Anion exchange separation of chromium and molybdenum from iron,vanadium, uranium and other elements in malonic acid solution

Summary Anion-exchange behaviour of chromium (III) and molybdenum (VI) was studied in malonate media. They form anionic complexes with malonic acid at pH 5.6. Various eluants, such as mineral acids and their salts were tested and a selectivity scale evolved. Cr and Mo were separated from Tl(I), alkali and alkaline earth elements by selective sorption and from Co(II), Ni(II), Mn(II), Zn(II) and Cd(II) by selective washing with water. They were separated from many other elements by selective elution. The sequential separation of Fe(III) V(IV), Cr(III), Mo(VI) and U(VI) was significant.     

Sorption-spectroscopy and test determination of uranium(VI) and iron(III) from a single sample on the solid phase of fiber materials filled with an AB-17 ion exchanger

Diffuse reflectance spectroscopy has been used for the study of the sorption of malonate and glycolate complexes of uranium(VI) and iron(III), present simultaneously in solution, onto the solid phase of fiber materials filled with an AB-17 anion exchanger. In the form of malonate complexes uranium(VI) is determined in 0.5 M HCl on substrate discs with immobilized Arsenazo III, while iron(III) is determined on substrate discs with potassium thiocyanate in 0.5 M HCl. The dependence of the analytical signals on the concentrations of U(VI) and Fe(III) is linear in the ranges 0.02–0.16 μg/mL; the detection limit is 0.01 μg/mL. The possibility of analysis of U(VI) and Fe(III) mixtures in ratio from 1: 5 to 5: 1 in the presence of 2-fold concentrations of Zr(IV), Th(IV), and Ti(IV), 5-fold concentrations of Bi(III), 10-fold concentrations of Cu(II), 20-fold concentrations of La(III), 100-fold concentrations of Ni(II) and Zn(II), and 200-fold concentrations of Co(II) and Ca(II) has been demonstrated. Standard color scales in the concentration range from 0.02 to 0.2 μg/mL have been used for the visual determination of uranium(VI) and iron(III).     

Synthesis and analytical properties of 3,4-dihydroxybenzaldehyde guanylhydrazone (3,4-DBGH)

Synthesis and analytical properties of 3,4-dihydroxy-benzaldehyde guanylhydrazone are described. The reagent was tested with 43 cations but only Co(II), Fe(II), Fe(III), Mo(VI), W(VI) and V(V) gave colored complexes. Spectral characteristics of the reagent are presented. Procedure for a selective a determination of Co(II), a sensitive determination of Fe(III) and determination of Mo(VI), W(VI) and V(V) in presence of large amounts of Fe(III) are reported. The method was applied for the determination (a) of Co(II) in presence of other cations at excess (b) of Fe(III) in a city drinking water sample without preconcentration and (c) of Mo(VI) in a standard steel sample.     

Study of the elementary processes involved in the selective oxidation of methane over MoOx/SiO2

Isolated molybdate species supported on silica are reported to have the highest specific activity and selectivity for the direct oxidation of methane to formaldehyde. The present investigation was undertaken to understand the elementary redox processes involved in the formation of formaldehyde over such species. A MoO(x)/SiO(2) catalyst was prepared with a Mo loading of 0.44 Mo/nm(2). On the basis of evidence from extended X-ray absorption fine structure (EXAFS) and Raman spectroscopy, the Mo atoms in this catalyst are present as isolated, pentacoordinated molybdate species containing a single Mo=O bond. Isotopic labeling experiments in combination with in-situ Raman spectroscopy were used to examine the reducibility of the dispersed molybdate species and the exchange of O atoms between the gas phase and the catalyst. It was established that treatment of MoO(x)/SiO(2) at 873 K under pure methane reduces the dispersed molybdate species to only a limited extent and results mainly in the deposition of amorphous carbon. During CH(4) oxidation to formaldehyde, the catalyst undergoes only a very small degree of reduction and typically only approximately 50-500 ppm of Mo(VI) is reduced to Mo(IV). Reactions carried out using CH(4) and (18)O(2) show that there is extensive scrambling of O atoms between the species in the gas phase and the catalyst. Additional experiments revealed that H(2)O formed in the reaction is the principal species responsible for the exchange of O atoms between the gas phase and the SiO(2) support. Low concentrations of H(2)O were observed to enhance the activity of MoO(x)/SiO(2) for CH(4) oxidation to formaldehyde. A mechanism for the oxidation of CH(4) over MoO(x)/SiO(2) was formulated in light of the observations made here and is discussed in the light of previous studies. It is proposed that peroxides are produced by the reaction of O(2) with a small concentration of reduced molybdate species and that the reaction of CH(4) with these peroxide species leads to the formation of formaldehyde. The proposed mechanism also accounts for the positive effects of low concentrations of H(2)O on the rate of formaldehyde formation.     

Adsorption-photometric determination of iron using silica with nitroso-R salt and nitroso-N salt functional groups

Adsorbents based on silica sequentially modified by polyhexamethylene guanidine and nitroso-R salt or nitroso-N salt are proposed for the preconcentration and adsorption-photometric determination of iron. It is shown that these adsorbents quantitatively recovered Fe(III) at pH 3.5–4.0 and Fe(II) at pH 4.5–7.0. In the adsorption of Fe(III) and Fe(II), intensely colored green complexes formed on the adsorbent surface. Based on the absence of signals in EPR spectra, it was concluded that iron in the oxidation state +2 was included into surface complexes with nitroso-R salt or nitroso-N salt. When Fe(III) interacted with nitroso-R salt or nitroso-N salt immobilized on the adsorbent surface, it was reduced to Fe(II). Diffuse reflection spectra of the surface complexes of iron(II) were broad bands with maxima at 720 and 710 nm. Procedures of the adsorption-photometric determination of iron in natural waters and snow samples were developed with the limit of detection of 0.05 μg of iron per 0.2 g of the adsorbent.     

溶胶-凝胶法制备Fe2(MoO4)3超微粒子催化剂

以硝酸铁和钼酸铵为原料，采用溶胶－凝胶法和微波加热技术制备了F 2(MoO4)3超微子催化剂，使用DTA－TG，IR，XRD以及BET比表面测试等手段，考察了制备条件对复合氧化物超微粒子形成、晶相和比表面积的影响。同时测试了该样品对甲苯选择性氧化制苯甲醛的催化性能。结果表明：制备Fe2(MoO4)2超微粒子的适宜条件为：初始溶液pH=1.0,mol柠檬酸：mol(铁＋钼）＝0．4。在此条件下制得的干凝胶，经微波加热处理后粒子的比表面积为36.4m^2/g，粒径约为35nm。在由甲苯气相选择氧化制苯甲醛的反应中表现出较高的催化活性。     

纳米孔碳负载Fe3O4催化剂上苯直接羟基化制苯酚

Fe3O4/CMK-3 was prepared by impregnation and used as a catalyst for the direct hydroxylation of benzene to phenol with hydro-gen peroxide. The iron species in the prepared catalyst was Fe3O4 because of the partial reduction of iron(III) to iron(II) on the surface of CMK-3. The high catalytic activity of the catalyst arises from the formation of Fe3O4 on the surface of CMK-3 and the high selectivity for phenol is attributed to the consumption of excess hydroxyl radicals by CMK-3. The effect of temperature,re...     

X-ray structurally characterized Mo (VI), Fe (III) and Cu (II) complexes of amide-imine conjugate: (bio)catalytic and histidine recognition studies

An amide-imine conjugate, (E)-N′-((2-hydroxybenzen-1-yl) methylene)-4-methylbenzohydrazide (H₂L^PTASAL), derived from 4-methyl-benzoic acid hydrazide (PTA) and 2-hydroxybenzaldehyde is used to prepare Mo (VI), Cu (II) and Fe (III) complexes. The X-ray structurally characterized complexes have been explored as catalyst for amine assisted asymmetric ring opening (ARO) of epoxide, carbon-heteroatom cross-coupling and ethyl benzene oxidation. In addition, their catecholase like activities have thoroughly been investigated. Moreover, the Cu (II) complex selectively recognizes histidine by fluorescence spectroscopy.     

Iron(III), cobalt(II) and copper(II) complexes bearing 8‐quinolinol encapsulated in zeolite?Y for the aerobic oxidation of styrene

A series of Fe(III), Co(II) and Cu(II) complexes of 8‐quinolinol were encapsulated into the supercages of zeolite? Y and characterized by X‐ray diffraction, SEM, N₂ adsorption/desorption, FT‐IR, UV–vis spectroscopy, elemental analysis, ICP‐AES and TG/DSC measurements. The encapsulation was achieved by a flexible ligand method in which the transition metal cations were first ion‐exchanged into zeolite Y and then complexed with 8‐quinolinol ligand. The metal‐exchanged zeolites, metal complexes encapsulated in zeolite–Y plus non‐encapsulated homogeneous counterparts were all screened as catalysts for the aerobic oxidation of styrene under mild conditions. It was found that the encapsulated complexes always showed better activity than their respective non‐encapsulated counterparts. Moreover, the encapsulated iron complex showed good recoverability without significant loss of activity and selectivity within successive runs. Heterogeneity test for this catalyst confirmed its high stability against leaching of active complex species into solution. Copyright © 2011 John Wiley & Sons, Ltd.     

On electrocatalysis in alkene–molybdenum(VI) system at Pt/acidic solution interface

The catalytic reduction of ethene, propene and 1-butene on a polycrystalline Pt electrode in strongly acidic medium containing Mo(VI) oxo-species has been examined by cyclic voltammetry taking into account the influence of perchloric acid and molybdate concentration as well as that of the scan rate on the cathodic current response. About tenfold increase in the reaction rate of each alkene investigated has been achieved at the optimum molybdate concentration of 1–2.5 mM in 4-M HClO₄ solution as a supporting electrolyte in comparison with that obtained in the absence of Mo(VI) oxo-species. It was ascertained that the catalytic reduction current strongly depends on the amount of cationic Mo(VI) oxo-species at the Pt electrode/solution interface. Simultaneously, the electroreduction of cationic Mo(VI) oxo-species was found to be effectively enhanced in the presence of alkene. According to the proposed reaction pathways, alkenes are reduced to alkanes via a non-faradaic reaction with Mo(V) and/or Mo(III) cationic moieties formed in the preceding reductive electron-transfer steps from the parent cationic Mo(VI) oxo-species. Continuous regeneration of the electroactive Mo(VI) and/or Mo(V) cationic oxo-species accounts for the observed catalytic phenomenon.     

A potentiometric study of the oxidation of cobalt(II) with gold(III) chloride in presence of 1,10 phenanthroline or 2,2'-bipyridine : A new titration of cobalt (II) and its application to nickel-base alloys

The redox reaction between cobalt(II) and gold(III) chloride in the presence of 1.10-phenanthroline or 2,2'-bipyridine was studied, and a titration of the cobalt(II) complex with a gold(III) chloride solution was developed. A 4-fold amount of 1,10-phenanthroline or 2,2'-bipyridine was necessary for rapid quantitative reaction; the permissible pH range was 1.5–5. The oxidation of the cobalt(II) complex proceeds rapidly at 40–50°C, and a direct potentiometric titration was possible. The following maximum errors were obtained: 3.3% for 0.2–1.0 mg Co, 2.0% for 1–5 mg Co, and 0.70% for 10–40 mg Co. The following ions did not interfere: Ni(II), Zn(II), Pb(II), Cd(II), Mn(II), Fe(II), Cr(III), Al(III), Th(IV), Se(IV), Ti(IV), U(VI), Mo(VI), SO^2-₄ and PO^3-₄. Even small quantities of silver(I), copper(II), palladium(II), mercury(II)and iron(III) interfered. The method was applied to the determination of high cobalt contents in high-temperature nickel-base alloys.     

Formation of a "less stable" polyanion directed and protected by electrophilic internal surface functionalities of a capsule in growth: [{Mo6O19}2- subset {Mo(VI)72Fe(III)30O252(ac)20(H2O)92}]4-

The spherical capsule skeleton of the host-guest system [{Mo6O19}2- subset {Mo(VI)72Fe(III)30O252(CH3COO)20(H2O)92}]4- 1a--built up by 12 {(Mo(VI))Mo(VI)5} type pentagonal units linked by 30 Fe(III) centers which span the unique icosahedral Archimedean solid, the icosidodecahedron--can now be constructed deliberately and with a simpler composition than before from an acidified aqueous molybdate solution containing the mentioned (virtual) pentagonal units; the encapsulated hexamolybdate--normally not formed in water--is built up in an unprecedented way concomitant with capsule growth, while being directed by the corresponding internal electrophilic surface functionalities.     

调控制备pH值对铁钼催化剂结构及性能的影响

通过调控共沉淀中钼酸铵溶液的酸度制备了系列铁钼催化剂,采用N_2吸附-脱附、Raman、XRD、SEM、H2-TPR等方法对催化剂的结构进行了表征,并考察了不同酸度条件下制备的铁钼催化剂的甲醇氧化制甲醛催化活性。结果表明,钼酸铵溶液酸度影响催化剂的粒径、形貌及表层铁、钼物种的分布与富集。恰当的钼酸铵溶液酸度范围,优化了催化剂表层MoO_3和Fe_2(MoO_4)_3物种的比例,改善了催化剂的催化氧化性能,有利于甲醇氧化制甲醛收率和选择性的提高。     

Synthesis, structure, and properties of a mixed-valent triiron complex of tetramethyl reductic acid, an ascorbic acid analogue, and its relationship to a functional non-heme iron oxidation catalyst system

The purple triiron(II,III,III) complex, [Fe(3)Cl(2)(TMRASQ)(4)(HTMRA)(2)] x C(5)H(12) (1 x C(5)H(12)), where H(2)TMRA is a tetramethyl reductic acid, 4,4,5,5-tetramethyl-2,3-dihydroxy-2-cyclopenten-1-one, and HTMRASQ is the semiquinone form of this ligand, was prepared from (Et(4)N)(2)[Fe(2)OCl(6)] and H(2)TMRA and characterized by X-ray crystallography, M?ssbauer spectroscopy, and redox titrations. The physical properties of the complex in solution are consistent with its mixed-valent character, as delineated by a solid-state structure analysis. Assignments of the iron and ligand oxidation states in the crystal were made on the basis of a valence bond sum analysis and the internal ligand geometry. As the first well-characterized iron complex of an ascorbic acid H(2)AA analogue, 1 provides insight into the possible coordination geometry of the family of complexes containing H(2)AA and its analogues. In the presence of air and H(2)TMRA, 1 is able to catalyze the oxidation of cyclohexane to cyclohexanol with remarkable selectivity, but the nature of the true catalyst remains unknown.     

Ligand topology variations and the importance of ligand field strength in non-heme iron catalyzed oxidations of alkanes

A series of iron(II)-bis(triflate) complexes [Fe(L)(OTf)2] containing linear tetradentate bis(quinolyl)-diamine and bis(quinolylmethyl)-diamine ligands with a range of ligand backbones has been prepared. The coordination geometries of these complexes have been investigated in the solid state by X-ray crystallography and in solution by 1H and 19F NMR spectroscopy. Because of the labile nature of high-spin iron(II) complexes in solution, dynamic equilibria of complexes with different coordination geometries (cis-alpha, cis-beta, and trans) are observed with certain ligand systems. In these cases, the geometry observed in the solid-state does not necessarily represent the only or even the major geometry present in solution. The ligand field strength in the various complexes has been investigated by variable-temperature (VT) magnetic moment measurements and by UV-vis spectroscopy. The strongest ligand field is observed with the most rigid ligand that generates [Fe(L)(OTf)2] complexes with a cis-alpha coordination geometry, and the corresponding [Fe(L)(CH3CN)2]2+ complex displays spin crossover behavior. The catalytic properties of the complexes for the oxidation of cyclohexane have been investigated using hydrogen peroxide as the oxidant. An increased flexibility in the ligand results in a weaker ligand field, which increases the lability of the complexes. The activity and selectivity of the catalysts appear to be related to the strength of the ligand field and the stability of the catalyst.     

Tensammetric determination of microgram amounts of vanadium by catalytic oxidation of o-aminophenol

A tensammetric method is proposed for the determination of microgram amounts of vanadium, based on catalysis of the oxidation of o-aminophenol with sodium chlorate in acidic solution (pH 2.0). The oxidation product gives a very sensitive tensammetric wave; under optimum conditions, the wave-height is proportional to the concentration of va vanadium. From 0.2 to 3.0 mug of vanadium can be determined in a final volume of 50 ml. Mo(VI), W(VI), Mn(VII), Ce(IV) and large amounts of Al(III) and Fe(III) cause positive errors, and Hg(II) and thiosulphate negative errors. Interference from Fe(III), Al(III) and Cu(II) can be eliminated by solvent with oxine at about pH 8.0.     

Metal-based anti-diabetic drugs: advances and challenges

The current status and likely future directions of complexes of V(V/IV), Cr(III), Mo(VI), W(VI), Zn(II), Cu(II), and Mn(III) as potential oral drugs against type 2 diabetes are reviewed. We propose a unified model of extra- and intracellular mechanisms of anti-diabetic efficacies of V(V/IV), Mo(VI), W(VI), and Cr(III), centred on high-oxidation-state oxido/peroxido species that inhibit protein tyrosine phosphatases (PTPs) involved in insulin signalling. The postulated oxidative mechanism of anti-diabetic activity of Cr(III) via carcinogenic Cr(VI/V) (which adds to safety concerns) is consistent with recent clinical trials on Cr(III) picolinate, where activity was apparent only in patients with poorly controlled diabetes (high oxidative stress), and the correlation between the anti-diabetic activities and ease of oxidation of Cr(III) supplements and their metabolites in vivo. Zn(II) and Cu(II) anti-diabetics act via different mechanisms and are unlikely to be used as specific anti-diabetics due to their diverse and unpredictable biological activities. Hence, future research directions are likely to centre on enhancing the bioavailability and selectivity of V(V/IV), Mo(VI), or W(VI) drugs. The strategy of potentiating circulating insulin with metal ions has distinct therapeutic advantages over interventions that stimulate the release of more insulin, or use insulin mimetics, because of many adverse side-effects of increased levels of insulin, including increased risks of cancer and cardiovascular diseases.     

Polymer Supported Schiff Base Complexes of Iron(III), Cobalt(II) and Nickel(II) Ions and their Catalytic Activity in Oxidation of Phenol and Cyclohexene

The polymer supported transition metal complexes of N,N′‐bis (o‐hydroxy acetophenone) hydrazine (HPHZ) Schiff base were prepared by immobilization of N,N′‐bis(4‐amino‐o‐hydroxyacetophenone)hydrazine (AHPHZ) Schiff base on chloromethylated polystyrene beads of a constant degree of crosslinking and then loading iron(III), cobalt(II) and nickel(II) ions in methanol. The complexation of polymer anchored HPHZ Schiff base with iron(III), cobalt(II) and nickel(II) ions was 83.30%, 84.20% and 87.80%, respectively, whereas with unsupported HPHZ Schiff base, the complexation of these metal ions was 80.3%, 79.90% and 85.63%. The unsupported and polymer supported metal complexes were characterized for their structures using I.R, UV and elemental analysis. The iron(III) complexes of HPHZ Schiff base were octahedral in geometry, whereas cobalt(II) and nickel(II) complexes showed square planar structures as supported by UV and magnetic measurements. The thermogravimetric analysis (TGA) of HPHZ Schiff base and its metal complexes was used to analyze the variation in thermal stability of HPHZ Schiff base on complexation with metal ions. The HPHZ Schiff base showed a weight loss of 58% at 500°C, but its iron(III), cobalt(II) and nickel(II) ions complexes have shown a weight loss of 30%, 52% and 45% at same temperature. The catalytic activity of metal complexes was tested by studying the oxidation of phenol and epoxidation of cyclohexene in presence of hydrogen peroxide as an oxidant. The supported HPHZ Schiff base complexes of iron(III) ions showed 64.0% conversion for phenol and 81.3% conversion for cyclohexene at a molar ratio of 1∶1∶1 of substrate to catalyst and hydrogen peroxide, but unsupported complexes of iron(III) ions showed 55.5% conversion for phenol and 66.4% conversion for cyclohexene at 1∶1∶1 molar ratio of substrate to catalyst and hydrogen peroxide. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 90.5% and 96.5% with supported HPHZ Schiff base complexes of iron(III) ions, but was found to be low with cobalt(II) and nickel(II) ions complexes of Schiff base. The selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was different with studied metal ions and varied with molar ratio of metal ions in the reaction mixture. The selectivity was constant on varying the molar ratio of hydrogen peroxide and substrate. The energy of activation for epoxidation of cyclohexene and phenol conversion in presence of polymer supported HPHZ Schiff base complexes of iron(III) ions was 8.9 kJ mol^?1 and 22.8 kJ mol^?1, respectively, but was high with Schiff base complexes of cobalt(II) and nickel(II) ions and with unsupported Schiff base complexes.     

Framed aromatic polyurethanes based on an anionic macroinitiator, 4,4'-diphenylmethane diisocyanate,and 4,4'-dihydroxy-2,2-diphenylpropane: Metal-complex modification

Metal complexes are prepared from poly(oxyethylene glycol) and iron(III) chloride and studied as modifiers of framed aromatic polyurethanes. The latter polymers are synthesized on the basis of macroinitiators, 4,4'-dihydroxy-2,2-diphenylpropane, and polyisocyanate, which is a mixture of 4,4'-diphenylmethane diisocyanate and its branched derivatives. The interaction of iron(III) chloride with poly(oxyethylene glycol) is accompanied by redox processes that lead to its degradation and partial reduction of Fe(III) to Fe(II). Aromatic polyurethanes are modified in the concentration range of metal complexes from 0.5 to 20%. At a concentration of metal complexes of 4–7%, the polymer shows high mechanical characteristics and excellent thermal stability. The framed structure of aromatic polyurethanes hampers the effective contacts of coordinately bonded Fe atoms that are present in various oxidation states.     

Analysis of iron(II)/iron(III) phytosiderophore complexes by nano-electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Nano-electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (nano-ESI-FTICRMS) was employed for the analysis of the phytosiderophore 2'-deoxymugineic acid (DMA) and the candidate ligand for the intracellular iron transport in plants nicotianamine (NA). Due to the zwitterionic nature of NA and DMA, complementary mass spectra were obtained in positive and negative ionization modes. The technique was also used for speciation of their complexes with Fe(II) and Fe(III), respectively. The species observed at pH 7.3 are the 1:1 Fe-ligand complexes and no evidence for the existence of dimeric complexes was observed. NA and DMA differ only by one mass unit. Consequently, in the system NA + DMA + Fe(II)/Fe(III), there are pairs of iron species (i.e. NA-Fe(II) and DMA-Fe(III)) with the same nominal mass, which differ only by approximately 0.02 mass units. It is shown that high-resolution MS accompanied by accurate mass data analysis allows the unequivocal identification of all four iron species (NA-Fe(II), NA-Fe(III), DMA-Fe(II), DMA-Fe(III)) in one solution without separation. We also addressed the possible alteration of the oxidation state of chelated iron under nano-ESI conditions, but no redox reactions were observed under optimized conditions.