Reactivity of bisthiosemicarbazones with Sn(II) and Sn(IV): The synthesis and structure of an eight-coordinate complex with two bis(thiosemicarbazone) ligands

Reaction of SnCl₂ with the bisthiosemicarbazone ligand ATSMH₂ led to the formation of the octahedral tin(IV) complex [Sn(ATSM)Cl₂] (1) comprising one doubly deprotonated ligand occupying the equatorial positions and two axial chlorides. Reaction with SnI₄ gave [Sn(ATSM)₂] (2), containing two doubly deprotonated ligands giving a distorted dodecahedral geometry. The complexes were characterised by elemental analysis, mass spectrometry, ¹³C and ¹¹⁹Sn CP/MAS NMR and in the case of complex 2 by X-ray diffraction.     

Encapsulation of bis(ethylenediamine) copper(II) complex in zeolite matrices

Bis(ethylenediamine) copper(II) complex was encapsulated in NaY, KL, Naβ and NaZSM-5 zeolite. The redox properties of metal complexes in neat and encapsulated state were studied by cyclic voltammetry. The redox potential of metal complex is altered towards negative value upon encapsulation in various zeolites. This may be due to axial interaction with various zeolite matrix. The redox properties of biological systems are also altered (cytochrome-C, and Vitamin-B₁₂) when they are immobilized on NaAlMCM-41 materials. The copper ethylenediamine complex in constrained environment shows higher activity for the oxidation of dimethyl sulfide compared to that of neat complex.     

Sn(IV)-Porphyrin-Based Nanostructures Featuring Pd(II)-Mediated Supramolecular Arrays and Their Photocatalytic Degradation of Acid Orange 7 Dye

Two robust Sn(IV)-porphyrin-based supramolecular arrays (1 and 2) were synthesized via the reaction of trans-Pd(PhCN)₂Cl₂ with two precursor building blocks (SnP¹ and SnP²). The structural patterns in these architectures vary from 2D to 3D depending on the axial ligation of Sn(IV)-porphyrin units. A discrete 2D tetrameric supramolecule (1) was constructed by coordination of {(trans-dihydroxo)[5,10-bis(4-pyridyl)-15,20-bis(phenyl) porphyrinato]}tin(IV) (SnP¹) with trans-PdCl₂ units. In contrast, the coordination between the {(trans-diisonicotinato)[5,10-bis(4-pyridyl)-15,20-bis(phenyl)porphyrinato]}tin(IV) (SnP²) and trans-PdCl₂ units formed a divergent 3D array (2). Axial ligation of the Sn(IV)-porphyrin building blocks not only alters the supramolecular arrays but also significantly modifies the nanostructures, including porosity, surface area, stability, and morphology. These structural changes consequently affected the photocatalytic degradation efficiency under visible-light irradiation towards acid orange 7 (AO) dye in an aqueous solution. The degradation efficiency of the AO dye in the aqueous solution was observed to be between 86% to 91% within 90 min by these photocatalysts.     

Preparation of Co-Sn alloys by electroreduction of Co(II) and Sn(II) in molten LiCl-KCl

Co-Sn alloys were prepared by an electrochemical route in molten LiCl-KCl between 400 and 550 °C. The Sn(IV)/Sn(II), Sn(II)/Sn(0) and Co(II)/Co(0) redox couples were studied by cyclic voltammetry and/or chronopotentiometry over the temperature range. The diffusion coefficient values of Co(II) ions were measured. For example, it was found that the D_Co(II) values deduced from chronopotentiometry range from D_Co(II) = 1.65 × 10⁻⁵ cm² s⁻¹ at 400 °C to 4.95 × 10⁻⁵ cm² s⁻¹ at 550 °C. The standard potential of the Co(II)/Co(0) redox couple in molten LiCl-KCl was measured at 400 °C: vs Cl₂/Cl⁻. Finally, Co-Sn alloys were prepared in potentiostatic mode. The influence of the temperature of molten LiCl-KCl, the applied potential and the deposition time on the morphology and the composition of the Co-Sn alloys were also investigated. For T > 450 °C, the following tendency has been observed: the more negative the potential, the higher the Sn content in the deposited alloy. Thus, depending on the operating conditions, pure CoSn or CoSn₂ can be prepared.     

Kinetics of Sn electrodeposition from Sn(II)–citrate solutions

The influence of solution chemistry on the electrodeposition of Sn from Sn(II)–citrate solutions is studied. The distribution of various Sn(II)–citrate complexes and citrate ligands is calculated and the results presented as speciation diagrams. At a SnCl₂·H₂O concentration of 0.22 mol/L and citrate concentration from 0.30 mol/L to 0.66 mol/L, SnH₃L⁺ (where L represents the tetravalent citrate ligand) is the main species at pH below about 1.2 and SnHL⁻ is the main species at pH above about 4. Polarization studies and reduction potential calculations show that the Sn(II)–citrate complexes have similar reduction potentials at a given solution composition and pH. However, the Sn(II)–citrate complexes become more difficult to reduce with higher total citrate concentration and higher solution pH. Nevertheless, SnHL⁻ which forms at higher pH is a favored Sn(II)–citrate complex for Sn electrodeposition due to better plated film morphology, likely as a result of its slower electroplating kinetics. Precipitates are formed from the Sn(II)–citrate solutions after adding hydrochloric acid (to lower the pH). Compositional and structural analyses indicate that the precipitates may have the formula Sn₂L.     

Kinetic behaviour of the Sn(IV)-Sn(II) couple in acidified concentrated bromide solutions at a glassy carbon rotating ring-disk electrode

Kinetic parameters of the Sn(IV)-Sn(II) couple are evaluated at a glassy carbon rotating ring-disk electrode in acidified concentrated bromide media. Both the oxidation and reduction are found to be first order in reactant and to proceed irreversibly. While the oxidation of Sn(II) shows no complications, the reduction of Sn(IV) is probably preceded by a homogeneous chemical reaction involving complexation with bromide ions. Only in highly concentrated bromide media (10 M) is a relatively undisturbed Sn(IV) reduction wave obtained.     

Comparison of Surface-Active Properties of (Alkyloxycarbonylmethyl)trimethylammonium Chlorides and Alkyltrimethylammonium Chlorides

Surface-active properties of cleavable surfactants with a betaine ester group—(n-alkyloxycarbonylmethyl)trimethylammonium chlorides, used as separation reagents—were investigated. Critical micelle concentrations, dispersing powers, and foaming powers were comparable to those of alkyltrimethylammonium chlorides with the same total number of carbon atoms. On the other hand, the solubilities of the four hydrophobic dyes N,N-dimethyl-3-nitroaniline, naphthalene, pyrene, and oil orange SS in the former surfactant solutions were equal to or slightly smaller than those in the solutions of the latter surfactants with the same alkyl chain length. The alkali hydrolysis yields of the formers approached 100% in aqueous buffer solution at pH 10 and 25 °C within 10 min, and the yield at pH 9 was dependent on the alkyl chain length. This type of surfactant was also found to be as an efficient separation reagent which disperses carbon black and solubilizes the above dyes into aqueous neutral solution and then separates them instantaneously and almost perfectly as precipitates when a small excess of NaOH is added.

Effect of Cobalt(II) Oxide and Manganese(IV) Oxide on Sintering of Tin(IV) Oxide

Additions of 0. 5 to 2. 0 mol% of CoO or MnO₂ onto SnO₂ promote densification of this oxide up to 99% of theoretical density. The temperature of the maximum shrinkage rate ( T_M ) and the relative density in the maximum densification rate (p*) during constant sintering heating rate depend on the dopant concentration. Thus, dopant concentration controls the densifying and nondensifying mechanisms during sintering. The densification of SnO₂ witih addition of CoO or MnO₂ is explained in terms of the creation of oxygen vacancies.     

Electrochemistry of Sn(II)/Sn in a hydrophobic room-temperature ionic liquid

The electrochemical reaction of Sn(II)/Sn was investigated in a room-temperature ionic liquid, 1-n-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) at 25 °C. The anodic dissolution of Sn metal proceeded by a two-electron transfer reaction with a current efficiency of nearly 100%. Electrodeposition of Sn on a Cu substrate is possible in BMPTFSI containing Sn(II). The formal potential of the Sn(II)/Sn is −0.57 V vs. Ag/Ag(I). The diffusion coefficient of Sn(II) was estimated to be ∼1 × 10⁻⁷ cm² s⁻¹ from chronoamperometric and chronopotentiometric techniques. The initial stage of nucleation of Sn on a polycrystalline Pt substrate was found to be classified into a three-dimensional progressive nucleation under diffusion control by chronoamperometry, suggesting the rate of nucleation is faster than that of crystal growth.     

Ion-Exchange Behavior of New and Novel Zirconium(IV)-Based Composite Cation-Exchangers

The synthesized polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers were characterized by Fourier transform infrared spectroscopy, UV spectra, X-ray diffraction, scanning electron microscope, thermogravimetric analysis, and conductivity studies. The ion-exchange capacities, effect of eluent concentration, elution time, elution behavior, and pH on ion-exchange capacity were also studied to exploit the ion-exchange capability of the composites. The study revealed that polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate ion exchangers are having excellent ion-exchange capacity values for K⁺ ion 1.36 and 1.44?meq?g^?1, respectively. The organic polymeric part of the composites provides mechanical and chemical stability, whereas the inorganic part supports the ion-exchange behavior and thermal stability. The increase in electrical conductivity is due to the inorganic and organic parts. A mechanism for the formation of the polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers is discussed, which may also be applied for the preparation of other composite ion exchangers. Sorption behavior of metal ions on the composites was studied in different solvent systems. On the basis of distribution coefficient values (K_d), it has been found that the cation-exchange materials are highly selective for Pb(II)-ions. Such modified composite materials can be applied as an electrochemically switchable ion exchanger for water treatment, especially water softening.     

Analytical and environmental applications of polyaniline Sn(IV) tungstoarsenate and polypyrrole polyantimonic acid composite cation-exchangers

Two organic–inorganic type composite materials were prepared via the incorporation of organic conducting polymers into the inorganic precipitates of multivalent metal acid salts to explore their analytical and environmental applications. Vital uses of these materials for the analyses of water pollution were demonstrated by the quantitative separation of Cd²⁺ and Hg²⁺ from some synthetic and real samples onto their columns. Separation and determination of Zn²⁺ and Fe²⁺ in the pharmaceutical preparations were also performed. The adsorption behavior of dichlorvos (insecticide) on the surface of polyaniline Sn(IV) tungstoarsenate was studied which indicating its usefulness in the decrease of environmental pollution load.     

Partitioning of Polymeric Plutonium(IV) in Winsor II Microemulsion Systems

Abstract

The hydrolysis and polymerization of Pu(IV) can cause serious problems during the aqueous processing of spent fuel and nuclear wastes. Several studies describing the liquid/liquid extraction behavior of polymeric Pu(IV) have been reported in the literature. In many cases, poor plutonium extraction was accompanied by the appearance of an interfacial crud or third phase. Invariably, poor mass balances were observed during the extraction of aged, colloidal Pu(IV). Extraction of colloidal Pu(IV) by microemulsion-based solvent extraction systems, however, is capable of attaining bulk phase mass balances for Pu of 100%. The Winsor II microemulsions discussed in this paper consisted of sodium bis(2-ethylhexyl) sulfosuccinate in hexane with either octylphenyl-N,N-diisobutylcarbamoylmethyl-phosphine oxide or tributyl phosphate as coextractant. Backextraction of plutonium from microemulsion phases was achieved by Pu encapsulation in silica particles that were produced by the acid-catalyzed hydrolysis and polymerization of tetraethoxysilane within the aqueous microdroplets of the microemulsion.     

颜料在水泥和水泥制品上的应用(二)

介绍水泥及其制品的颜色本质、着色剂和着色方法、着色理论,对彩色水泥、砂浆、混凝土、砖瓦等列出着色实例。     

Synthesis and study of photocatalytic oxide nanocomposites of titanium(IV) and cobalt(II)

The phase formation, texture, and photocatalytic activity of synthesized oxide nanocomposites of titanium(IV) and cobalt(II) have been studied in relation to the cobalt content and temperature of heat treatment. The high photocatalytic activity of optimum compositions has been recorded within the spectral range of visible light with λ ≥ 670 nm.     

Stability constants of adipate complexes of copper(II), nickel(II), zinc(II), cobalt(II), uranyl(II) and thorium(IV) determined by electrophoresis

Stability constants of Copper(II), Nickel(II), Cobalt(II), Zinc(II), Uranyl(II) and Thorium(IV) adipates have been determined by paper electrophoresis. Adipic acid (0.005 mol dm^?3) was added to the background electrolyte: 0.1 mol dm^?3 HClO₄. The proportions of (CH₂)₄COOH COO^? and (CH₂)₄C₂O⁼₂ were varied by changing the pH of the electrolyte. These anions yielded the complexes Zn(CH₂)₄COOH COO⁺, Co(CH₂)₄COOH COO⁺, Ni(CH₂)₄COOH COO⁺, Th(CH₂)₄COOH COO³⁺, Th[(CH₂)₄COOH COO]₄, Cu(CH₂)₄ C₂O₄ and UO₂[(CH₂)₄(C₂O₄)]^2?₂, whose stability constants are found to be 10^2.8, 10^2.8, 10^3.2, 10^5.2, 10^15.3, 10^2.7 and 10^11.8 respectively (μ = 0.1, temp. 40°C).     

Tetraalkylphosphonium Ionic Liquid Encapsulation in Alginate Beads for Cd(II) Sorption from HCl Solutions

Cyphos IL 105 (tetraalkylphosphonium dicyanamide) was immobilized in alginate capsules (IL vesicle entrapped in a biopolymer layer, as shown by SEM-EDX analysis). This material was tested for efficient Cd(II) sorption from HCl solutions. The concentration of HCl and chloride ions hardly influenced metal sorption that proceeds through ion exchange between Cd(II) (under the form of CdCl₄^2?) and 2 dicyanamide groups. The sorption capacity (at saturation of the resin) proportionally increased with IL content (respecting the 1:2 stoichiometry between Cd(II) and the phosphonium cation). The uptake kinetics are well described by the Crank’s equation (resistance to intraparticle diffusion) and by the pseudo-second order rate equation (chemical reaction rate).     

Removal of Copper (II) and Nickel (II) Ions from Aqueous Solutions by a Composite Chitosan Biosorbent

Abstract

A composite chitosan biosorbent (CCB) was prepared by coating chitosan on to ceramic alumina. The adsorption characteristics of the sorbent for copper and nickel ions were studied under batch equilibrium and dynamic flow conditions at pH 4.0. The equilibrium adsorption data were correlated with Langmuir, Freundlich, and Redlich‐Peterson models. The ultimate monolayer capacities, obtained from Langmuir isotherm, were 86.2 and 78.1 mg/g of chitosan for Cu(II) and Ni(II), respectively. In addition, dynamic column adsorption studies were conducted to obtain breakthrough curves. After the column was saturated with metal ions, it was regenerated with 0.1 M sodium hydroxide. The regenerated column was used for a second adsorption cycle.     

Dithiooxamide-Immobilized Microalgal Residue for the Selective Recovery of Pd(II) and Pt(IV)

Microalgal residue was chemically modified by immobilizing a functional group of dithiooxamide to prepare a novel type of adsorbent. This adsorbent exhibited high adsorption affinity and selectivity for Pd(II) and Pt(IV) whereas the adsorption of coexisting base metal ions was negligible. From the adsorption isotherms, this adsorbent was found to exhibit remarkably high adsorption capacity. The thermodynamic parameters indicated that the adsorption is governed by an endothermic reaction. The effective separation of Pd(II) and Pt(IV) from Cu(II) was confirmed also by a dynamic adsorption test. The effectiveness of elution of adsorbed Pd(II) and Pt(IV) was 85% and 96%, respectively.     

Electrophoretic studies of mixed ligand complexes in solution—copper(II), nickel(II), cobalt(II), uranyl(II) and thorium(IV)—tartarate—nitrilotriacetate

Paper electrophoresis has been used for the study of the equilibria in mixed ligand complex systems in solution. The method is based on the migration of a spot of a metal ion, with the complexants added in the background electrolyte (0.1 M perchloric acid), at a fixed pH. The concentration of one of the complexants [A] is kept constant, while that of second ligand [L] is varied. A graph of—log [L] against mobility is used to obtain information on the formation of the mixed ligand complex, and to calculate the stability constant. Using this technique, the values of overall stability constant of the complex metal—tartarate—nitrilotriacetate have been found to be 10^12.25, 10^5.98, 10^?3.56, and 10^3.74 for Cu(II), Ni(II), Co(II), UO₂(II) and Th(IV) complexes, respectively at μ = 0.1 and temp. = 40°C.