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1.
The possibility of selective extraction and multiple concentration of copper in the form of ultrafine precipitate from dilute Cu2+-Zn2+ solutions by using a suitable sorbent and an effective mode of its regeneration was demonstrated. The extraction was performed in the dynamic mode in column-type reactors filled with an aminoanionite as a selective complexing sorbent, the regeneration of which was conducted by chemical reduction of Cu2+ in the ionite after its saturation. It was established that saturation-reduction cycles repeated many times result in the accumulation of metallic copper at the surface and in the bulk of the sorbent. The mechanism of the process includes the formation of complexes of copper and zinc with amino groups of the ionite and the subsequent displacement of Zn2+ ions from the anionite due to its higher affinity to Cu2+ ions followed by the conversion of Cu2+ ions to an unsorbable form (dispersed metallic copper). It was demonstrated that the presence of dispersed copper stimulates the additional sorption of Cu2+ ions via redox conproportionation. This method makes it possible to obtain a degree of concentration of copper ions in three cycles >300% higher than that attainable in the purely ion-exchange mode (without chemical reduction).  相似文献   

2.
The sorption of molybdenum(VI) by KU-2 × 8 and AV-17 × 8 ionites from solutions in hydrochloric acid (1 × 10−5−6 N) was studied. Changes in the sorption of molybdenum(VI) by cationite and anionite were observed. The isoelectric point of molybdenum in solutions in hydrochloric acid was determined from sorption and electrical migration measurements.  相似文献   

3.
The sorption of copper cations by the complex-forming AM-7 anionite was studied. It was shown that the sorption of copper ions from aqueous solutions was satisfactorily described by the Langmuir equation. The linear approximation to this equation can be used to determine the maximum sorption capacity of the complex-forming anionite. Two independent methods for the determination of the characteristics of the ionite complex (the sorption capacity, stability constant, and coordination number) were considered: the determination of the stability constant from the distribution coefficient and from the data on the destruction of ammonia copper complexes brought in contact with the deprotonated ionite form. In both cases, the calculated stability constants of ionite complexes and the coordination numbers are in satisfactory agreement.  相似文献   

4.
Poly(hydroxamic acid) ligand was synthesized using ester functionalities of cellulose‐graft‐poly(methyl acrylate) copolymer, and products are characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, high‐resolution transmission electron microscopy, and X‐ray photoelectron spectroscopy analysis. The poly(hydroxamic acid) ligand was utilized for the sensing and removal of transition metal ions form aqueous solutions. The solution pH is found a key factor for the optical detection of metal ions, and the reflectance spectra of the [Cu‐ligand]n+ complex were observed to be the highest absorbance 99.5% at pH 6. With the increase of Cu2+ ion concentration, the reflectance spectra were increased, and a broad peak at 705 nm indicated that the charge transfer (π‐π transition) complex was formed. The adsorption capacity with copper was found to be superior, 320 mg g?1, and adsorption capacities for other transition metal ions were also found to be good such as Fe3+, Mn2+, Co3+, Cr3+, Ni2+, and Zn2+ were 255, 260, 300, 280, 233, and 223 mg g?1, respectively, at pH 6. The experimental data show that all metal ions fitted well with the pseudo‐second‐order rate equation. The sorption results of the transition metal ions onto ligand were well fitted with Langmuir isotherm model (R2 > 0.98), which implies the homogenous and monolayer character of poly(hydroxamic acid) ligand surface. Eleven cycles sorption/desorption process were applied to verify the reusability of this adsorbent. The investigation of sorption and extraction efficiency in each cycle indicated that this new type of adsorbent can be recycled in many cycles with no significant loss in its original detection and removal capability. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

5.
In this work, a series of batch experiments were carried out to investigate the effect of various environmental factors such as contact time, pH, ionic strength, coexisting electrolyte ions, humic substances and temperature on the sorption behavior of illite towards 64Cu(II). The results indicated that 64Cu(II) sorption on illite achieved equilibrium quickly. The pH- and ionic strength-dependent sorption suggested that 64Cu(II) sorption on illite was dominated by ion exchange or outer-sphere surface complexation at pH < 7, whereas the pH-dependent and ionic strength-independent sorption indicated that the sorption process was mainly attributed to inner-sphere surface complexation at pH > 7. A positive effect of humic substances on 64Cu(II) sorption was found at pH < 6.5, whereas a negative effect was observed at pH > 6.5. The Langmuir and Freundlich models were used to simulate the sorption isotherms of 64Cu(II) at three different temperatures of 293, 313, and 333 K. The thermodynamic parameters (ΔH 0, ΔS 0, and ΔG 0) of 64Cu(II) sorption on illite were calculated from the temperature dependent sorption isotherms, and the results indicated that the sorption of 64Cu(II) on illite was endothermic and spontaneous. From the experimental results, it is possible to conclude that illite has good potentialities for cost-effective treatments of 64Cu(II)-contaminated wastewaters.  相似文献   

6.

Abstract  

A new one-dimensional polymeric copper(I)–thiocyanate complex with the Schiff base ligand N,N′-bis(3,4-dimethoxybenzylidene)butane-1,4-diamine, {Cu2((μ N,N′ -3,4-MeO-ba)2bn)(μ1,3-NCS)2} n , was synthesized and characterized by elemental analysis, 1H and 13C NMR, FT–IR spectroscopy, and thermal analysis. The thermal behavior of the complex was studied using thermogravimetry in order to evaluate thermal stability and thermal decomposition pathways. The molecular structure of the complex was determined by single-crystal X-ray diffraction which revealed that the coordination geometry around the copper(I) ion is distorted trigonal. The Schiff base ligand (3,4-MeO-ba)2bn acts as a bis-monodentate and bridging ligand (μ N,N′ ) and coordinates via two N atoms to the metal centers and adopts an E,E conformation. The coordination spheres of the metal atoms are completed by the N and S atoms from two thiocyanate anion bridges (μ1,3-NCS), forming a zigzag chain propagating along [001].  相似文献   

7.
The interaction between the Co sulfide coating formed on a glassy carbon electrode and Cu(I)-ammonia complexes solution was investigated by cyclic voltammetry in 0.1 M KClO4, 0.1 M NaOH and 0.05 M H2SO4 solutions. It was determined that, after treating the cobalt sulfide coating formed by two deposition cycles with Cu(I)-ammonia complexes (0.4 M, pH 8.8–9.0, τ=180 s, T=25±1°C), an exchange occurs between the coating components and Cu(I). Copper(I) substitutes 75% of the Co(III) compounds present in the coating (~1.81×10–7 mol cm–2) because of Cu2O (1.36×10–7 mol cm–2) formation. The rest of the Co(II) and Co(III) sulfide compounds are also replaced by copper with formation of Cu2– x S with a stoichiometric coefficient close to 2 (~1.9). After modifying the cobalt sulfide coatings with Cu(I) ions, the total amount of metal (Co+Cu) increases, owing to the sorption of Cu(I) compounds. In addition, the number of deposition cycles decreases from 3 to 1.5 [1 cycle involves cobalt sulfide layer formation and 0.5 cycle is attributed to modifying by Cu(I) ions]. The coatings modified in the above-mentioned manner may be successfully used for plastic electrochemical metallization as Cu2– x S coatings formed by three deposition cycles. Electronic Publication  相似文献   

8.
A theoretical investigation at the density functional theory level (B3LYP) has been conducted to elucidate the impact of ligand basicity on the binding interactions between ethylene and copper(I) ions in [Cu(η 2-C2H4)]+ and a series of [Cu(L)(η 2-C2H4)]+ complexes, where L = substituted 1,10-phenanthroline ligands. Molecular orbital analysis shows that binding in [Cu(η 2-C2H4)]+ primarily involves interaction between the filled ethylene π-bonding orbital and the empty Cu(4s) and Cu(4p) orbitals, with less interaction observed between the low energy Cu(3d) orbitals and the empty ethylene π*-orbital. The presence of electron-donating ligands in the [Cu(L)(η 2-C2H4)]+ complexes destabilizes the predominantly Cu(3d)-character filled frontier orbital of the [Cu(L)]+ fragment, promoting better overlap with the vacant ethylene π*-orbital and increasing Cu → ethylene π-backbonding. Moreover, the energy of the filled [Cu(L)]+ frontier orbital and mixing with the ethylene π*-orbital increase with increasing pK a of the 1,10-phenanthroline ligand. Natural bond orbital analysis reveals an increase in Cu → ethylene electron donation with addition of ligands to [Cu(η 2-C2H4)]+ and an increase in backbonding with increasing ligand pK a in the [Cu(L)(η 2-C2H4)]+ complexes. Energy decomposition analysis (ALMO-EDA) calculations show that, while Cu → ethylene charge transfer (CT) increases with more basic ligands, ethylene → Cu CT and non-CT frozen density and polarization effects become less favorable, yielding little change in copper(I)–ethylene binding energy with ligand pK a. ALMO-EDA calculations on related [Cu(L)(NCCH3)]+ complexes and calculated free energy changes for the displacement of acetonitrile by ethylene reveal a direct correlation between increasing ligand pK a and the favorability of ethylene binding, consistent with experimental observations.  相似文献   

9.
Protolytic equilibria and complexation of N-(2-carboxyethyl)anthranilic acid (H2CEAnt) with copper(II) ions in aqueous solutions were studied by UV spectroscopy and pH potentiometry. The H2CEAnt compound has no zwitterionic structure, and the protons are localized on the carboxy groups. The acid ionization constants of H3CEAnt+ (T = 25 °C, I = 0.1 M KNO3) are pK 0 = 1.3±0.2 (=NH2 +), pK 1 = 3.88±0.02 (Alk-COOH), and pK 2 = 5.28±0.02 (Ar-COOH). The model of complexation of H2CEAnt with copper(II) ions involves two deprotonated complexes [Cu(CEAnt)] and [Cu(CEAnt)2]2− (logβ = 6.31±0.04 and 8.0±0.2, respectively). The [Cu(CEAnt)(H2O)]⋅H2O complex was synthesized by the reaction of H2CEAnt with (CuOH)2CO3, and its structure was established by X-ray diffraction. The coordination polyhedron of Cu is intermediate between the tetragonal pyramid and trigonal bipyramid. The CEAnt2− ligand serves as a tetradentate chelating bridging ligand (Cu-O, 1.944(3) and 1.950(3) Å; Cu-O', 2.195(4) Å; Cu-N, 2.016(5) Å), and the fifth position of the polyhedron is occupied by a water molecule (Cu-Ow, 1.976(4) Å). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1518–1523, July, 2005.  相似文献   

10.
Three macrocyclic ligands and their complexes with copper(II) salts (with anions Cl, NO 3 , and NCS) were prepared and investigated using a combination of microanalytical analysis, melting point, molar conductance measurement, magnetic susceptibility measurement, and electronic, IR and ESR spectral studies. Ligands L1, L2, and L3 having N4, N4O2, and N4S2 core, respectively, and all the donor atoms of these ligands are bonded with Cu, which is confirmed by a seven-line pattern observed at half-field in the frozen (H2O: MeOH = 10: 1 at pH 10) solution ESR spectrum. The polycrystalline ESR data (g = 2.20–2.27, g = 2.01–2.05, and A = 120–270) of all the complexes together with the high asymmetry geometry suggest that all complexes appear to be near the static distortion (CuN4O2 and CuN4S2 chromophore geometry). The electronic spectra of the complexes involve two bands at the same intensity corresponding to a cis-distorted octahedral geometry. A common structural feature of both ligand L2 and ligand L3 is that two different donor atoms at five-membered heterocyclic aromatic ring due to this N4O2 and N4S2 chromophore form stable six-membered chelate rings with metals via these two, Cu-O and Cu-S, new interactions comparatively to the first macrocyclic ligand, which has four-membered N,N′-chelate rings. The cyclic voltammetric studies point to a two-step electron transfer indicating the reduction of the two copper atoms to copper(I), i.e., Cu(III)Cu(II) ⇄ Cu(II)Cu(I) ⇄ Cu(I)Cu(0). The molar conductance for the complexes corresponds to 1: 2 and is nonelectrolyte in nature. The magnetic moment (μeff) of the complexes lie in the range between 1.80–1.96 μB. Finally, these complexes were screened for their antimicrobial activity against Aspergillus-niger of fungal strains. The text was submitted by the authors in English.  相似文献   

11.
N-(3-Hydroxypropyl)-β-alanine was synthesized by the reacti on of 3-aminopropanol with acrylic acid. From this ligand and basic copper carbonate, bis(N-(3-hydroxypropyl)-β-alaninato)dicopper(II) [Cu2 (C6H11NO3)2] was obtained. The structures of the chelating agent and the copper complex were studied by X-ray diffraction. The Cu(II) coordination polyhedron is a distorted square pyramid. Each ligand forms six-membered β-alaninate and propanolamine chelate rings. The propoxy group functions as a bridge. In the crystal structure, the molecules form intermolecular coordination bonds C=O→Cu, which are perpendicular to the layers. The EPR signal typical of dimeric copper complexes is not observed due to low occupancy of the excited paramagnetic triplet state. The weak paramagnetic signal from monomeric copper complex allowed recording of the 1H NMR spectrum of [Cu2 (Pro-ala) 2] with characteristic line broadening and contact shift. It follows from the obtained data that on dissolution, the complex dissociates by 40% to give monomeric copper complexes.  相似文献   

12.
Alginate beads (ABs) immobilized with hydrous zirconium oxide (ZO) were used as a hybrid adsorbent (ZO@AB) for the effective removal of copper ions [Cu(II)] from aqueous phase. ZO@AB was characterized using X‐ray photoelectron spectroscopy to confirm the impregnation of ABs with ZO and the adsorption of Cu(II) onto ZO@AB. The maximum equilibrium sorption capacity of ZO@AB for Cu(II) was 63.1 mg·g−1 at pH 5. The Cu(II) removal rate was high at the beginning of reaction, with >90% adsorption within 24 hours, and equilibrium was achieved within 48 hours. The adsorption of Cu(II) onto ZO@AB was well described by pseudo‐second‐order kinetic model (R2 > 0.99), and the monolayer nature of sorption was supported by the Langmuir model (R2 > 0.99). The sorption process was endothermic, favorable, and spontaneous in nature. Regarding the reusability of the adsorbent, its sorption capacity remained satisfactory (>90%) throughout the 5 consecutive cycles (regeneration in 0.1 mol·L−1 HCl). The stoichiometric ratio of released calcium ions [Ca(II)] to adsorbed copper ions [Cu(II)] was approximately 1:1, confirming that ion exchange was the main mechanism for removal of Cu(II) from aqueous phase. The developed adsorbent (ZO@AB) shows promise as a candidate for the effective and selective removal of Cu(II) from aqueous phase.  相似文献   

13.
The dinuclear copper complex (α-cyano-4-hydroxycinnamic acid (CHCA) copper salt (CHCA)4Cu2), synthesized by reacting CHCA with copper oxide (CuO), yields increased abundances of [M + xCu − (x−1)H]+ (x = 1–6) ions when used as a matrix for matrix-assisted laser desorption ionization (355 nm Nd:YAG laser). The yield of [M + xCu − (x−1)H]+ (x = 1∼6) ion is much greater than that obtained by mixing peptides with copper salts or directly depositing peptides onto oxidized copper surfaces. The increased ion yields for [M + xCu − (x−1)H]+ facilitate studies of biologically important copper binding peptides. For example, using this matrix we have investigated site-specific copper binding of several peptides using fragmentation chemistry of [M + Cu]+ and [M + 2Cu − H]+ ions. The fragmentation studies reveal interesting insight on Cu binding preferences for basic amino acids. Most notable is the fact that the binding of a single Cu+ ion and two Cu+ ions are quite different, and these differences are explained in terms of intramolecular interactions of the peptide-Cu ionic complex.  相似文献   

14.
Cathodic stripping methods are described for the determination of traces of thiocyanate ions down to 2 × 10-8 mol l-1 and Cu(II) ions down to 1 × 10-8 mol l-1. The method involves electrolytic accumulation of copper(I) thiocyanate on the surface of a hanging mercury drop electrode followed by stripping of the deposit during the cathodic scan. For the determination of thiocyanate, a copper amalgam electrode can be used. Examples of application of the method for the determination of traces of thiocyanate in common salts, in saliva and urine as well as for the determination of copper(II) ions in tap water are described.  相似文献   

15.
Summary.  The synthesis, crystal structure and physical properties of the complex obtained from the reaction between the polyoxometalate anion [PMo12O40]3−, copper(II) and the ligand 1-(2-chloroethyl)tetrazole (teec) are described. This compound has been synthesized as a model for designing materials containing both magnetic polyoxometalate anions and iron(II) spin-crossover cations. The compound, with formula [Cu(teec)5]2[Cu(teec)6][PMo12O40]2·2H2O, consists of alternating layers of polyoxometalates and cationic complexes. Both, five and six coordinated Cu(II) ions are present, each positioned in different layers. Despite these layers having a similar width, the layer of pentacoordinated Cu(II) ions contains twice as many cationic complexes as the layer of hexacoordinated Cu(II) ions. This unusual coexistence of complexes with different coordination number is most likely caused by the steric hindrance induced by the bulky polyoxometalates in the layer of pentacoordinated Cu(II) which prevents the presence of a sixth teec ligand. Corresponding author. E-mail: haasnoot@chem.leidenuniv.nl Received June 5, 2002; accepted June 12, 2002  相似文献   

16.
 The synthesis, crystal structure and physical properties of the complex obtained from the reaction between the polyoxometalate anion [PMo12O40]3−, copper(II) and the ligand 1-(2-chloroethyl)tetrazole (teec) are described. This compound has been synthesized as a model for designing materials containing both magnetic polyoxometalate anions and iron(II) spin-crossover cations. The compound, with formula [Cu(teec)5]2[Cu(teec)6][PMo12O40]2·2H2O, consists of alternating layers of polyoxometalates and cationic complexes. Both, five and six coordinated Cu(II) ions are present, each positioned in different layers. Despite these layers having a similar width, the layer of pentacoordinated Cu(II) ions contains twice as many cationic complexes as the layer of hexacoordinated Cu(II) ions. This unusual coexistence of complexes with different coordination number is most likely caused by the steric hindrance induced by the bulky polyoxometalates in the layer of pentacoordinated Cu(II) which prevents the presence of a sixth teec ligand.  相似文献   

17.
A device has been developed for the measurement of copper(II) ions (Cu2+) in aqueous medium. The device reported here is an electrochemical transistor which consists of two platinum electrodes separated by 100 μm spacing and bridged with an anodically grown film of polycarbazole. Polycarbazole film (undoped form) is observed to be highly selective for the Cu(II) ions. In a completed device, the conductivity of the polycarbazole film changes on addition of Cu(II) ions. The change in conductivity is attributed to the conformational changes in the polymer phase on occupation of the Cu(II) ions, without affecting electron/proton transfer. The device turns on by adding 2.5 × 10−6 M Cu(II) ions and reaches a saturation region beyond 10−4 M Cu(II) ion concentrations. In the above concentration range, the device response [I D vs. log Cu(II) ion concentration] is linear. The selectivity of the device for other metal ions such as Cu(I), Ni(II), Co(II), Fe(II), Fe(III), Zn(II) and Pb(II) is also studied. Received: 6 April 1999 / Accepted: 20 August 1999  相似文献   

18.
Three novel heterobimetallic polymers with Hg(SCN)42? as a linker have been synthesised and characterized by means of IR, EPR, magnetic measurements and single crystal X-ray. All the obtained compounds [Cu(bpzm)Hg(SCN)4]n (1), [Cu(bdmpzm)Hg(SCN)4]n (2) and [Cu(dpa)Hg(SCN)4]n (3) form supramolecular framework structures. The 1 creates a three-dimensional coordination polymer, and 2 and 3 form two-dimensional nets extending along crystallographic (0 1 0) plane. Each octahedrally coordinated Cu(II) atom of 1 connects to four mercury ions through four thiocyanate bridges, and each Hg(II) ion is bridged with four copper ions via four thiocyanate bridges. The Cu(II) ions of 2 and 3 display a pyramidal coordination geometry, and they are connected to three mercury ions through three thiocyanate bridges, one thiocyanate ion is nonbridging group.  相似文献   

19.
This paper describes the synthesis and characterization of a fluorescent ion-imprinted polymer (IIP) for selective determination of copper ions in aqueous samples. The IIP has been prepared using a novel functional monomer, 4-[(E)-2-(4′-methyl-2,2′-bipyridin-4-yl)vinyl]phenyl methacrylate (abbreviated as BSOMe) that has been spectroscopically characterized in methanolic solution, in the absence and in the presence of several metal ions, including Cd(II), Cu(II), Hg(II), Ni(II), Pb(II), and Zn(II). The stability constant (2.04 × 108 mol−2 l2) and stoichiometry (L2M) of the BSOMe complex with Cu(II) were extracted thereof. Cu(II)-IIPs were prepared by radical polymerization using stoichiometric amounts of the fluorescent monomer and the template metal ion. The resulting cross-linked network did not show any leaching of the immobilized ligand allowing determination of Cu(II) in aqueous samples by fluorescence quenching measurements. Several parameters affecting optosensor performance have been optimized, including sample pH, ionic strength, or polymer regeneration for online analysis of water samples. The synthesized Cu(II)-IIP exhibits a detection limit of 0.04 μmol l−1 for the determination of Cu(II) in water samples with a reproducibility of 3%, exhibiting an excellent selectivity towards the template ion over other metal ions with the same charge and close ionic radius. The IIP-based optosensor has been repeatedly used and regenerated for more than 50 cycles without a significant decrease in the luminescent properties and binding affinity of the sensing phase.  相似文献   

20.
Temperature was shown to substantially influence the swelling of KB-2e3 polyacrylic and KB-4P2 polymethacrylic ionites cross-linked by triethylene glycol dimethacrylate (TEGDM) and divinylbenzene (DVB). Maximum swelling changes as the temperature increased were observed for the Ca form of the KB-4P2 ionite. Swelling and contraction of polymethacrylic cationite grains as the temperature decreased and increased occurred at equal fairly high rates, whereas the sorption of water by the polyacrylic cationite in the calcium form cross-linked by TEGDM occurred much more slowly than desorption.  相似文献   

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