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1.
Interaction of the lacunary [alpha-XW9O33](9-) (X = As(III), Sb(III)) with Cu(2+) and Zn(2+) ions in neutral, aqueous medium leads to the formation of dimeric polyoxoanions, [(alpha-XW9O33)2M3(H2O)3](12-) (M = Cu(2+), Zn(2+); X = As(III), Sb(III)), in high yield. The selenium and tellurium analogues of the copper-containing heteropolyanions are also reported: [(alpha-XW9O33)2Cu3(H2O)3](10-) (X = Se(IV), Te(IV)). The polyanions consist of two [alpha-XW9O33] units joined by three equivalent Cu(2+) (X = As, Sb, Se, Te) or Zn(2+) (X = As, Sb) ions. All copper and zinc ions have one terminal water molecule resulting in square-pyramidal coordination geometry. Therefore, the title anions have idealized D3h symmetry. The space between the three transition metal ions is occupied by three sodium ions (M = Cu(2+), Zn(2+); X = As(III), Sb(III)) or potassium ions (M = Cu(2+); X = Se(IV), Te(IV)) leading to a central belt of six metal atoms alternating in position. Reaction of [alpha-AsW9O33](9-) with Zn(2+), Co(2+), and Mn(2+) ions in acidic medium (pH = 4-5) results in the same structural type but with a lower degree of transition-metal substitution, [(alpha-AsW9O33)2WO(H2O)M2(H2O)2](10-) (M = Zn(2+), Co(2+), Mn(2+)). All nine compounds are characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. The solution properties of [(alpha-XW9O33)2Zn3(H2O)3](12-) (X = As(III), Sb(III)) were also studied by 183W-NMR spectroscopy.  相似文献   

2.
The serendipitous discovery of a 3D [Cu(CO(3))(2)(2-)](n) network with the topology of the 4(2)6(4) sodalite net in [Cu(6)(CO(3))(12)(CH(6)N(3))(8)].K(4).8H(2)O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M(6)(CO(3))(12)(CH(6)N(3))(8)]Na(3-)[N(CH(3))(4)].xH(2)O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO(3))(2)(2-)](n) sodalite-like framework, but containing K(+) rather than Na(+), of composition [Ca(6)(CO(3))(12)(CH(6)N(3))(8)]K(3)[N(CH(3))(4)].3H(2)O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH(3))(4)(+) ions are located at their centers. Structures fall into two classes depending on the metal, M(II), in the framework. One type, the BC type (Im3m), comprising the compounds for which M(2+) = Ca(2+), Mn(2+), Cu(2+), and Cd(2+), has a body-centered cubic unit cell, while the second type, the FC type (Fd3c), for which M(2+) = Mg(2+), Fe(2+), Co(2+), Ni(2+), and Zn(2+), has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands.  相似文献   

3.
Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.  相似文献   

4.
The sorption of Cu, Pb, and Zn onto natural lake particles, suspended in 0.005 M NaNO3 solution and in a natural lake water (Esthwaite Water, Cumbria, UK), was studied as a function of pH and time in a series of laboratory experiments, under environmentally realistic conditions. The sorption of all three metals increased with increasing pH and reaction time (2 h and 7 days). In 0.005 M NaNO3 solution, the well-defined sorption edges spanned 2–2.5 pH units for Cu and Pb, and ≈ 4 pH units for Zn. In the natural lake water, the Cu sorption edge was broader and both Cu and Zn were less strongly sorbed. The binding stability decreased in the order Pb>Cu>Zn. Competitive adsorption onto surface sites appeared to be the main factor determining the observed sorption behaviour. Application of a macroscopic metal exchange model to the 7 day NaNO3 results enabled the surface site concentration to be estimated as 0.79 ± 0.07 mmol g−1. The modelling exercise suggested that an observed shift in the sorption edge of Zn, in the presence of Pb and Cu, was due to competition for surface sites. The experimental data are in good general agreement with field observations of trace metal behaviour in Cumbrian lakes. The almost total sorption of Pb by lake particles throughout the in-situ pH range is compatible with previous field measurements including trace metal budgets and residence times. Dissolved Zn concentrations in the lake are lower than predicted by the sorption experiments, but the lower lake concentrations are consistent with the previously observed scavenging of Zn by planktonic algae. Both the decreased sorption of Cu in the experiments with natural lake water, compared to that in NaNO3 solution, and the relatively small-scale removal of dissolved Cu by particles in the lake itself can partially be explained by humic complexation.  相似文献   

5.
The kinetics of sorption of Cu(2+) on a Saudi clay mineral (bentonite) was investigated at 20+/-0.5 degrees C using different weights of the clay (0.5, 1.0, 1.5, and 2 g). Each weight represents a certain sample size. The order of the process appeared to be 1 with respect to the Cu(2+), and 112 with respect to the clay surface area. The rate was found to depend on internal diffusion.,which produced a decrease in the specific rate of sorption as a function of time. Sorption characteristics were described using two site Langmuir isotherms. The desorption experiments proved that Cu(2+) ions are chemisorbed on the bentonite surface. The maximum adsorption obtained was 909 mg Cu(2+)/g clay. This value is of great significance, as it is much higher than any reported one.  相似文献   

6.
Hydrotalcite-like compounds (layered double hydroxides, LDHs) containing varying amounts of Al(3+), Zr(4+), and Zn(2+) or Mg(2+) in the metal hydroxide layer have been synthesized and characterized by various physicochemical methods. The adsorption behavior of uncalcined (as-synthesized) and calcined LDHs have been investigated for Cr(2)O(7)(2-) and SeO(3)(2-). The mixed oxides, obtained on calcination at 450 degrees C, exhibit high adsorption capacities for Cr(2)O(7)(2-) (1.6-2.7 meq/g) and SeO(3)(2-) (1.1-1.5 meq/g), where adsorption occurs through rehydration. Substitution of Zr(4+) in the LDHs, for either M(2+) or Al(3+) ions, increases the adsorption capacity up to 20%, thus providing an alternative way to enhance the adsorption capacity of this type of material. The high adsorption capacity of these materials could be successfully used for removal of undesirable anions from water and also for synthesis of intercalated materials with tailored acidobasicity.  相似文献   

7.
A poly(amine ester) dendrimer with naphthyl units (G1N6) has been synthesized as a fluorescent chemosensor for metal ions. We investigated the metal-ion recognition of G1N6 by adding each of Ag(+), Al(3+), Ba(2+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(3+), Mg(2+), Ni(2+), and Zn(2+) in acetonitrile solution. Large changes were observed in the fluorescence spectra of G1N6 upon the addition of Al(3+), Cu(2+), and Zn(2+).  相似文献   

8.
Selected metal-organic frameworks exhibiting representative properties--high surface area, structural flexibility, or the presence of open metal cation sites--were tested for utility in the separation of CO(2) from H(2) via pressure swing adsorption. Single-component CO(2) and H(2) adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn(4)O(BTB)(2) (MOF-177, BTB(3-) = 1,3,5-benzenetribenzoate), Be(12)(OH)(12)(BTB)(4) (Be-BTB), Co(BDP) (BDP(2-) = 1,4-benzenedipyrazolate), H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (Cu-BTTri, BTTri(3-) = 1,3,5-benzenetristriazolate), and Mg(2)(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H(2)/CO(2) gas mixtures relevant to H(2) purification and precombustion CO(2) capture, respectively. In the former case, the results afford CO(2)/H(2) selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal-organic frameworks with a high concentration of exposed metal cation sites, Mg(2)(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO(2)/H(2) separations.  相似文献   

9.
The synthesis, activation, and heats of CO(2) adsorption for the known members of the M(3)(BTC)(2) (HKUST-1) isostructural series (M = Cr, Fe, Ni, Zn, Ni, Cu, Mo) were investigated to gain insight into the impact of CO(2)-metal interactions for CO(2) storage/separation applications. With the use of modified syntheses and activation procedures, improved BET surface areas were obtained for M = Ni, Mo, and Ru. The zero-coverage isosteric heats of CO(2) adsorption were measured for the Cu, Cr, Ni, Mo, and Ru analogues and gave values consistent with those reported for MOFs containing coordinatively unsaturated metal sites, but lower than for amine functionalized materials. Notably, the Ni and Ru congeners exhibited the highest CO(2) affinities in the studied series. These behaviors were attributed to the presence of residual guest molecules in the case of Ni(3)(BTC)(2)(Me(2)NH)(2)(H(2)O) and the increased charge of the dimetal secondary building unit in [Ru(3)(BTC)(2)][BTC](0.5).  相似文献   

10.
Tetravalent metal phosphates (M=Zr, Ti, and Sn) were prepared and characterized by XRD, surface properties, and TG-DTA. The cation exchange and sorption behavior of these metal phosphates toward transition metal ions such as Cu(2+), Co(2+), and Ni(2+) have been studied comparatively as a function of temperature and concentration. The adsorption process was found to increases with increase in temperature and concentration. The selectivity order for alpha-titanium and alpha-tin phosphates is Cu(2+)>Co(2+)>Ni(2+), whereas for alpha-zirconium phosphate it is Cu(2+)>Ni(2+)>Co(2+). The ion exchange capacity of alpha-titanium phosphate is greater than those of other phosphates, which is explained on the basis of the surface behavior, disorderness of the system, degree of hydrolysis of incoming guest adsorbate metal ions, and structural steric hindrance of the exchangers during adsorption and sorption. The distribution coefficient, Gibbs free energy, enthalpy, and entropy values indicate that the ion-exchange processes are spontaneous.  相似文献   

11.
Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3-10. Five background electrolyte cations (Li(+), Na(+), K(+), Ca(2+), and Mg(2+)) with a concentration of 0.01 M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu(2+), could significantly enhance the adsorption and higher concentration of Cu(2+), stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu(2+) could enhance the adsorption via acting as a bridge ion to form goethite-Cu(2+)-tetracycline surface complex because Cu(2+) could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.  相似文献   

12.
The porosity and hydrogen storage properties for the dehydrated Prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn) are reported. Argon sorption isotherms measured at 87 K afford BET surface areas ranging from 560 m2/g for Ni3[Co(CN)6]2 to 870 m2/g for Mn3[Co(CN)6]2; the latter value is comparable to the highest surface area reported for any known zeolite. All six compounds show significant hydrogen sorption at 77 K and 890 Torr, varying from 1.4 wt % and 0.018 kg H2/L for Zn3[Co(CN)6]2 to 1.8 wt % and 0.025 kg H2/L for Cu3[Co(CN)6]2. Fits to the sorption data employing the Langmuir-Freundlich equation give maximum uptake quantities, resulting in a predicted storage capacity of 2.1 wt % and 0.029 kg H2/L for Cu3[Co(CN)6]2 at saturation. Enthalpies of adsorption for the frameworks were calculated from hydrogen isotherms measured at 77 and 87 K and found to increase with M varying in the order Mn < Zn < Fe < Co < Cu < Ni. In all cases, the binding enthalpies, which lie in the range of 5.3-7.4 kJ/mol, are higher than the 4.7-5.2 kJ/mol measured for Zn4O(1,4-benzenedicarboxylate)3.  相似文献   

13.
Metal-organic frameworks with unsaturated metal centers in their crystal structures, such as Ni/DOBDC and Mg/DOBDC, are promising adsorbents for carbon dioxide capture from flue gas due to their high CO(2) capacities at subatmospheric pressures. However, stability is a critical issue for their application. In this paper, the stabilities of Ni/DOBDC and Mg/DOBDC are investigated. Effects of steam conditioning, simulated flue gas conditioning, and long-term storage on CO(2) adsorption capacities are considered. Results show that Ni/DOBDC can maintain its CO(2) capacity after steam conditioning and long-term storage, whereas Mg/DOBDC does not. Nitrogen isotherms for Mg/DOBDC show a drop in surface area after steaming, corresponding to the decrease in CO(2) adsorption, which may be caused by a reduction of unsaturated metal centers in its structure. Conditioning with dry simulated flue gas at room temperature only slightly affects CO(2) adsorption in Ni/DOBDC. However, introducing water vapor into the simulated flue gas further reduces the CO(2) capacity of Ni/DOBDC.  相似文献   

14.
Tewari PK  Singh AK 《Talanta》2001,53(4):823-833
A new chelating resin is prepared by coupling Amberlite XAD-2 with pyrocatechol through an azo spacer, characterized (by elemental analysis, IR and TGA) and studied for preconcentrating Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The sorption is quantitative in the pH range 3.0-6.5, whereas quantitative desorption occurs instantaneously with 2 M HCl or HNO(3) The sorption capacity has been found to be in the range 0.023-0.092 mmol g(-1) of resin. The loading half time (t(1/2)) is 1.4, 4.8, 1.6, 3.2, 2.3 and 1.8 min, respectively for Cd, Co, Cu, Fe, Ni and Zn. The tolerance limits of electrolytes NaCl, NaBr, NaNO(3), Na(2)SO(4) and Na(3)PO(4) in the sorption of all the six metal ions (0.2 mug ml(-1)) are reported. The Mg(II) and Ca(II) are tolerable with each of them (0.2 mug ml(-1)) up to a concentration level of 0.01-1.0 M. The enrichment factor has been found to be 200 except for Fe and Cu for which the values are 80 and 100, respectively. The lowest concentration of metal ion for quantitative recovery is 5, 10, 20, 25, 10 and 10 mug l(-1) for Cd, Co, Cu, Fe, Ni and Zn, respectively. The simultaneous determination of all these metal ions is possible and the method has been applied to determine all the six metal ions in tap and river water samples (RSD相似文献   

15.
Macroscopic sorption studies indicated that Pb sorption capacity was independent of pH over the pH range 5-7, while sorption as a function of reaction time up to two weeks for systems with no bulk precipitate phases showed continuous Pb uptake on dolomite. This could be due to diffusion of Pb into the micropores of dolomite as well as an increase in surface sites caused by particle size reduction during suspension mixing. Normalized XANES spectra for systems undersaturated with respect to Pb carbonate precipitates resembled the spectrum of Pb4(OH)4(4+), suggesting that Pb is mainly coordinated to dolomite as an inner-sphere surface complex. On the other hand, the XANES spectrum for 10(-3) M Pb at 1 atm CO2(g) in a 2 M Mg(NO3)2 background electrolyte solution resembled that of cerussite, while a sample at 5 x 10(-4) M Pb in equilibrium with air and 2 M Mg(NO3)2 resembled that of hydrocerussite. EXAFS analyses of sorption samples in chloride solutions showed that there were only first-shell contributions under 1 atm CO2(g), while higher shell contributions from Ca/Mg were seen at 10(-3.42) atm CO2(g). On the other hand, EXAFS samples prepared in nitrate solutions showed noticeable differences in speciation under different reaction conditions-from outer-sphere surface complexes at low Pb concentrations and pH, to inner-sphere surface complexes at moderate Pb concentrations and neutral pH, to the formation of Pb carbonate precipitates at the highest Pb loadings.  相似文献   

16.
Novel efficient complexing resins—poly(vinylbenzyl pyridinium salts) fabricated through poly(vinylbenzyl halogene-co-divinylbenzene) quaternization of N-decyloxy-1-(pyridin-3-yl)ethaneimine and N-decyloxy-1-(pyridin-4-yl)ethaneimine—were tested as adsorbents of Pb(II), Cd(II), Cu(II), Zn(II), and Ni(II) from aqueous solutions. The structure of these materials was established by 13C CP-MAS NMR, X-ray photoelectron spectroscopy, elemental analysis, and Fourier transform infrared spectroscopy, as well as thermogravimetric and differential thermal analyses. The textural properties were determined using scanning electron microscopy and low-temperature N2 sorption. Based on the conducted sorption studies, it was shown that the uptake behavior of the metal ions towards novel resins depended on the type of functionalities, contact time, pH, metal concentrations, and the resin dosage. The Langmuir model was investigated to be the best one for fitting isothermal adsorption equilibrium data, and the corresponding adsorption capacities were predicted to be 296.4, 201.8, 83.8, 38.1, and 39.3 mg/g for Pb(II), Zn(II), Cd(II), Cu(II), and Ni(II), respectively. These results confirmed that owing to the presence of the functional pyridinium groups, the resins demonstrated proficient metal ion removal capacities. Furthermore, VBBr-D4EI could be successfully used for the selective uptake of Pb(II) from wastewater. It was also shown that the novel resins can be regenerated without significant loss of their sorption capacity.  相似文献   

17.
An "off-on" Zn(2+) and "on-off" Cu(2+) fluorescent chemosensor C was designed and synthesized. The binding of C and Zn(2+)/Cu(2+) is chemically reversible by the addition of EDTA disodium solution; moreover, the fluorescence emission signal of ZnC decreased with the addition of Cu(2+), demonstrating that ZnC could detect Cu(2+)via metal displacement.  相似文献   

18.
The inorganic-organic hybrid magnesium aminoethyl phosphonate (Mg(AEP)(H(2)O), particle diameter: 20 nm; specific surface area: 322(10) m(2) g(-1); pore volume: 0.9(1) cm(3) g(-1)) shows reversible CO(2) sorption (152(5) mg g(-1)) at high pressure (≤110 bar). In contrast, N(2) uptake remains below 1.0(1) mg g(-1). Based on this selectivity (~100%) Mg(AEP)(H(2)O) expands the range of materials available for CO(2) capture.  相似文献   

19.
In this work, porous carbons with well-developed pore structures were directly prepared from a weak acid cation exchange resin (CER) by the carbonization of a mixture with Mg acetate in different ratios. The effect of the Mg acetate-to-CER ratio on the pore structure and CO(2) adsorption capacities of the obtained porous carbons was studied. The textural properties and morphologies of the porous carbons were analyzed via N(2)/77K adsorption/desorption isotherms, SEM, and TEM, respectively. The CO(2) adsorption capacities of the prepared porous carbons were measured at 298 K and 1 bar and 30 bar. By dissolving the MgO template, the porous carbons exhibited high specific surface areas (326-1276 m(2)/g) and high pore volumes (0.258-0.687 cm(3)/g). The CO(2) adsorption capacities of the porous carbons were enhanced to 164.4 mg/g at 1 bar and 1045 mg/g at 30 bar by increasing the Mg acetate-to-CER ratio. This result indicates that CER was one of the carbon precursors to producing the porous structure, as well as for improving the CO(2) adsorption capacities of the carbon species.  相似文献   

20.
A chiral polymer incorporating an (R,R)-salen moiety was synthesized by the polymerization of (R,R)-1,2-diaminocyclohexane with 2,5-dibutoxy-1,4-di(salicyclaldehyde)-1,4-diethynyl-benzene by a nucleophilic addition-elimination reaction. The fluorescence responses of the (R,R)-salen-based polymer toward various metal ions were investigated by fluorescence spectra. Compared with other cations, such as Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Hg(2+), and Pb(2+), Zn(2+) can lead to a pronounced fluorescence enhancement as high as 7.8-fold together with an obvious blue-shift change of the chiral polymer. More importantly, the fluorescent color of the polymer changed to bright blue instead of weak yellow after addition of Zn(2+), which can be easily detected by the naked eye. The results indicate that this kind of chiral polymer, incorporating an (R,R)-salen moiety as a receptor in the main chain backbone, can exhibit high sensitivity and selectivity for Zn(2+) recognition.  相似文献   

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