Coordination polymers, 1. Magnetic,spectral, and thermal properties of coordination polymers derived from terephthalaldehyde bis(S-benzyldithiocarbazate)

New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements. The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: $ {\rm Zn} \simeq {\rm Fe} > {\rm Co} > {\rm Ni} > {\rm Min} \simeq {\rm Cu}$ Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.     

Effect of the nature and degree of crosslinking on the catalase‐like activity of polystyrene‐supported schiff base‐metal complexes

Catalase‐like activity of the metal complexes of various crosslinked polystyrene‐supported Schiff bases were carried out and correlated with the nature and degree of crosslinking in the polymer support. Polystyrenes with 2–20 mol % ethyleneglycol dimethacrylate (EGDMA), 1,4‐butanediol dimethacrylate (BDDMA) and 1,6‐hexanediol diacrylate (HDODA) were used as polymer supports. functions of diethylenetriamine and salicylaldehyde were incorporated to the chloromethylpolystyrene by polymer analogous reactions and complexed with Fe(II), Fe(III), Co(II), Ni(II), and Cu(II) ions. The metal uptake decreased in the order: Cu(II) > Co(II) > Ni(II) > Fe(III) > Fe(II), and extent of metal uptake by the various crosslinked system varied with the nature and degree of the crosslinking agent. The polymeric ligands and the metal complexes were characterized by various analytical techniques. The catalytic activities of these metal complexes were investigated towards the decomposition reaction of hydrogen peroxide. Generally among the various metal complexes, the catalytic activities decreased in the order: Co(II) > Cu(II) > Ni(II) > Fe(III) ? Fe(II). With increasing rigidity of the crosslinking agent their catalytic activity also decreased. Of the various crosslinked systems, the catalytic activity decreased in the order: HDODA‐ > BDDMA‐ > EGDMA‐crosslinked system. Also, the catalytic activity is higher for low crosslinked systems and decreased further with increasing degree of crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1271–1278, 2004     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Adsorption Behavior of Iminodiacetic Acid Type of Chelating Gel Prepared from Waste Paper

Abstract

Adsorption gel was prepared from waste recycled paper by immobilizing iminodiacetic acid (IDA) functional group by chemical modification. The gel exhibited good adsorption behavior for a number of metal ions viz. Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. The order of selectivity was found to be as follows: Cu(II)>Pb(II)>Fe(III)>Ni(II)～Cd(II)～Co(II). From the adsorption isotherms, the maximum adsorption capacity of the gel for both Cu(II) and Pb(II) was found to be 0.47 mol/kg whereas that for Cd(II) was 0.24 mol/kg. A continuous flow experiment for Cd(II) showed that the gel can be useful for pre‐concentration and complete removal of Cd(II) from aqueous solution.     

Activated carbon sorbent with thioetheric sites—preparation and characterization

An activated carbon sorbent containing thioetheric sites (ACTS) was prepared by modification of the activated carbon with 2,2′-thiodiethanol. The specific surface area, pore volume, concentration of oxygen-containing groups and sulfur content of the sorbent were determined. The sorption behavior towards ions of some precious metals—Au(III), Pt(IV), Pd(II) and heavy metals—Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II) was studied. Selectivity towards gold, palladium and platinum in the pH range 1–9 was observed. The capacity for gold was 80 mg g⁻¹. The sorption of Au(III) at pH 1 is not affected by milligram amounts of Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II). The sorbed gold species is Au(0).     

Cationic Mobility Via Cation-Exchange Mechanism on Poly(8-Hydroxyquinoline) Matrix

The insertion of Al(III) cation into a poly(8-Hydroxyquinoline) (PHQ) instead of some metal ions such as Co(II), Ni(II), Zn(II) or Fe(III) ions via cation-exchange mechanism has been studied by several techniques. The presence of Al(III) and the absence of Co(II) cations has been proved by elemental analysis of the polymer chelates product. Molecular mechanics (MM+) calculations showed that the potential energy (PE, kJ mol⁻¹) of the optimum molecular geometric structure (OMG) of the PHQ–Al(III) matrix is about seventy-six (76.185) greater than the PE of the PHQ–Co(II) complex. The TGA thermograms show that the PHQ–Al(III) matrix is thermally unstable than the PHQ–Co(II) complex under the same conditions. These observations indicate that the PHQ–Al(III) is expanded coil-like form. So, the thermal decomposition of PHQ–Al(III) complex is easy than the compacted coil-likes form of PHQ–Co(II) complex. The incorporation of Al(III) ion via cation-exchange properties have been investigated by spectrophotometric technique. The decrease of the absorbance at about ~370 nm of PHQ–Co(II) complex associated with increasing concentration of Al(III) revealed the replacement of that metal ion by Al(III) into PHQ chain. The cation-exchange constant (K _ex) of the divalent ions [Ni(II), Co(II), Cr(II), Zn(II), Mn(II), Mg(II) and Cu(II)] from PHQ–M(II) by the additions of Al(III) according to the following series: Ni(II) > Co(II) > Cr(II) > Cu(II) > Zn(II) > Mn(II) > Mg(II).     

Evaluation of sorption behavior of polymethylene-bis(2-hydroxybenzaldehyde) for Cu(II), Ni(II), Fe(III), Co(II) and Cd(II) ions

Poly[5,5??-methylene-bis(2-hydroxybenzaldehyde)1,2-phenylenediimine] resin was prepared and characterized by employing elemental, thermal analysis, FTIR, and UV?Cvisible spectroscopy. The metal uptake behavior of synthesized polymer towards Cu(II), Co(II), Ni(II), Fe(III) and Cd(II) ions was investigated and optimized with respect to pH, shaking speed, and equilibration time. The sorption data of all these metal ions followed Langmuir, Freundlich, and Dubinin?CRadushkevich isotherms. The Freundlich parameters were computed 1/n?=?0.31?±?0.02, 0.3091?±?0.02, 0.3201?±?0.05, 0.368?±?0.04, and 0.23?±?0.01, A?=?3.4?±?0.03, 4.31?±?0.02, 4.683?±?0.01, 5.43?±?0.03, and 2.8?±?0.05?mmol?g^?1 for Cu(II), Co(II), Ni(II), Fe(III), and Cd(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantity (??H) in the range of 36.72?C53.21?kJ/mol. Using kinetic equations (Morris?CWeber and Lagergren equations), values of intraparticle transport and the first-order rate constant was computed for all the five metals ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination by atomic absorption spectrometer. It was found that the adsorption capacity values for metal-ion intake followed the following order: Cd(II)?>?Co(II)?>?Fe(III)?>?Ni(II)?>?Cu(II).     

Metal sorption on macroporous poly(GMA-co-EGDMA) modified with ethylene diamine

Two samples of macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), with different porosity parameters were synthesized by suspension copolymerization and modified by ring-opening reaction of the pendant epoxy groups with ethylene diamine (EDA). The samples were characterized by mercury porosimetry, FT-IR spectroscopy and elemental analysis. The sorption rate of the modified copolymer, poly(GMA-co-EGDMA)-en for Cu(II) ions determined under non-competitive conditions was relatively rapid, i.e. the maximum capacity was reached within 30 min. Batch sorption capacities for Cu(II), Fe(II), Mn(II), Cd(II), Zn(II), Pb(II), Cr(III) and Pt(IV) ions were determined under non-competitive conditions in the pH range 1.25–5.5 at room temperature. The maximum sorption capacities of poly(GMA-co-EGDMA)-en under non-competitive conditions were 1.30 mmol/g for Pt(IV) at pH 5.5, 1.10 mmol/g for Cu(II) at pH 5.5, 1.06 mmol/g for Pb(II) at pH 1.25 and 0.67 mmol/g for Cd(II) ions at pH 5.5. The selectivity of poly(GMA-co-EGDMA)-en towards Cu(II), Co(II), Ni(II), Pb(II) and Pt(IV) ions was investigated under competitive conditions. Poly(GMA-co-EGDMA)-en showed high selectivity for Pt(IV) over Cu(II), Co(II), Ni(II) and Pb(II) ions at pH 2.1. At pH 5.5, the metal sorption capacities of poly(GMA-co-EGDMA)-en decreased in the order: Cu(II) > Co(II) > Pt(IV) ≈ Ni(II) > Pb(II). Regeneration of the Cu(II), Ni(II) and Pb(II) loaded poly(GMA-co-EGDMA)-en with 2 M H₂SO₄ showed that the polymer can be reused in several sorption/desorption cycles.     

Spectral and electrochemical investigation of octanitro substituted metal phthalocyanines

A simple and convenient method has been developed for the synthesis of 1,3,8,10,15,17,22,24-octanitrophthalocyanine derivatives MPcON's [M = Fe(III)Cl, Zn(II), Co(II), Cu(II) and Ni(II)]. The compounds were prepared from 3,5-dinitrophthalic acid in the presence of ammonium chloride, urea and catalytic quantity of ammonium molybdate in nitrobenzene solvent; the complexes were characterized by elemental analysis, electronic and IR spectra and powder XRD. The electrochemical redox properties of the complexes were studied using glassy carbon and platinum electrodes in non-aqueous media employing tetra butyl ammonium perchlorate as supporting electrolyte.     

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) ≈ Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) can be easily achieved by varying of the metal center. In addition, mechanism speculation is also presented to elucidate the dependence of catalytic behaviors on metal and cocatalyst.     

Cation effects in the oxidative coupling of methane on phosphate catalysts

The conversion of methane and the selectivities to the various products have been measured at 700 and 775 °C on a variety of phosphates of La(III), Zr(IV), V(V), Cr(III), Mn(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), B(III), Pb(II), Bi(III) and Sm(III) in the presence and absence of carbon tetrachloride. The conversions reach as high as 30 and 49% at 700 and 775 °C, respectively, with methane and oxygen at partial pressures of 200 and 25 Torr, respectively. The highest C₂₊ selectivities (61 and 82%, respectively) were obtained for lead(II) phosphate at 700 and 775 °C, respectively. In general the conversions and C₂₊ selectivities are enhanced on addition of carbon tetrachloride (1.1 Torr) to the feedstream, although there are notable exceptions. Significantly high selectivities to formaldehyde are observed with a number of the catalysts, in particular 32% with boron(III)phosphate.     

Affinage electrolytique des ferronickels

Electrorefining of ferronickels is possible in a cell without diaphragm with the electrolyte CaCl₂ 5 M at 98°C.Behavior of the following impurities have been studied: Ag(I), Au(III), Bi(III), Cd(II), Co((II), Cu(I), Fe(II), Hg(II), Ni(II), Pb(II), Pd(II), Sb(III) and Sn(II).The electrochemical system Ni(II)/Ni(O)is much more reversible in this electrolyte and the only other electrochemical system which appears at the same potential is Cu(I)/Cu(O).Ferronickels of 23.2;72.2 and 94.4% in nickel have been refined in this medium without purification of the electrolyte. Nickel of a purity between 98.7 and 99.7% is obtained.In order to increase the nickel purity and for continuous operation of the method a purification of the electrolyte is necessary. Two methods are proposed: anion exchange resin and liquid—liquid extraction with tri-n-butyl phosphate (TBP).Partition coefficients and ion-exchanger capacities are given for following impurities: Fe(III), Fe(II), Co(II), Cu(II), Mn(II), Zn(II), Cr(III) and Pb(II).Percent extracted by TBP for following impurities are given: Fe(III), Fe(II), Co(II), Cu(II), Zn(II), Mn(II), Cr(III), Pb(II), Al(III), Bi(III), Sb(III) and Sn(IV).A continuous purification of the electrolyte by ion-exchange has been done in the refining of a ferronickel 94.4% in nickel. Nickel obtained is 99.74%.CaCl₂ 5 M appears to be a good electrolyte for electro-refining of nickel.     

Removal of Heavy Metals and Other Cations from Wastewater Using Zeolites

Abstract

Zeolites from abundant natural deposits were investigated by the Bureau of Mines for efficiently cleaning up mining industry wastewaters. Twenty-two zeolites were analyzed by X-ray diffraction and inductively coupled plasma analysis (ICP). These included clinoptilolite, mordenite, chabazite, erionite, and phillipsite. The zeolites were primarily in the sodium or calcium form, but potassium and magnesium counter ions were also present. Bulk densities of a sized fraction (minus 40, plus 65 mesh) varied from 0.48 to 0.93 g/cc. Heavy metal ion exchange loading values on two clinoptilolites ranged from 1.6 meq/g for lead to 0 meq/g for mercury in single ion tests. The selectivity series was determined to be Pb>Cd>Cs>Cu(II)>Co(II)>Cr(III)>Zn>Ni(II)>Hg(II). Sodium was the most effective exchangeable ion for ion exchange of heavy metals. Wastewater from an abandoned copper mine in Nevada was used to test the effectiveness of clinoptilolite for treating a multiion wastewater. Aluminum, Fe(III), Cu(II), and Zn in the copper mine wastewater were removed to below drinking water standards, but Mn(II) and Ni(II) were not. Calcium and NH₄ were absorbed preferentially to all heavy metal cations except Pb. Adsorbed heavy metals were eluted from zeolites with 3-pct NaCl solution. Heavy metals were concentrated in the eluates up to 30-fold relative to the waste solution. Anions were not adsorbed by the zeolites.     

Adsorption of copper(II), cobalt(II), and iron(III) ions from aqueous solutions on poly(ethylene terephthalate) fibers

The adsorption behavior of poly(ethylene terephthalate) (PET) fibers towards copper(II), cobalt(II), and iron(III) ions in aqueous solutions was studied by a batch equilibriation technique. Influence of treatment time, temperature, pH of the solution, and metal ion concentration on the adsorption were investigated. Adsorption values for metal ion intake followed the following order: Co(II) > Cu(II) > Fe(III). One hour of adsorption time was found sufficient to reach adsorption equilibrium for all the ions. The rate of adsorption was found to decrease with the increase in the temperature. Langmuir adsorption isoterm curves were found to be significant for all the ions studied. The heat of adsorption values were calculated as −5, −2.8, and −3.6 kcal/mol for Cu(II), Co(II), and Fe(III) ions, respectively. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1935–1939, 1998     

Removal of heavy metals and neutralisation of acid mine drainage with un-activated attapulgite

Unactivated attapulgite was characterised and utilised as an adsorbent for the removal of heavy metal and neutralisation of acid mine drainage (AMD) from a gold mine. Adsorption experiments were carried out by agitation of a fixed amount of attapulgite with a fixed volume of AMD in a thermostatic shaker for varying times. Attapulgite showed that it can neutralise acid mine drainage as the pH after 4 h was 7.11. The results showed that metal ion removal after 4 h was 100% for Cu(II) and Fe(II), 93% for Co(II), 95% for Ni(II) and 66% for Mn(II) using a 10% (w/v) attapulgite loading. The experimental data best fit the Langmuir Isotherm with maximum adsorption capacities for Cu(II), Co(II), Mn(II), Fe(II) and Ni(II) being 0.0053, 0.0044, 0.0019, 0.01, and 0.0053 mg/g, respectively. The adsorption process fitted well the pseudo first order kinetics for Co(II) and Cu(II) and pseudo second order for Ni(II), Mn(II) and Fe(II). Thermodynamic data show that Cu(II), Co(II), Fe(II) and Ni(II) adsorption was thermodynamically spontaneous whilst Mn(II) was not thermodynamically spontaneous. The process is endothermic for Cu(II), Co(II), Mn(II), and Ni(II) and exothermic for Fe(II). Spent attapulgite (attapulgite that has already been used to remove metals) could be reused twice without regeneration.     

Binding Properties of a Polymer Having Amidoxime Groups with Proton and Metal Ions

Abstract

The proton-binding behavior of a polymer having amidoxime groups was examined by the potentiometric titration method. Adsorptive properties of the polymer for UO₂(VI), Mg(II), Fe(II), Ni(III), Co(II), Ni(II), Cu(II), and Zn(II) were also examined at very low concentrations in the 1–9 pH range. The amidoxime polymer possesses adsorptive affinities of the following order: (Mg(II), Ca(II)) < Zn(II) < Co(II) < Ni(II) < Cu(II) < UO₂(VI). These adsorptive affinities are reasonably explained by the proton-binding and the metal ion-complexing abilities of the ligand, and are discussed from the standpoint of uranium recovery from seawater.     

Transition Metal Ion Complexation and Extraction by Hydroxamate Functionalised p-Tert-Butylcalix[4]Arenes

The functionalisation of macrocyclic p-tertbutylcalix[4]arenes at the lower rim with hydroxamic acid and proline hydroxamic acid groups gives the calixarenes chelating properties similar to siderophores. The (1)H NMR spectrum of p-tertbutylcalix[4]arene tetrahydroxamic acid shows a broad band at 10.8 ppm in DMSO-d(6) attributed to NHOH protons. Diffuse reflectance spectral analysis of PVC membranes containing the calixarene hydroxamic acids show absorption bands at 485 nm and 504 nm following contact with aqueous solutions of Fe(III) and V(V) respectively. The pH dependency of this extractive selectivity is examined for Fe(III), Co(II), Pb(II), Mn(II), Cu(II) and Ni(II) using a solid phase extraction approach. Spectrophotometric evidence for the complexation of Cu(II) in methanol by p-tertbutylcalix[4]arene tetraproline acid is also provided.     

Study of the degradation of polyurethanes. I. The effect of various metal acetylacetonates on the photodegradation of polyurethanes

Photodegradation of polyurethanes based on polyester diol-diphenylmethane-p,′p-diisocyanate in the absence and presence of various metal acetylacetonates (Ti, V, Cr, Mn, Co(II), Co(III), Fe, Ni, Cu, Zn, Mg, Al, and Sn) was carried out; and the effect of these metal compounds on the degradation was examined by investigating the changes in the stress–strain properties and infrared- and ultraviolet-visible spectra of the polymer. The results obtained were as follows: Co(III), Co(II), Cu, Ti, and Sn acetylacetonates substantially enhanced the photo-oxidation of the polyurethane; and Al, Ni, and Zn acetylacetonates scarcely affected, or slightly retarded, it. The other metal acetylacetonates accelerated more or less the photo-oxidation of the polymer. Co(III), Co(II), and Cu acetylacetonates extremely degradation. Wavelength of the irradiated light was responsive to photochemical reactions of functional groups in the polymer. C? N and C? O bonds of urethane groups were very accessible to the photo-irradiation both without and with a glass filter, while methylene groups were rather stable to the irradiated light longer than 300 nm, through a glass filter. The effect of the metal compounds on the coloration of the polymer was also consistent with that of mechanical strength and infrared spectral changes.     

Electrochemical copper (II) sensor based on chitosan covered gold nanoparticles

This study outlines a new sensing platform based on glassy carbon electrodes modified by gold nanoparticles (AuNPs) for the determination of heavy metal. A glassy carbon electrode was modified by chitosan stabilized AuNPs. AuNPs were prepared by reducing gold salt with a polysaccharide chitosan. Here, chitosan acted as a reducing/stabilizing agent. The AuNPs were characterized with UV–Visible absorption spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Chitosan covered AuNPs were immobilized on the glassy carbon electrode for the determination of Cu (II) in aqueous solutions. The electrochemical determination of Cu (II) ions was performed using the differential pulse voltammetry technique. Some parameters for Cu (II) determination, such as pH, preconcentration time and electrolysis potential of Cu (II), were optimized. The detection limit was calculated as 5 × 10^?9 mol L^?1 by means of the 3:1 current-to-noise ratio. The interference of Cr(III), Fe(II), Ni(II), Pb(II), Mg(II), Zn(II), Ba(II) ions was investigated and showed a negligible effect on the electrode response. Recovery studies were carried out using tap water.     

Synthesis and properties of hydrophilic polymers. IX. Synthesis,biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

The synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) with pendant carboxylic groups of high molar mass (132 kg mol^?1) is described. The polycondensate was hydrolytically and microbiologically degradable with conventional microbiological methods. The metal‐complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution with the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by thermogravimetric analysis to be 182 mg g^?1 of polymer. According to the retention profiles determined as a function of the filtration factor with LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, as indicated by retention values of about 100% at pH 5. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 650–657, 2003