.

Structure and thermal stability of novel fluorophosphate glasses

A systematic investigation on glass formation in the PbF2-InF3-BaHPO4 ternary system has been carried out. These glasses have characterized by IR spectra, Raman spectra and differential thermal analysis. The results show that the structure of these glasses is mainly affected by BaHPO4 and InF3 contents. With decreasing BaHPO4 content, the glass structure gradually transforms from metaphosphate to polyphosphate. When InF3 content is low, it mainly acts as network modifier, when its content is high; it enters glass matrix and forms In(O,F)(6) groups connecting the polymerized phosphorus oxygen species. PbF2 mainly acts as network modifier in this system. Systematic variations of the glass transition temperature and the thermal stability index agree well with these results. The most stable glass with Delta T = 230 degrees C and S = 21.79 K is obtained. (c) 2004 Elsevier B.V. All rights reserved.

Influence of phosphate precursors on the structures of sodium aluminophosphate sols, gels and glasses

Transparent and homogeneous aluminophosphate gels and glasses have been widely synthesized through an aqueous sol-gel route, extending significantly the glass-forming range compared to that accessible via the melt-cooling route. Different phosphorus precursors, sodium polyphosphate (NaPO3) and orthophosphate species (NaH2PO4 and/or H3PO4) were compared with regard to the macroscopic properties and the microscopic structure of the resultant gels and glasses as characterized by extensive high-resolution liquid- and solid-state NMR. Sodium polyphosphate solution results in a substantially wider composition range of homogenous gel formation than orthophosphate solutions, and the two routes produce significant structural differences in the sol and xerogel states. Nevertheless, the structures of the glasses obtained upon gel annealing above 400 degrees C are independent of the P-precursors used. (c) 2007 Elsevier B.V. All rights reserved.

ScAlMgO_4晶体的生长缺陷

采用提拉法生长出φ30 mm×55 mm的ScAlMgO4晶体。在晶体生长过程中有轻微的挥发,粉末X射线衍射分析表明:挥发物质为MgO单相。运用扫描电镜、光学显微镜以及高分辨X射线衍射仪对晶体中的包裹物、开裂、生长条纹和小角晶界缺陷进行了研究。结果表明:温度梯度和热应力是形成晶体中缺陷的主要原因。通过合理设计温场,控制固-液界面的形状及冷却过程的降温速率,可以提高晶体的完整性。

Effects of Arsenate on Microcystin Content and Leakage of Microcystis Strain PCC7806 Under Various Phosphate Regimes

Both arsenic pollution and eutrophication are prominent environmental issues when considering the problem of global water pollution. It is important to reveal the effects of arsenic species on cyanobacterial growth and toxin yields to assess ecological risk of arsenic pollution or at least understand naturally occurring blooms. The sensitivity of cyanobacteria to arsenate has often been linked to the structural similarities of arsenate and phosphate. Thus, we approached the effect of arsenate with concentrations from 10(-8) to 10(-4) M on Microcystis strain PCC7806 under various phosphate regimes. The present study showed that Microcystis strain PCC7806 was arsenate tolerant up to 10(-4) M. And such tolerance was without reference to both content of intra- and extra-cellular phosphate. It seems that arsenate involved the regulation of microcystin synthesis and cellular polyphosphate contributed to microcystin production of Microcystis responding to arsenate, since there was a positive linear correlation of the cellular microcystin quota with the exposure concentration of arsenate when the cells were not preconditioned to phosphate starvation. It is presumed that arsenate could help to actively export microcystins from living Microcystis cells when preconditioned to phosphate starvation and incubated with the medium containing 1 mu M phosphate. This study firstly provided evidence that microcystin content and/or release of Microcystis might be impacted by arsenate if it exists in harmful algal blooms. (C) 2008 Wiley Periodicals, Inc. Environ Toxicol 24:97 94, 2009.

An effective method for enhancing metal-ions' selectivity of ionic liquid-based extraction system: Adding water-soluble complexing agent

Selective extraction-separation of yttrium(Ill) from heavy lanthanides into 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)mim][PF6]) containing Cyanex 923 was achieved by adding a water-soluble complexing agent (EDTA) to aqueous phase. The simple and environmentally benign complexing method was proved to be an effective strategy for enhancing the selectivity of [C(n)mim] [PF6]/[Tf2N]-based extraction system without increasing the loss of [C(n)mim](+). (c) 2007 Elsevier B.V. All rights reserved.

Promoting carbonization of polypropylene during combustion through synergistic catalysis of a trace of halogenated compounds and Ni2O3 for improving flame retardancy

The effect of combination between a trace of halogenated compounds (such as ferric chloride and ammonium bromide) and Ni2O3 particles on the carbonization of polypropylene (PP) was investigated during combustion. The results showed a synergistic catalysis of combined halogenated compounds with Ni2O3 in promoting the formation of the residual char during combustion. The investigation on the promotion mechanism showed that halide radical releasing from halogen-containing additives worked as a catalyst to accelerate dehydrogenation-aromatization of degradation products of PR which promote the degradation products to form the residual char catalyzed by nickel catalyst.

Highly 3,4-Selective Polymerization of Isoprene with NPN Ligand Stabilized Rare-Earth Metal Bis(alkyl)s. Structures and Performances

Deprotonation of (ArNHPPh2NAr2)-N-1 (H[NPN](n), n = 1 - 10) by Ln(CH2SiMe3)(3)(THF)(2) (Ln = Lu, Y, Sc, Er) generated a series of rare-earth metal bis(alkyl) complexes [NPN](n)Ln(CH2SiMe3)(2)(THF)(2) (1-10), which under activation with [Ph3C][B(C6F5)(4)] and AliBu(3) were tested for isoprene polymerization. The correlation between catalytic performances and molecular structures of the complexes has been investigated. Complexes 1-5 and 8, where Ar-1 is nonsubstituted or ortho-alkyl-substituted phenyl, adopt trigonal-bipyramidal geometry. The Ar-1 and Ar-2 rings are perpendicular in 1-4 and 8 but parallel in 5. When Ar-1 is pyridyl, the resultant lutetium and yttrium complexes 9a and 9b adopt tetragonal geometry with the ligand coordinating to the metal ions in a N,N,N-tridentate mode, whereas in the scandium analogue 9c, the ligand coordinates to the Sc3+ ion in a N,N-bidentate mode. These structural characteristics endow the complexes with versatile catalytic performances, With increase of the steric bulkiness of the ortho-substituents Ar-1 and Ar-2, the 3,4-selectivity increased stepwise from 81.6% for lutetium complex 1 to 96.8% for lutetium complex 6 and to 97.8% for lutetium complex 7a. However, further increase of the steric bulk of the ligand led to a slight drop of 3,4-selectivity for the attached complex 5 (95.1%).

Copolymerization of ethylene with norbornene catalyzed by cationic rare earth metal fluorenyl functionalized N-heterocyclic carbene complexes

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH2SiMe3)(2) (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH2SiMe3)(2) ((tBu)Flu-NHC = 2,7-(Bu2C13H6CH2CH2)-Bu-t(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified N-heterocyclic carbene (Ind-NHC)Ln(CH2SiMe3)(2) (Ind-NHC = C9H6CH2CH2(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (3a); Lu (3d)), under the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed varied catalytic activities toward homo- and copolymerization of ethylene and norbornene. Among which the scandium complexes, in spite of ligand type, exhibited medium to high catalytic activity for ethylene polymerization (10(5) g mol(Sc)(-1) h(-1) atm(-1)), but all were almost inert to norbornene polymerization. Remarkably, higher activity was found for the copolymerization of ethylene and norbornene when using Sc based catalytic systems, which reached up to 5 x 10(6) g mol(Sc)(-1) h(-1) atm(-1) with 2a. The composition of the isolated copolymer was varying from random to alternating according to the feed ratio of the two monomers (r(E) = 4.1, r(NB) = 0.013).

Synthesis of the first rare earth metal bis(alkyl)s bearing an indenyl functionalized N-heterocyclic carbene

Treatment of indenyl-modified imidazolium bromide [C9H7CH2CH2(NCHCHN(C6H2Me3-2,4,6)CH)Br] ((IndH-NHC-H)Br) with rare earth metal tetra(alkyl) lithium (Ln(CH2SiMe3)(4)Li(THF)(4)) or with (trimethylsilylmethyl)lithium (LiCH2SiMe3) and rare earth metal tris(alkyl)s (Ln(CH2SiMe3)(3)(THF)(2)) sequentially afforded the first NHC-stabilized monomeric rare earth metal bis(alkyl) complexes (Ind-NHC)Ln(CH2SiMe3)(2) (1, Ln = Y; 2, Ln = Lu; 3, Ln = Sc) via double-deprotonation reactions. Complexes 1-3 are THF-free isostructural monomers. The monoanionic Ind-NHC species bond to the central metal ion in a eta(5):kappa(1) constrained geometry configuration (CGC) mode, which combine with the two cis-located alkyl moieties to form a tetrahedron ligand core, leading to the chirality of the complexes. Under the presence of activators AlEt3 and [Ph3C][B(C6F5)(4)], complex 2 showed catalytic activity toward the polymerization of isoprene to afford 3,4-regulated polyisoprene (91%).