Fe2+-modified Vermiculite for the Removal of Chromium (VI) from Aqueous Solution

A novel adsorbent: Fe²⁺-modified vermiculite was prepared in a two-step reaction. Adsorption experiments were carried out as a function of pH, contact time, and concentration of Cr(VI). It was found that Fe²⁺-modified vermiculite was particularly effective for the removal of Cr(VI) at pH 1.0. The adsorption of Cr(VI) reached equilibrium within 60 min, and the pseudo-second-order kinetic model best described the adsorption kinetics. The adsorption data follow the Langmuir model more than the Freundlich model. At pH 1.0, the maximum Cr(VI) sorption capacity (Q _max ) was 87.72 mg · g^?1. Desorption of Cr(VI) from Fe²⁺-modified vermiculite using NaOH treatment exhibited a higher desorption efficiency by more than 80%. The sorption mechanisms including electrostatic interaction and reduction were involved in the Cr (VI) removal. The results showed that Fe²⁺-modified vermiculite can be used as a new adsorbent for Cr(VI) removal which has a higher adsorption capacity and a faster adsorption rate.     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.     

Foam‐like polymer/clay aerogels which incorporate air bubbles

The structure/property relationships of polymer/clay aerogels interfused with uniformly distributed air bubbles were examined. Through the incorporation of a polyelectrolyte in a montmorillonite(MMT) clay solution, the viscosity was systematically changed by the addition of ions with different charges. The bubbles were achieved via high speed mixing and were stabilized through the use of the surfactant sodium dodecyl sulfate (SDS). As the charge of the ion increased from +1 (Na⁺ ions) to +2 (Ca²⁺ ions) to finally +3 (Al³⁺ ions), the modulus of the resultant aerogels increased. The foamed polymer/clay aerogels showed a reduction in thermal conductivity while retaining similar mechanical properties to unfoamed polymer/clay aerogels. The most promising composition was one which contained 5% MMT clay/5% poly(vinyl alcohol)/0.5% xanthum gum/0.5% SDS/0.2% Al₂(SO₄)₃·6(H₂O) possessing a density of 0.083 g/cm³, an average modulus of 3.0 MPa, and a thermal conductivity of 41 W/m·K. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39546.     

Zr K-edge XAS study on ZrO<Subscript>2</Subscript>-pillared aluminosilicate

The ZrO₂-pillared clay with high acidic property has been prepared by reacting 1 wt% colloidal suspension of Na⁺-montmorillonite with 1 N aqueous solution of ZrOCl₂·8H₂O and by subsequent heating. The evolution of local structure around zirconium of the intercalant stabilized in-between aluminosilicate layers upon intercalating, drying, and pillaring condition has been systematically studied by X-ray absorption spectroscopy, and compared to those of reference compounds such as ZrO₂, and ZrOCl₂ · 8H₂O and its 1 N aqueous solution. The intercalated zirconium species was identified as the Zr-tetramer, [Zr₄(OH)₁₄(H₂O)₁₀]²⁺, with an average molecular volume of 10 × 10 Å² and a thickness of 4.5 Å. Also it becomes more condensed upon drying and eventually transforms to a zirconium oxide pillar upon calcination.     

Electrokinetic and rheological properties of Na-bentonite in some electrolyte solutions

Electrokinetic and rheological properties of Na-bentonite suspensions were investigated in the presence of various electrolyte solutions including LiCl, NaCl, KCl, NH₄Cl, NaClO₄, CH₃COONa, NaNO₃, Na₂SO₄, Na₃PO₄, CuCl₂, MnCl₂, CaCl₂, BaCl₂, NiCl₂ and AlCl₃. It was found that divalent cations (Cu²⁺, Mn²⁺, Ca²⁺, Ba²⁺ and Ni²⁺) and trivalent cation (Al³⁺) were potential determining cations for the Na-bentonite suspensions. Trivalent cation, Al³⁺, changed the surface charge of Na-bentonite from negative to positive. The zeta potential measurements showed that monovalent counter-cations and mono-, di- and tri-valent anions were indifferent ions for the Na-bentonite suspensions. The plastic viscosity and the Bingham yield stress values of the Na-bentonite suspensions were also determined in the presence of electrolyte solutions.     

Synthesis and characterization of new bis(crown ether)s of Schiff base type containing recognition sites for sodium and nickel guest cations

New bis(crown ether) ligands of Schiff base type ( 2 – 4 ) containing recognition sites for sodium and nickel guest cations have been synthesized by the condensation of two equivalents of 4′-formyl-5′-hydroxy(benzo-15-crown-5) ( 1 ) with diamines, H₂N–(CH₂)_n–NH₂(n = 2–4). Homonuclear ditopic crystalline 2 : 1 (Na⁺ : ligand) complexes ( 2a – 4a , 2b – 4b ) of the ligands with NaSCN and NaClO₄ have been prepared. The NaClO₄ complexes of 3 and 4 ( 3b and 4b ) form heteronuclear tritopic crystalline complexes with Ni²⁺ cations of stoichiometry 2 : 1 : 1 (Na⁺ : Ni²⁺ : ligand). A homonuclear monotopic Ni²⁺ complex has also been prepared by the reaction with Ni(CH₃COO)₂ · 6H_2O. The UV-VIS spectra of 2 – 4 and their NaClO₄ complexes ( 2b – 4b ) are studied in different solvents including acidic and basic media. In polar solvents, tautomeric equilibria (phenol–imine, O–H…︁N and ketoamine, O…︁H–N forms) are present, as supported by the UV-VIS data.     

Removal of Cr(VI) From Aqueous Solution by Turkish Vermiculite: Equilibrium,Thermodynamic and Kinetic Studies

Abstract

The adsorption of Cr(VI) from aqueous solution by Turkish vermiculite were investigated in terms of equilibrium, kinetics, and thermodynamics. Experimental parameters affecting the removal process such as pH of solution, adsorbent dosage, contact time, and temperature were studied. Equilibrium adsorption data were evaluated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Langmuir model fitted the equilibrium data better than the Freundlich model. The monolayer adsorption capacity of Turkish vermiculite for Cr(VI) was found to be 87.7 mg/g at pH 1.5, 10 g/L adsorbent dosage and 20°C. The mean free energy of adsorption (5.9 kJ/mol) obtained from the D–R isotherm indicated that the type of sorption was essentially physical. The calculated thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) showed that the removal of Cr(VI) ions from aqueous solution by the vermiculite was feasible, spontaneous and exothermic at 20–50°C. Equilibrium data were also tested using the adsorption kinetic models and the results showed that the adsorption processes of Cr(VI) onto Turkish vermiculite followed well pseudo-second order kinetics.     

Chemical Processes During Energy‐Saving Preparation of Lightweight Ceramics

Lightweight glass‐ceramic material similar to foam glass was obtained at 700°C–800°C directly from alkali‐activated silica clay and zeolitized tuff without preliminary glass preparation. It was characterized by low bulk density of 100–250 kg/m³ and high pore size homogeneity. Chemical processes occurring in alkali‐activated silica clay and zeolitized tuff were studied using X‐ray diffraction, thermal gravimetry, IR‐spectroscopy, and scanning electron microscopy. Pore formation in both compositions is caused by dehydration of hydrated sodium polysilicates (Na₂O·mSiO₂·nH₂O), formed during alkali activation. Additional pore‐forming gas source in alkali‐activated zeolitized tuff is trona, Na₃(CO₃)(HCO₃)·2H₂O, formed during interaction between unbound NaOH and CO₂ and H₂O from air. Influence of mechanical activation of raw materials on chemical processes occurring in alkaline compositions was also studied.     

Dissolution mechanism of colemanite in sulphuric acid solutions

Boron compounds are very important raw materials in many branches of industry and their uses have been increasing and expanding continuously. Colemanite, one of the most common boron minerals, has a monoclinic crystal structure with a chemical formula of 2CaO·3B₂O₃·5H₂O and is used usually in the production of boric acid. The present study concerns and investigation of the dissolution mechanism of colemanite in H₂SO₄ solution and the effect of acid concentration, the effect of SO₄⁻² ion on the dissolution process, using H₂SO₄, HCI+H₂SO₄ and H₂SO₄+Na₂SO₄ solutions. The analysis of the experimental data shows that increasing H₃O⁺ acid concentration increased the dissolution rate, but increasing SO₄⁻² concentration reduced dissolution rate because of the precipitation of a solid film of CaSO₄ and CaSO₄·H₂O.     

Structural-microstructural characterization and optical properties of Eu3+,Tb3+-codoped LaPO4·nH2O and LaPO4 nanorods hydrothermally synthesized with microwaves

Rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·nH₂O single-crystal nanorods with the compositions La_0.99999-xEu_xTb_0.00001PO₄·nH₂O (x?=?0–0.03), La_0.99999-yTb_yEu_0.00001PO₄·n′H₂O (y?=?0–0.010), and La_0.99999-zTb_zEu_0.000007PO₄·n′′H₂O (z?=?0–0.012) were hydrothermally synthesized with microwaves. It is shown that the Eu³⁺,Tb³⁺ codoping does not affect the thermal stability of these nanorods, which is due to the formation of substitutional solid solutions with both Eu³⁺ and Tb³⁺ replacing La³⁺ in the crystal lattice. Moreover, it is also shown that monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ single-crystal nanorods can be obtained by calcining their rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·(n,n′ or n′′)H₂O counterparts at moderate temperature in air, and that they are thermally stable. It is also observed that, for the same Eu³⁺,Tb³⁺-codoping content, the monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ nanorods exhibit higher photoluminescent efficiency than the rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄· (n,n′ or n′′)H₂O nanorods. Moreover, it is found that the highest photoluminescence emission corresponds to the monazite-type La_0.96999Eu_0.02Tb_0.00001PO₄ nanorods for the La_0.99999-xEu_xTb_0.00001PO₄ system. However, for those compositions energy transfer from Tb³⁺ to Eu³⁺ does not occur. In addition, for an efficient energy transfer to occur, a content of at least 1?mol% Tb³⁺ is needed in all the studied materials.     

Characteristics of thin-film nanofiltration membranes at various pH-values

Salt rejection and ion selectivity of NF-255 and NF-45 nanofiltration (NF) membranes were investigated. The rejection of two cations (Na⁺, Ca²⁺) and two anions (Cl⁻, SO_4²⁻) which are common in natural and in industrial wastewater, were studied as a function of pH at permanent pressure and temperature. The ion rejection of NF membranes were investigated in single salt solutions like NaCl, CaCl₂, Na₂SO₄, CaSO₄, and in multicomponent systems that contained all the previous ions. We found that, there is a minimum rejection of the Na⁺ and Cl⁻ ions between pH 4-5 in NF-255 and between pH 7-8 in NF-45. The rejection of calcium ions were increased in each case at lower pH in both membranes. However the pH value where the ion rejection behaviour of membranes changed, were different: pH 4 in NF-255 and pH 8 in NF-45. In NF-45 the chloride ion has negative rejection which depends on the quality of ions and the pH. We found that below pH values of 4 the selectivity of mono- and multivalent cations considerable increased in NF-255. This phenomena may be used for separation of calcium ions from sodium ions from weakly acidic (hydrochloric and sulfuric acid) solution, e.g. regeneration solution of sodium form softening ion exchangers.     

Effects of some plating variables on the electrodeposition of catalytically active nickel-thallium alloy powders

The electrodeposition of nickel-thallium alloy powders was investigated from a selected bath of the composition 0.0125 NiSO₄·6H₂O, 0.01 TICI, 0.10 (NH₄)₂SO₄, 0.10 H₃BO₃ and 0.07 Na₂SO₄·10 H₂O (mol dm^?3). The effects of the pH of the bath, deposition current density and deposition time on the cathodic polarisation, current efficiency and composition of the electrodeposited alloy were determined. The properties of the electrodeposits examined, as a function of the above-mentioned variables, were surface morphology and catalytic activity towards the decomposition of 0.4% H₂O₂ solution. It was found from this investigation that the operating variables influence to a great extent the current efficiency, composition and surface morphology of the electrodeposited alloys; and the catalytic activity is primarily controlled by the surface morphology.     

Ferrous-Ferric Ratio and CEC Changes on Deferration of Weathered Micaceous Vermiculite

Ferrous iron in the layers increased 2-fold or more on deferration of coarser fractions of micaceous vermiculite naturally weathered from biotite (Colorado and Transvaal sources). The ferric iron content of the layers was decreased by the deferration treatment but the original content was restored by subsequent H₂O₂ treatment. Sesquioxide coatings on micaceous vermiculite from Colorado, examined electron microscopically, were composed predominantly of Fe₂O₃ (80 to 85 percent), along with Al₂O₂ and SiO₂. The CEC increased from 64 to 95 meq per 100 g in the fraction coarser than 1000 microns and 50 to 64 meq per 100 g in the fraction 2–0.2, microns in diameter, as a result of removal by deferration of positively charged sesquioxide coating which had originally blocked a portion of the CEC. Although treatment with H₂O₂ after deferration restored the Fe³⁺ content to approximately the original value, the CEC was not affected probably because of deprotonation OH^? → O^2? + H⁺ occurring simultaneous with Fe²⁺ → Fe³⁺.     

Electrochemical preparation of cuprous oxide powder: Part I. Basic electrochemistry

The preferred process for the production of cuprous oxide powder is via the anodic dissolution of copper in alkaline solution of sodium chloride. The principal reactions are as follows: $$\begin{gathered} Cu + nCl^ - = CuCl_n^{1 - n} (n = 2, 3) \hfill \\ 2H_2 O + 2e = H_2 \uparrow + 2OH^ - \hfill \\ 2CuCl_n^{1 - n} + 2OH^ - = Cu_2 O \downarrow + 2nCl^ - + H_2 O \hfill \\ \end{gathered} $$ In the present investigation the basic electrode processes were studied systematically under a broad range of conditions using linear sweep voltammetry. Variables studied include the concentration of sodium chloride and sodium hydroxide (i.e., alkalinity), temperature of the solution, two categories of additives (an inhibitor for preventing the deposition of spongy metallic copper powder on the cathodes, and a chemical reducing agent for reducing the cupric ions to the cuprous state), and the effect of carbonate ions (resulting from the spontaneous absorption of carbon dioxide from the air by sodium hydroxide). Useful guidelines concerning the electrolysis conditions, additives, and the concentration limit of carbonate ions have been established. The proper operating conditions can be considered to be as follows: 80–85°C, NaCl 240–260 gl^?1, NaOH below 1 gl^?1. Conditions pertaining to the use of additives are the following: calcium gluconate 0–5 gl^?1, Na₂CrO₄ below 0.5 gl^?1, Na₂Cr₂O₇ below 0.25 gl^?1, NH₂OH·HCl below 2.5 gl^?1, N₂H₄·H₂O below 2.5 gl^?1, sucrose 0–5 gl^?1. Special attention must be given to eliminate or reduce the presence of carbonate ions in the electrolyte below 0.25 gl^?1 Na₂CO₃.     

复合法制备高膨胀率膨胀蛭石

对蛭石样品采用新型的化学-热处理法制备膨胀蛭石,并对制备的膨胀蛭石样品进行形貌、XRD、DSC分析.结果表明:复合法制备的膨胀蛭石层与层之间分离的较为彻底,气孔壁薄,效果明显优于高温膨胀蛭石;双氧水在蛭石层间分解释放氧气撑开蛭石层间未引起蛭石结构的变化,膨胀蛭石结构破坏时的温度与蛭石原矿一致,不影响蛭石的热性能,复合法制备的膨胀蛭石在高温条件下结构破坏后不会形成新物相.     

First two-dimensional framework material constructed from bicapped Keggin structure clusters: [Cu(en)2(H2O)]{[PMoVI8VIV6O42Cu(en)2][Cu0.5(en)]3} · 5.5H2O

The hydrothermal reaction of CuCl₂ · 2H₂O, Na₂MoO₄ · 2H₂O, NH₄VO₃, ethylenediamine (en) and H₃PO₄ yields a novel two-dimensional open-framework material. The extended structure consists of a network of {PMo₈V₆O₄₂ [Cu(en)₂]}⁵⁻ cages, with each cage connected to three other neighboring units via [Cu(en)₂]²⁺ bridging groups.     

Divalent metal complexes of formylhydrazine: Syntheses and crystal structures of M(CH4N2O)2(H2O)2·2NO3 (M = Zn,Co)

The syntheses and crystal structures of Zn(CH₄N₂O)₂(H₂O)₂·2(NO₃) (1) and Co(CH₄N₂O)₂(H₂O)₂·2(NO₃) (2), the first well-characterised metal complexes of formylhydrazine (fh), are described. In both compounds, the fh acts as an N,O-bidentate ligand in a centrosymmetric [M(fh)₂(H₂O)₂]²⁺ cation, with charge balance supplied by nitrate counter ions. The packing for the two compounds are quite different: in 1, chains of [Zn(fh)₂(H₂O)₂]²⁺ units are seen in the triclinic unit cell, whereas in the monoclinic structure of 2, sheets of cations occur. This might arise because the conformations of the five-membered chelate rings for the ligands are slightly different, with that for 2 showing a greater degree of puckering.     

Appraisal of microwave-assisted ion-exchange in mordenite by crystal structure analysis

Transition metal-containing mordenite have been prepared by solid state ion exchange with microwave irradiation of mechanical mixtures of CoCl₂·6H₂O, NiCl₂·6H₂O and CuCl₂·2H₂O with mordenite at 750?W microwave power and for 10?C20?min treatment time. The prepared transition metal-mordenite were characterized by X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FT-IR), simultaneous TG and DTA thermal analyses (TG/DTA), surface area measurement (BET), and diffuse reflectance spectroscopy (DRS). The results show that Co²⁺, Ni²⁺, and Cu²⁺ metal ions are actually incorporated into mordenite pores. The extra-framework locations of metal cations were determined Rietveld refinement of XRD data, performed in the Cmcm space group for all three samples. Three metal sites were located: the first site is in an almost perfect boat-shaped coordination with framework oxygen??s, the second site is poorly coordinated while the third metal cation site was found at the center of mordenite cage in six-fold coordination to water molecules.     

Synthesis and microstructure of single-crystalline cobalt oxyhydroxide and topotactic transformation to cobalt oxide

Plate-like cobalt oxyhydroxide (β-CoOOH, heterogenite) single crystals, with a width of ~5 mm and a thickness of ~100 μm, were successfully synthesized using a simple method of heating a mixture of Co₃O₄ and NaOH in air at 650°C, and then soaking the resultant crystals in water at room temperature. The crystals were topotactically formed from sodium cobalt oxyhydrate (Na_0.2(H₃O)_0.54CoO₂·0.48H₂O) by ion exchange between Na⁺ and H₃O⁺, and by intercalation of water molecules in the as-grown NaCoO₂ crystals. The sodium cobalt oxyhydroxide crystals had spherical nanopores with diameters of ~5 nm.     

Characterization of acidic pumice and determination of its electrokinetic properties in water

In this study some characterization tests of acidic pumice were performed using various techniques such as Mercury Intrusion Porosimetry (MIP), Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Thermal Analysis (DTA–TG), FTIR and its electrokinetic properties in water such as zeta potential (ZP), isoelectrical point (IEP), indifferent, specifically adsorbing and potential determining ions were determined. The results showed that (i) pore dimensions of the irregular or oval and fibrous cavities of the pumice varied between 0.05 μm and 2 mm depending on its particle size and these cavities usually did not intersect each other; (ii) as the pumice particle size decreases, both total pore volume and total pore surface area significantly decrease as well; (iii) pumice maintained its thermal stability approximately up to 900 °C; (iv) pumice had a negative surface charge between pH 1.8 and 11.4; and (v) Cl^?, Br^? SO₄^2?, Na⁺, Al(OH)₂⁺ and Ca²⁺ ions were indifferent, C₁₆H₃₃(CH₃)₃N⁺, Al³⁺ and Al(OH)²⁺ cations were specifically adsorbing and, H⁺ and OH^? ions were potential determining ions for acidic pumice.