The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivativ...The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.展开更多
A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmon...A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmonic vibrational frequency calculations have been performed on the AX～U4（）1A1 state of O3 and AX～U4（）2B1 state of O-3. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of O-3. The theoretical spectrum obtained by employing CCSD（T）/6-311+G（2d,p） values are in excellent agreement with the observed one. In addition, the equilibrium geometry parameters, re（OO）= 0.135?5±0.000?5 nm and θe（O-O-O） =114.5±0.5°, of the AX～U4（）2B1 state of O-3, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.展开更多
本文提出了一种可快速计算Anion-π作用强度的方法。该方法包含静电、极化和范德华作用。我们将取代苯的C≡N、C―F和C―H化学键作为键偶极,通过阴离子和取代苯的键偶极间相互作用来计算静电作用,根据键偶极大小随着环境变化而改变来计...本文提出了一种可快速计算Anion-π作用强度的方法。该方法包含静电、极化和范德华作用。我们将取代苯的C≡N、C―F和C―H化学键作为键偶极,通过阴离子和取代苯的键偶极间相互作用来计算静电作用,根据键偶极大小随着环境变化而改变来计算极化作用。文中所需参数由模拟CCSD(T)/CBS势能曲线而确定。将本文方法应用于一系列卤素阴离子和取代苯间的Anion-π相互作用的快速计算,并与CCSD(T)/CBS方法的计算结果进行了比较。计算结果表明,本文方法得到的势能曲线与CCSD(T)/CBS势能曲线符合很好;与CCSD(T)/CBS方法的计算结果比较,本文方法预测平衡分子间距离均方根偏差为0.004 nm,相互作用能均方根偏差为2.81 k J?mol^(-1),说明本文方法合理可靠。本文方法可望在相关分子材料设计模拟领域发挥作用。展开更多
A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, ...A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, propionate, oxalate, succinate, glutarate, fluoride, chloride and sulfate were separated and determined in 33 min. The samples were pretreated with solid-phase extraction, which has high selectivity for removing a large number of metallic ions in the Bayer liquors, and filtered with a 0.45 μm filter membrane before being injected into the ion chromatographic system. The separation of six organic acids and three inorganic anions was achieved on an IonPac AS11-HC column with KOH as the eluent, and the detection was performed by a conductivity detection mode. No interference is found in the presence of fluorate, chlorate and sulphate when organic acids are determined. The calibration graphs of peak area for all the analytes are linear over a wide range. The relative standard derivation of the peak area of analytes is less than 2.14%. Under optimum conditions the detection ranges from 0.2 to 100.0 mg/L. The average recoveries of the added standards are between 94.3% and 102.8%.展开更多
By using the experimental approach of dropping liquid, the coupling of three anionic wetting agents with ten dust samples of sulfide ores was studied, and particularly the wetting effects of the wetting agents on the ...By using the experimental approach of dropping liquid, the coupling of three anionic wetting agents with ten dust samples of sulfide ores was studied, and particularly the wetting effects of the wetting agents on the sulfide dust influenced by factors of agent concentration and sulfate additive in the wetting agent solutions were investigated. The results show that when the solution temperature is about 20 ℃, all the selected wetting agents are effective to most dust samples, but the effect is different. Wetting agents are more effective to the dust which is difficult to be wetted. Wetting agent solution with sodium sulfate can improve the wetting ability of sulfide dust. For sodium dodecyl benzene sulfonate, the suitable concentration of sodium sulfate is 12 mmol/L. The cost of wetting agents can be reduced because the sodium sulfate is much cheaper than many surfactants. Since the dust of sulfide ores is composed of various minerals and elements, the whole effect of depressing dust should be considered while innovating a wetting agent.展开更多
The separation of Co 2+ from Zn 2+ , Cd 2+ by anion exchange chromatography was discussed. The chromatographic column containing anion resin 201×7 which was saturated with a solution of ammonium chloride. The eff...The separation of Co 2+ from Zn 2+ , Cd 2+ by anion exchange chromatography was discussed. The chromatographic column containing anion resin 201×7 which was saturated with a solution of ammonium chloride. The effects of the eluant acidity and eluant composition on the separation were investigated. The results indicate that this anion exchange chromatography is suitable to the separation of Co 2+ from Zn 2+ , Cd 2+ , and the condition of separation is simple and convenient. When the column is saturated with NH 4Cl solution (2.0 mol/L, pH=4.0), the separation can be completed effectively. Zn 2+ and Cd 2+ can also be separa ted when different eluants are used and the pure solution with high concentration of Zn 2+ , Cd 2+ respectively can be obtained ea sily.展开更多
In this work,the Fukui functions of the two ~2P resonance states of Be,a ~2P resonance state of Mg~–,and a ~2D resonance state of Ca~– have been determined.The trajectories of these resonance states,in conjunction w...In this work,the Fukui functions of the two ~2P resonance states of Be,a ~2P resonance state of Mg~–,and a ~2D resonance state of Ca~– have been determined.The trajectories of these resonance states,in conjunction with the complex rotation of the Hamiltonian,were used to determine their wave functions.The electron densities,Fukui functions,and values of the hyper-radius<r^2>were computed from these wave functions.The Fukui functions have negative regions in the valence shell in addition to the inner shell regions,indicating screening effects of the outer temporary electron.Selected configuration interactions with up to quadruple excitations were used along the trajectories and for computing the final wave function.Based on this data,the densities,Fukui functions,and<r^2>were calculated.展开更多
Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃ for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the...Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃ for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the morphology, particle size, surface area and configuration of the precursors were studied. The results show that the reactions of urea with aluminium nitrate and aluminium chloride result in agglomerates gels with bad filtering performance, the morphology is fibrillar. Aluminium sulphate-urea reactions result in the direct formation of amorphous powders with good filtering performance, of which morphology are regular spherical particles with larger granularity and smaller surface area. The reaction of mutual compound of aluminium sulphate and aluminium nitrate with molar ratio of 40:60 with urea can produce precursor with good filtering performance, spherical morphology, and uniform granularity distribution in the particle size range of 2-3 μm.展开更多
The adsorbabilities of the unmodified and modified bauxite tailings for Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ） ions were investigated. Batch experiments were carried out to determine the removal rate as a function of adsorben...The adsorbabilities of the unmodified and modified bauxite tailings for Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ） ions were investigated. Batch experiments were carried out to determine the removal rate as a function of adsorbent dosage, solution pH value and shaking time. The results show that the maximum removal rates of Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ ） are respectively 99%, 99% and 90% by using the modified bauxite tailings. The isoelectric point of the unmodified bauxite tailings is 3.6, and that of the modified bauxite tailings is 5.0, which shifts to lower pH values in Cr（Ⅵ） solution. This indicates a specific adsorption of the anionic species on the modified bauxite railings. A new band of Cr2O72 appears in the FTIR, showing that Cr（Ⅵ） is adsorbed on the modified bauxite railings in the form of chemistry adsorption. The adsorption data of Cr（Ⅵ） on the modified bauxite tailings are well described by Freundlich model. The investigations of kinetic models show that pseudo-second-order kinetic model provides the best correlation for the experimental data.展开更多
Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided ...Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided some information for anion recognition.It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl-.展开更多
By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variationa...By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.展开更多
A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations wit...A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form primary amine functionalized polymers are discussed; the efficiency of functionalization depends on the molecular weight of the polymeric organolithium(PLi). Efficient functionalizations are observed for PLi with n>10 000 g/mol. The poor functionalization yields using ketimines with enolizable hydrogens is explained. The use of N -trimethylsilyldiphenylcarbimide as a quantitative primary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized polymers using N -(benzylidene)methylamine as the functionalization agent are presented.展开更多
Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V...Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.展开更多
基金Project(51274242)supported by the National Natural Science Foundation of ChinaProject(2015CX001)supported by the Innovation-driven Plan in Central South University,China
文摘The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.
基金SupportedbytheNationalNaturalScienceFoundationofChina(No.20073042)TheNaturalScienceFoundationofAnhuiProvince (No .2 0 0 1kj2 63zc)
文摘A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmonic vibrational frequency calculations have been performed on the AX～U4（）1A1 state of O3 and AX～U4（）2B1 state of O-3. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of O-3. The theoretical spectrum obtained by employing CCSD（T）/6-311+G（2d,p） values are in excellent agreement with the observed one. In addition, the equilibrium geometry parameters, re（OO）= 0.135?5±0.000?5 nm and θe（O-O-O） =114.5±0.5°, of the AX～U4（）2B1 state of O-3, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.
基金supported by the National Natural Science Foundation of China(21173109,21573098)~~
文摘本文提出了一种可快速计算Anion-π作用强度的方法。该方法包含静电、极化和范德华作用。我们将取代苯的C≡N、C―F和C―H化学键作为键偶极,通过阴离子和取代苯的键偶极间相互作用来计算静电作用,根据键偶极大小随着环境变化而改变来计算极化作用。文中所需参数由模拟CCSD(T)/CBS势能曲线而确定。将本文方法应用于一系列卤素阴离子和取代苯间的Anion-π相互作用的快速计算,并与CCSD(T)/CBS方法的计算结果进行了比较。计算结果表明,本文方法得到的势能曲线与CCSD(T)/CBS势能曲线符合很好;与CCSD(T)/CBS方法的计算结果比较,本文方法预测平衡分子间距离均方根偏差为0.004 nm,相互作用能均方根偏差为2.81 k J?mol^(-1),说明本文方法合理可靠。本文方法可望在相关分子材料设计模拟领域发挥作用。
基金Project(2005CB623702) supported by the National Key Basic Research Program of China
文摘A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, propionate, oxalate, succinate, glutarate, fluoride, chloride and sulfate were separated and determined in 33 min. The samples were pretreated with solid-phase extraction, which has high selectivity for removing a large number of metallic ions in the Bayer liquors, and filtered with a 0.45 μm filter membrane before being injected into the ion chromatographic system. The separation of six organic acids and three inorganic anions was achieved on an IonPac AS11-HC column with KOH as the eluent, and the detection was performed by a conductivity detection mode. No interference is found in the presence of fluorate, chlorate and sulphate when organic acids are determined. The calibration graphs of peak area for all the analytes are linear over a wide range. The relative standard derivation of the peak area of analytes is less than 2.14%. Under optimum conditions the detection ranges from 0.2 to 100.0 mg/L. The average recoveries of the added standards are between 94.3% and 102.8%.
文摘By using the experimental approach of dropping liquid, the coupling of three anionic wetting agents with ten dust samples of sulfide ores was studied, and particularly the wetting effects of the wetting agents on the sulfide dust influenced by factors of agent concentration and sulfate additive in the wetting agent solutions were investigated. The results show that when the solution temperature is about 20 ℃, all the selected wetting agents are effective to most dust samples, but the effect is different. Wetting agents are more effective to the dust which is difficult to be wetted. Wetting agent solution with sodium sulfate can improve the wetting ability of sulfide dust. For sodium dodecyl benzene sulfonate, the suitable concentration of sodium sulfate is 12 mmol/L. The cost of wetting agents can be reduced because the sodium sulfate is much cheaper than many surfactants. Since the dust of sulfide ores is composed of various minerals and elements, the whole effect of depressing dust should be considered while innovating a wetting agent.
文摘The separation of Co 2+ from Zn 2+ , Cd 2+ by anion exchange chromatography was discussed. The chromatographic column containing anion resin 201×7 which was saturated with a solution of ammonium chloride. The effects of the eluant acidity and eluant composition on the separation were investigated. The results indicate that this anion exchange chromatography is suitable to the separation of Co 2+ from Zn 2+ , Cd 2+ , and the condition of separation is simple and convenient. When the column is saturated with NH 4Cl solution (2.0 mol/L, pH=4.0), the separation can be completed effectively. Zn 2+ and Cd 2+ can also be separa ted when different eluants are used and the pure solution with high concentration of Zn 2+ , Cd 2+ respectively can be obtained ea sily.
文摘In this work,the Fukui functions of the two ~2P resonance states of Be,a ~2P resonance state of Mg~–,and a ~2D resonance state of Ca~– have been determined.The trajectories of these resonance states,in conjunction with the complex rotation of the Hamiltonian,were used to determine their wave functions.The electron densities,Fukui functions,and values of the hyper-radius<r^2>were computed from these wave functions.The Fukui functions have negative regions in the valence shell in addition to the inner shell regions,indicating screening effects of the outer temporary electron.Selected configuration interactions with up to quadruple excitations were used along the trajectories and for computing the final wave function.Based on this data,the densities,Fukui functions,and<r^2>were calculated.
基金Project(5JJ3010) supported by the Natural Science Foundation of Hunan Province, China
文摘Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃ for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the morphology, particle size, surface area and configuration of the precursors were studied. The results show that the reactions of urea with aluminium nitrate and aluminium chloride result in agglomerates gels with bad filtering performance, the morphology is fibrillar. Aluminium sulphate-urea reactions result in the direct formation of amorphous powders with good filtering performance, of which morphology are regular spherical particles with larger granularity and smaller surface area. The reaction of mutual compound of aluminium sulphate and aluminium nitrate with molar ratio of 40:60 with urea can produce precursor with good filtering performance, spherical morphology, and uniform granularity distribution in the particle size range of 2-3 μm.
基金Project(2005CB623701) supported by the Major State Basic Research Development Program of China
文摘The adsorbabilities of the unmodified and modified bauxite tailings for Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ） ions were investigated. Batch experiments were carried out to determine the removal rate as a function of adsorbent dosage, solution pH value and shaking time. The results show that the maximum removal rates of Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ ） are respectively 99%, 99% and 90% by using the modified bauxite tailings. The isoelectric point of the unmodified bauxite tailings is 3.6, and that of the modified bauxite tailings is 5.0, which shifts to lower pH values in Cr（Ⅵ） solution. This indicates a specific adsorption of the anionic species on the modified bauxite railings. A new band of Cr2O72 appears in the FTIR, showing that Cr（Ⅵ） is adsorbed on the modified bauxite railings in the form of chemistry adsorption. The adsorption data of Cr（Ⅵ） on the modified bauxite tailings are well described by Freundlich model. The investigations of kinetic models show that pseudo-second-order kinetic model provides the best correlation for the experimental data.
基金Project (21302232) supported by the National Natural Science Foundation of China
文摘Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided some information for anion recognition.It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl-.
文摘By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
文摘A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form primary amine functionalized polymers are discussed; the efficiency of functionalization depends on the molecular weight of the polymeric organolithium(PLi). Efficient functionalizations are observed for PLi with n>10 000 g/mol. The poor functionalization yields using ketimines with enolizable hydrogens is explained. The use of N -trimethylsilyldiphenylcarbimide as a quantitative primary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized polymers using N -(benzylidene)methylamine as the functionalization agent are presented.
文摘Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.
