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1.
《分离科学与技术》2012,47(10):1335-1346
Abstract

Some selective transport systems for heavy metallic ions through a supported liquid membrane (SLM) containing a 2,2′-dipyridyl derivative ligand, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline (bathocuproine), 2,9-dimethyl-1,10-phenanthro-line (neocuproine), or 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline), were investigated. The transport of copper(I, II), cadmium(II), zinc(II), lead(II), and cobalt(II) ions was accomplished with a halogen ion such as chloride, bromide, or iodide ion as a pairing ion species for any SLM. The ranking of the permeability of the metallic ions was Cu+,2+, Zn2+, Cd2+ ? Pb2+, Co2+. When the oxidation-reduction potential gradient was used as a driving force for metallic ions, the transport of Cu+ ion was higher than those of Cd2+ and Zn2+ ions for any SLM containing bathocuproine, neocuproine, or bathophenanthroline. On the other hand, in the transport system which used the concentration gradient of pairing ion species, the permeability of the Cu2+ ion decreased whereas that of the Cd2+ ion increased. Moreover, it was found that the different selectivity for the transport of metallic ions is produced by using various pairing ion species.  相似文献   

2.
ABSTRACT

Thermodynamics of alkali and alkaline earth metal ions/hydrogen ions exchange on a fibrous cerium(IV) hydrogen phosphate have been investigated. Selectivities for alkali and alkaline earth metal ions increase in the order; Na+<<K+<Rb+<Cs+ and Mg2+<Ca2+<Sr2+<Ba2+, respectively. The enthalpy changes for alkali metal and Ba2+ ions/H+ exchange are negative, those for the other alkaline earth metal ions/H+ exchange are positive, indicating that the enthalpy changes for monovalent ions are more favorable than those for divalent ions. In comparison with ions of the same valency, the enthalpy change decreases with the atomic number of the metal ion corresponding to a decrease in the entropy change of dehydration in response to enthalpy-entropy compensation.  相似文献   

3.
《分离科学与技术》2012,47(2):338-345
Selective recognition of alkali and alkaline earth metal ion pairs viz.Li+, Na+, K+, Mg2+ and Ca2+ is of great biological importance. Design and synthesis of ionophores and receptor molecules capable of selectively binding and transporting substrates (neutral and ionic) are based on molecular recognition and used to develop membrane separation systems. This has potential applications in analytical, environmental, and biomimetic chemistry. We have designed and synthesized new series of anthraquinone derived single and double armed ionophores. Supermolecules have been isolated with these synthetic podands as host and metal ions as guest. Interaction has been confirmed by melting point (m.p.), infrared red (IR), and proton nuclear magnetic resonance (1H NMR) spectral analysis and cyclic voltammetric studies. Further, the liquid liquid extraction, bulk liquid membrane (BLM) transport, and supported liquid membrane (SLM) transport studies using polytetrafloroethylene membrane, cellulose nitrate membrane, onion membrane and egg shell membrane, have been done to find out the selectivity of these ionophores for various metal ions. Among the two liquid membrane systems used SLMs is more efficient than BLMs. It is found that double armed and bridged ionophores (A3 to A8) show better extraction ability than single armed ionophores (A1, A2) and ionophore A3 is calcium selective.  相似文献   

4.
Carrier-assisted transport through liquid membranes is one of the important applications of supramolecular chemistry. This work investigates the use of synthetic carrier (ionophore) for the separation of metal ions. We have tested the effect of structure of ionophore on the separation of metal ions. For this purpose, we have used a new series of non-cyclic ionophores having different end groups and chain length (R1–R5). 1,5 bis (2-naphthyloxy)-3-oxapentane (R1), 1,8 bis (2-naphthyloxy)-3,6-di-oxaoctane (R2), 1,11 bis (2-naphthyloxy)-3,6,9-tri-oxaundecane (R3) 1,11-(dianthraquinonyloxy) 3,6,9-trioxaundecane (R4), 1,8 (dianthraquinonyloxy) 3, 6-dioxaoctane (R5) have been used in extraction, bulk liquid membrane (BLM) and supported liquid membrane (SLM) transport of alkali (Li+, Na+, K+) and alkaline earth metal cations (Ca2+, Mg2+). The supported liquid membrane consisted of a porous cellulose nitrate and and an onion membrane support impregnated with ionophore using chloroform as a solvent. The results reveal that ionophores R1, R2 and R3 are better extractants for K+ while R4 and R5 are better extractants for Ca2+. Among these ionophores R3 and R4 are best extractants for K+ and Ca2+ ions. The results of BLM reveal that ionophores R1, R2 and R3 transport Na+ at a greater extent, while R4 and R5 transport Ca2+ and K+ at a greater extent. In SLM experiments using a cellulose nitrate membrane support, it was observed that naphthyl end group bearing ionophores (R1–R3) transports Na+ > K+, and anthraquinone bearing ionophores (R4 and R5) transport K+ > Na+ > Ca2+ respectively. In the onion membrane support R4 transports Ca2+ and Na+ equally and R5 transports K+ selectively. On comparing the membrane support, the cellulose nitrate membrane is found better support for the transport of metal ions. The results suggest that due to the presence of different end groups and chain lengths the selectivity of non-cyclic ionophores towards metal ions is enhanced. Thus selectivity of ionophores may have fruitful application in ion selective electrodes and separation of metal ions.  相似文献   

5.
The thermodynamics of alkali and alkaline earth metal ion exchange on a layered zirconium sulphophosphonate having the general composition Zr(O3PC6H4SO3H) ×(HPO4) 2?× yH2O have been investigated. Enthalpy and entropy changes accompanying the M2+ - H+ exchange (M = Na+, Cs+, Mg2+ and Ba2+)were determined by the temperature variation method. For the monovalent ions, Na+ and Cs+, the enthalpy terms favor exchange whereas the entropy terms are unfavorable. In contrast, for the divalent ions, Mg2+ and Ba2+, the exchange is due to highly favorable entropy terms.  相似文献   

6.
The effects of Li+, Na+, K+, Mg2+ and Zn2+ ions on the activity and enantioselectivity of Candida rugosa lipase (CRL) were investigated in a biphasic medium composed of phosphate buffer solution (containing a metal ion within a 50–500 mM concentration range) and isooctane. The hydrolytic activities of CRL towards p‐nitrophenyl acetate were measured after incubation of the enzyme in the presence of metal ions for 24 h, and they were compared to that obtained after incubation in the absence of any metal ion. The CRL activity was stimulated by the chloride salts of Li+, K+ and Mg2+ for all concentrations considered and the highest enhancement was achieved by Li+ with a 1.24–1.75 fold increase observed. The effects of metal ions on the enantioselectivity of CRL were investigated by performing the hydrolysis of racemic Naproxen methyl ester in the same biphasic medium containing Li+, Na+, K+, Mg2+ and Zn2+ ions. The addition of metal ions increased the hydrolysis rate by ca. 1.31–1.45 fold relative to the control, whereas the enantiomeric excess of product increased slightly in the presence of the metal ions. The effect of Triton X‐100 on the activity and enantioselectivity of the CRL was also investigated by employing 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 mM concentrations of it in phosphate buffer solution of the biphasic medium. High concentrations of Triton X‐100 stimulated the enzyme activity up to 1.66 fold after 24 h incubation. Triton X‐100 increased the hydrolysis rate almost independently of the concentration.  相似文献   

7.
ABSTRACT

The ion exchange behavior of three sodium micas (phlogopite, Ward's Sci.; phlogopite, Suzorite Inc., biotite, Ward's Sci.) towards Li+, K+, Rb+, Cs+, Mg2+. Ca2+, Sr2+, Ba2+, Pb2+ Hg2+, Co2+, Cu2+ Cd2+ and Zn2+ ions has been studied. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and concentration equilibrium constants as a function of metal loading and temperature were analyzed. Sodium micas exhibit high affinity for heavy alkali metals with the selectivity order Rb+ > Cs+ > K+. By studying the cesium uptake in the presence of NaNO3, CaCl2, NaOH, NaOH+KOH, HNO3 electrolytes (in the range of 0.01–6 M) it was found that sodium micas could remove cesium efficiently in neutral and alkaline media, which make them promising for certain types of nuclear waste treatment.  相似文献   

8.
Lithium may be recovered from the Dead Sea brines by a process which combines membrane separation with ion-exchange. Solvent-polymeric membranes based on alkyl-arylphosphates cause selective permeation of lithium ions with Br3 as counter ions. Addition of the derivatives of neutral “crown” ethers did not improve their performance and an adverse effect, due to the decrease in the fluidity of the membrane system, was observed. Incorporation of ionizable “crown” ethers compatible with the system may, however, be advantageous; pH gradients could act as a driving force for transport of lithium in such systems. Membranes prepared with (2-ethylhexyl)-diphenyl phosphate (Santicizer 141) gave the best results from the point of view of selectivity of Li+ transport vs. Mg2+ and Ca2+. Maintenance of ca. 10−3 M concentrations of Br2 in the end-brine solutions gives optimal membrane performance. No significant change in membrane permeability and selectivity occurred during six months of their operation. Lithium ions in the product solution of the membrane separation process may be further separated from the residual Mg2+ and Ca2+ ions and concentrated up to 1 M by ion exchange processes. Lithium may be precipitated from such solutions, free from alkaline earth ions, as Li2CO3.  相似文献   

9.
The adsorptive properties of A-Mn02for mono and divalent metal ions were investigated by pH titration and by measurements of the distribution coefficients(Kd's) of the metal ions. The pH titration curve showed an apparently monobasic acid type for a H+-Li+exchange. Those for H+-K+and H+-Cs+exchanges were nearly the same as that for blank titration. The lithium ion uptake increased with increasing solution pH and reached 5 meq/g at pH 11. X-ray diffraction analyses showed that the adsorption of lithium ions caused an increase in the lattice constant of a cubic unit cell. The potassium and cesium ion uptakes were nearly zero over a pH range between 4 and 11. A-Mn02showed a remarkably high Kd value for lithium ions, compared to a cation exchange resin. The selectivity sequences were Na+< K+< Rb+< Cs+<< Li+for alkali metal ions, Mg2+< Ca2+< Sr2+< Ba2+for alkaline earth metal ions, and Ni2+< Zn2+< Co2+< Cu2+for transition metal ions.  相似文献   

10.
《分离科学与技术》2012,47(12-13):1813-1823
Abstract

The macrocycle-mediated flaxes of the alkali and alkaline earth metal cations have been determined in a H2O-CH2Cl2-H2O bulk liquid membrane system. Water-insoluble proton-ionizable macrocycles of the triazolo type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H+ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. Transport of the alkali cations only occurred when the source phase pH was greater than the aqueous pKa value for the carriers. Transport increased regularly with increasing source phase pH. Transport of alkaline earth cations from neutral pH source phases was minimal. The alkali cation selectivity order was K+ > Rb+ > Cs+ > Na+ > Li+ for the l8-crown-6 sized macrocycles, while little selectivity was observed with the 15-crown-5 sized macro-cycle.  相似文献   

11.
Mn4+ doped aluminate materials with efficient red emission are promising components for warmer white light-emitting diodes. However, it still remains as a challenge on increasing its luminous efficiency. For Mn4+ doped aluminate phosphors, co-dopants such as Li+, Mg2+, Na+, Si4+, or Ge4+ ions are often added to tailor the photoluminescence properties of phosphors during preparing process. However, the role of the ions is still in debate. In this work we took BaMgAl10O17:Mn (BMA:Mn) and α-Al2O3:Mn as examples to study the effects of Li+, Mg2+, Na+, and Si4+ on their luminescent properties. The energy levels induced by the co-dopants and some possible intrinsic defects of hosts (Al2O3) were calculated using the first-principles method. It is found that the Mg2+ and Na+ ions, compared with Li+ and Si4+, can prefer to form hole-type defects which enhance the valence stability of Mn4+ and thus enhance the emission intensity of the as-prepared phosphors.  相似文献   

12.
Novel membranes based on sulfonated poly (phenylene oxide) (SPPO) was developed. SPPO membranes in the hydrogen form were converted to metal ion forms. The effect of exchange with metal ions including monovalent (Li+, Na+, K+), divalent (Mg2+, Ba2+, Ca2+) and trivalent (Al3+) ions was investigated in terms of permeation rate and permeation rate ratios for CO2 and CH4 gases. Both dense homogeneous membranes and thin‐film composite (TFC) membranes were studied for their gas separation characteristics. The effect of membrane preparation conditions and operating parameters on the membrane performance were also investigated. The selectivity of the TFC membrane increased as the cationic charge density increased as a result of electrostatic cross‐linking. TFC membrane of very high selectivity was achieved by coating a thin layer of SPPO‐Mg on a PES substrate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 735–742, 2000  相似文献   

13.
《分离科学与技术》2012,47(7):1779-1789
Abstract

Three ion-sieve-type manganese oxides, HMnO(Li), HMnO(Na), and HMnO(K), were prepared by acid treatments of Li+-, Na+-, and K+-introduced manganese oxides, respectively. Three oxides were obtained from γ-MnO2 and the corresponding alkali metal hydroxides by heating at 600°C. The ion-exchange properties of the adsorbents were investigated by pH titration, Kd measurements, and the adsorption of metal ions from seawater. The selectivity sequences of alkali metal ions were Na+ < Cs+ < Rb+ < K+ < Li+ for HMnO(Li) and Li+ Na+ < Cs+ < K+ < Rb+ for HMnO(Na) and HMnO(K). The high selectivity of Li+ on HMnO(Li) can be ascribed to an ion-sieve effect of spinel-type manganese oxide which was produced from LiMn2O4 Since HMnO(Na) and HMnO(K) had [2 × 2] tunnels of edge-shared [MnO6] octahedra, the high selectivities of K+ and Rb+ on these samples were used to explain that the sizes of the [2 × 2] tunnels were suitable for filling ions of about 1.4 Å in radius in a stable configuration. The order of metal-ion uptake from seawater was Sr2+ < K+ < Mg2+ < Ca2+ < Na+ < Li+ for HMnO(Li), Li+ < Sr2+ < Mg2+ < Ca2+ < Na+ < K+ for HMnO(Na), and Li+ < Sr2+ < Ca2+ < Mg2+ < K+ < Na+ for HMnO(K).  相似文献   

14.
Cationic exchange membranes were prepared with 2,3-epithiopropyl methacrylate (ETMA)–methacrylic acid (MAc) copolymer. Transport of alkali metal ions against their concentration gradient through the membranes was investigated by using the system which contains HCl (left side) and alkali metal solution including two kinds of alkali hydroxides (right side). The effect of ultraviolet (UV) irradiation on the selective transport of alkali metal ions through the ETMA–MAc copolymer membranes was investigated. The membranes were irradiated with a 6-W low pressure mercury lamp at a distance of 10 cm at room temperature in air. The transport selectivity could be increased by using UV-irradiated membranes and the selectivity increased with increasing irradiation time up to 2–3 h, although the transport rate of alkali metal ions decreased with increasing time of UV irradiation. The maximum selectivity of K+/Na+, Na+/Li+, and K+/Li+ were 1.7, 2.0, and 4.2, respectively. In order to explain this phenomena, the effect of UV irradiation on the properties of the membranes was studied. It was concluded that the increase of the selectivity is attributed to the formation of the dense membrane by photocrosslinking of the membrane by UV irradiation.  相似文献   

15.
Ribose-protected thioguanosine (TG) exhibited remarkable preference for cesium over other alkali metal (Na+, K+, Rb+) and alkaline earth metal ions (Mg2+, Ca2+, Sr2+, Ba2+) in acetonitrile by 1H NMR measurements. Furthermore, TG displayed excellent sensitivity for cesium even under 500/1 NaCl/CsCl and KCl/CsCl environments. The most distinct feature is that only in a cesium environment, the thioamide NH peak becomes highly broadened and finally disappeared, and the amino NH2 peak shows a downfield shift, suggesting that TG-based 1H NMR spectroscopic probe is factually useful for the detection of cesium from solid cesium-containing sources in organic solvents.  相似文献   

16.
Cation exchange membranes (CEMs) hold promise for efficient and environment‐friendly lithium extraction from salt‐lake brine. However, development and practical application of CEMs are significantly hindered by the low Li+ permeation and permselectivity. Herein, novel hybrid CEMs are developed by dispersing lithium ion‐sieves (LMO) into sulfonated poly(ether ether ketone) matrix. Two kinds of LMOs are synthesized including acidified LMO (HMO) and its sulfonation compound (HMO‐S). The physicochemical property and separation performance of hybrid membranes are systematically investigated. The uniformly dispersed HMO and HMO‐S enhance the thermal, mechanical stability, and swelling resistance of hybrid membranes. Furthermore, these fillers obviously reduce the area resistance from 8.0 to less than 6.0 Ω cm?2. Importantly, the unique Li+ transfer channels in HMO/HMO‐S efficiently elevate the Li+ permeation by up to 66%. While the “ion‐sieve effect” of the channels weakens the migration of Mg2+ and K+, thus notably rising Li+/Mg2+ and Li+/K+ permselectivities by ≈5 times, which is difficult to realize with conventional fillers. Comparing with HMO, HMO‐S shows higher improvement for permselectivity because of the reduced area resistance of the resultant hybrid membrane. This study paves a way to design and development of selective Li+ exchange membranes for transport and separation applications.  相似文献   

17.
Three reactive and functional polymers were synthesized by reacting formaldehyde with the phenolic Schiff bases derived from 4,4′-diaminodiphenylsulfone and o-, m-, and p-hydroxybenzaldehydes, respectively. The metal ion uptake behavior of these resins towards Cu2+, Ni2+, Co2+, and UO2 2+ ions in dilute aqueous media was studied. The optimum conditions for the absorption of metal ions were determined by varying the various parameters like contact time, size of the sorbents, concentration of the metal ion solutions, and the pH of the reaction medium. Suitable conditions were ascertained for preferential adsorption of the above metal ions from the salt solutions containing other interfering ions such as Na+, K+, and Mg2+. Presence of these alkali and alkaline earth metal ions in the salt solutions did not affect the adsorption behavior of the resins. It was observed that the structural features of the resins have a profound effect on the uptake characteristics. The position of the OH group present in the meta position with respect to the imine nitrogen atom in the resin, demonstrated a significant influence on the extent of metal ion adsorption by the resin. Out of the three resins reported here, the resin derived from the Schiff base of m-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone showed higher efficiency in uptake of metal ions from the solutions than the corresponding resins derived from the Schiff bases of o- and p-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone.  相似文献   

18.
Cyclic voltammetric studies of thin films of electrosynthesized (ES)-Ni(OH)2 and Co(OH)2 in different alkaline electrolytes suggest that the mechanism of oxidation is different from the mechanism of reduction. While the metal ion (alkali or alkaline earth metal) intercalation-deintercalation from the electrolyte into the film provides the driving force, the reduction reaction takes place heterogeneously independent of the electrolyte concentration, whereas oxidation takes place homogeneously across a nebulously defined electrode-electrolyte interphase. ES-Ni(OH)2 permits facile intercalationdeintercalation of alkali metal ions Li+, Na+ and K+, irrespective of their ionic size, while the reactions of ES-Co(OH)2 are sensitive to ionic size, requiring larger potentials in KOH compared to LiOH. In the alkaline earth metal hydroxides, both Ni(OH)2 and Co(OH)2 films show greater reversible characteristics in the order Ba(OH)2 > Sr(OH)2 > Ca(OH)2. This may be trivially related to the order of the solubilities of the three hydroxides.  相似文献   

19.
ABSTRACT

Spherically granulated sodium aluminosilicophosphate (APS) of the empirical formula Na4Al4PS18O46.5 18H2O was synthesized by a gel method. The APS was characterized by elemental analysis, X-ray diffraction, TGA and 27AI, 28Si and 31P MAS NMR spectroscopy methods. Ion exchange of alkali, alkaline earth and some other divalent metal cations by APS was studied in batch conditions. It was found that the APS has a cation exchange capacity of 2.5 meq/g and exhibits rapid kinetics of ion exchange. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and the corrected selectivity coefficients as a function of metal loading were analyzed. It was found that APS exhibits a high affinity for cesium ion, a moderate affinity for some heavy metal cations (Pb2+, Zn+) and a low affinity for alkali and alkaline earth metal ions. A testing of the APS in complex solutions suggests that it could be a promising exchanger for treatment of some specific nuclear waste and contaminated environmental and biological liquors from radioactive cesium and toxic heavy metal ions.  相似文献   

20.
Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na2O concentration of 12.7 mol%. We used these glasses to investigate the influence of R = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm as R increases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na+, Ca2+, and Mg2+) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless of R and the leaching of modifier cations resulted in a silica-rich layer in the surface. The leaching of Ca2+ and Mg2+ ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function of R. The leaching of Na+ ions varied monotonically; the thickness of the Na+ depletion layer increased from ~100 nm at R = 0 to ~200 nm at R = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re-arrangement or re-polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.  相似文献   

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