Adsorption behavior and adsorption mechanism of Cu(Ⅱ) ions on amino-functionalized magnetic nanoparticles

Amino-functionalized magnetic nanoparticle （NH2-MNP） were prepared by a sol-gel approach. The adsorption behavior of Cu（II） ions on NH2-MNP was discussed systematically by batch experiments. The effects of initial Cu（II） ions concentration, time, pH and temperature were investigated. In kinetic studies, the pseudo-second-order model was successfully employed, and the pseudo-first-order model substantiated that Cu（II） adsorption on NH2-MNP was a diffusion-based process. Langmuir model and Dubinin-Radushkevich model （R2〉0.99） were more corresponded with the adsorption isotherm data of Cu（II） ions than Freundlich model. The adsorption capacity was increased with the increment of temperature and pH. NH2-MNP remains excellent Cu（II） recoveries after reusing five adsorption and desorption cycles, making NH2-MNP a promising candidate for repetitively removing heavy metal ions from environmental water samples. According to the results obtained from adsorption activation energy and thermodynamic studies, it can be inferred that the main adsorption mechanism between absorbent and Cu（II） ions is ion exchange-surface complexation.

Raman spectroscopy and ionic structure of Na_3AlF_(6-)Al_2O_3 melts

Raman spectrum of molten cryolite was recorded. Based on the new understanding of the scattering coefficients, contents of various structural entities in acidic NaF-AlF3 melts at 942-1 024 ℃ in previous research were reanalyzed. The new quantitative analysis results show that when cryolite ratio（CR） is less than 2, AlF4- is the dominant anion in the melts, and its mole fraction is about 0.70 for melts with CR=1.5 and 0.50 for melts with CR=2. When CR is more than 2.5, the mole fraction of AlF6^3- is relatively large, which is around 0.45 for melts with CR=2.5. Ionic structure of Na3AlF6-Al2O3 melts was investigated by UV-Raman spectroscopy. Octahedral AlF6^3- and tetrahedral AlF4- are proved to exist with possible partial replacement of F- by O^2-. Al2O2F4^2- with a large scattering coefficient also exists in the melts in which alumina concentration is more than 4% （mass fraction）. The increase of temperature causes blue-shift of the bands in the Raman spectra.

MS/MS Study of Deoxydinucleotides Bound with Alkali-metal Ions Using ESI-MS

Positive ion ESI-MS has been used to examine the fragmentation pathways of the complex ions of deoxydinucleotides with H+, Na+, K+ by LCQ instrument. It had been found that the dissociation varied markedly due to the differences of the base sequence. The alkali-metal ion binding site and the characterization of dissociation were directed by the size of metal ion, the sequence of base and the steric hindrance.

Identification of Complex Ions of Nb(V)in FLINAK-O^(2-)System by Infrared Spectra

The FT-IR spectra for K_2NbF_7-FLINAK-O^(2-) solution were measured and compared with the spectra of crystalline K_2NbF_7 and K_2NbOF_6.The results show that the niobium fluoro-complex and/or oxyfluoro-complex ions are presented in these solutions.NbF_7^(2-) complex ion is the predominant species in Nb(V)-FLINAK solution(not considering oxide impurity).The influence of O^(2-) on the oxyfluoro-complex ions shows that NbOF_6^(3-) as a stable monooxyfluoro-complex anion presented in FLINAK-O^(2-) systems and the number of NbOF_6^(3-) species are increased with increasing of O^(2-) when molar ratio of O^(2-)/Nb(V) is less than 1.

Computerized Simulation on the Structure of Cryolite-Alumina Melts

Monte Carlo calculations were performed on liquid ionic solution of saturated alumina in cryolite melt containing a total of 205 ions. The local structure and radial distribution functions of the melt were computerized by Monte Carlo method at 1283 K. It has been found that there exist the complex ionic clusters such as AlOF_3^(2-), AlOF_4^(3-), AlF_4^-, AlF_5^(2-), AlOF_2^- etc., as well as oxygen-bridge and flourine-bridge ionic clusters. In the melt studied, Al^(3+) ions tend to have preferential even coordination number of 4F^- ions.

Adsorption and reduction of platinum(Ⅳ) chloride complex ions on activated carbon

The adsorption kinetics of platinum（IV） chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt（IV） chloride complex ions, temperature, rate of mixing and pH. It was found that the value of activation energy of the studied process is equal to 19.7 kJ/mol. From the ICP MS analysis it was confirmed that platinum ions （Pt（IV） and Pt（II）） are removed from the solution due to the adsorption and are further reduced to the metallic state. Such mechanism was confirmed by XPS analysis which showed that on the carbon surface three forms of platinum species, i.e. Pt（0）, Pt（II） and Pt（IV）, exist. The presence of platinum in the solution at different oxidation states was also confirmed spectrophotometrically by identification of their characteristic absorption bands. The metallic form of Pt present on the surface of activated carbon was observed in the form of small spherical islands with the diameter not exceeding 500 nm. Those islands consist of smaller, flake-shape particles with a thickness of about 35 nm.

Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.

REPLACED SITE OF Eu^(2+) ION IN THE COMPLEX FLUORIDES WITH THE PEROVSKITE CRYSTAL STRUCTURE

The replaced site of Eu^(2+) ion is dependent on the electronegativity difference of the cations in complex fluorides.In the mixed fluoride KMgF_3:Eu^(2+),Eu^(2+) ion occupies K^+ site,its emission spectrum is a sharp line and its valence-state is stable.

Synthesizes and Characterization Studies of Some Metal Ion Complexes with EOSBE and MOSBE

This work includes synthesis of 2,2＇-（5,5＇-（ethane-1,2-diyl）bis（1,3,4-oxadiazole-5,2diyl））bis（sulfanediyl）dibenzenamine （EOSBE） and 2,2＇-（5,5＇-methylenebis（1,3,4-oxadiazole-5,2-diyl）bis（sulfanediyl））dibenzenamine （MOSBE）. All synthesized ligands were characterized by IR, ^1H-NMR, ^13C-NMR, UV-visible spectroscopies and molar conductivity. A series of complexes with a general formula [M2LCl4]. Where M（Ⅱ） = Co, Ni, Cu and Zn; L = EOSBE and MOSBE were synthesized in basic media using KOH solution. In these complexes both ligands are bidentate ligands coordinated through sulfur and nitrogen. All complexes have been characterized by IR-spectra, UV-visiblc spectra, conductivity and magnetic susceptibility.

Adsorption of uranyl complex ions on hydrous titanium oxide (HTO)——Ⅱ Infrared spectrum investigation

-The i. r. spectra of Na4 [UO2 (CO3)3], Na [UO2 (OH)3] and the surface species of uranium on HTO underthe condition of flowing natural seawater and concentrated seawater (NaCl-NaHCO3-U) were recorded, with the bands of urany! of surface species obtained and the finding that iigands of surface species besides HTO are mainly water and OH, and there are some CO32- groups under the condition of natural seawater. Some relations between the complex properties and the j. r. spectroscopic characters for uranyl complexes were studied, and the transferred change quantity of surface complex was calculated.Structure models for surface species of adsorption are herein presented and the mechanism for uranium adsorption is deduced.

Detection of Hydrogen Peroxide Photogenerating from a Hypocrellin B Derivative

In order to f urther improve the photosensitizing activity of hypocrellin B(HB), the complex o f 5,8 di Br HB with Al 3+ was designed and synthesized in high yield. Th e complex of aluminium ion with 5,8 di Br HB is a new water soluble perylene quinonoid derivative with enhanced absorption over HB in the phototherapeutic wi ndow (600-900 nm). Electron paramagnetic resonance (EPR) measurement and 9,10 diphenyl anthracene bleaching methods were used to investigate the photosensiti zing activity of [Al 2(5,8 di Br HB)Cl 4] n in the prese nce of oxygen. Singlet oxygen, superoxide anion radical, hydroxyl radical can be generated by [Al 2(5,8 di Br HB)Cl 4] n photosensit ization. The results showed that the production of hydroxyl radical ( · OH) by [Al 2(5,8 di Br HB)Cl 4] n photosensitization comes from the Fenton Haber Weiss reaction and the decom position of DMPO 1O 2 adduct. Formation of H 2O 2 as one of main intermedi ates in the photogeneration of hydroxyl radical was detected by using the cataly zed oxidation of the DPD reagent by the POD enzyme method. Moreover, the experim ents of EPR spin trap and catalase enzyme excluded the effect of organoperoxide on DPD oxidization. These results further support the proposed mechanism of · OH formation.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.

Density and ionic structure of NdF_3-LiF melts

NdF3-LiF melts are commonly used in the electrolysis process of metallic neodymium production. Research on the density and ionic structure of the electrolyte is important for its close connection with the electrolysis mechanism and process. In this paper, the density of LiF-NdF3 melts was studied by the Archimedes method. The results showed that the density decreased with increasing temperature and LiF contents. The changing law was discussed and explained in terms of the micro ionic structure of the melts....

Ion–solvent chemistry in lithium battery electrolytes: From mono-solvent to multi-solvent complexes

The building of safe and high energy-density lithium batteries is strongly dependent on the electrochemical performance of working electrolytes, in which ion–solvent interactions play a vital role. Herein, the ion–solvent chemistry is developed from mono-solvent to multi-solvent complexes to probe the solvation structure and the redox stability of practical electrolytes. The decrease in energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of solvents in lithium-ion solvation shells becomes less significant as the number of coordinated solvents increases, but both the HOMO and LUMO energies of the coordinated solvents remain lower than those of free solvents. A positive and approximately linear relationship was found between the decrease in the HOMO/LUMO energy and the average binding energy between Li+ and the coordinated solvents. A binary-solvent complex model further highlight the significant importance of the electrolyte solvation environment in regulating electrolyte stability, and it is essential to consider electrolyte stability from the perspective of ion–solvent complexes. These fresh insights into the energy chemistry of multi-solvent complexes provide critical references for electrolyte design and cell optimization.

Theoretical Studies on Complexes of Calcium Ion with Amino Acids

The complexes formed by calcium ion and 12 common amino acids were investigated systematically in the gas phase at the level of MP2/6-311＋＋G（d,p）//MP2/6-3 1G（d,p）.The results show that the salt-bridge structure is the most preferred motif for Ca2＋ binding aliphatic amino acids without heteroatom in the side chain,while charge-solvated（CS） structure is the most preferred motif for Ca2＋ binding other amino acids except for glutamine and lysine.IR spectra of Gln-Ca2＋ and Asn-Ca2＋ complexes were calculated and compared well with the available experiments.From the study in aqueous solution,the bidentate salt-bridge structure was determined to be the most favorable for all the twenty kinds of amino acids to chelate Ca2＋ to both the oxygen atoms of the negatively carboxylate group in the backbone.

Effect of Mixing on Properties and Microstructure of Magnesium Oxychloride Cement

This paper investigated the effect of mixing on the properties of magnesium oxychloride cement, such as apparent viscosity, setting time, compressive strength, and specific strength as well. The phase composition and crystallographic structure of the cement were determined by X-ray diffraction and scanning electron microscopy. The results indicate that the increases of stirring rate and mixing time change apparent viscosity distinctly, shorten setting time and enhance mechanical property. Magnesium oxychloride cement after mixing for 20 min exhibits the optimal mechanical performance. The effect of stirring rate on the phase composition of magnesium oxychloride cement dominates over the effect of mixing time. The increases of stirring rate and mixing time can increase the dispersion state and accelerate the neutralization, thus promoting the strength of magnesium oxychloride cement due to the formation of stable 5·1·8 phase, needle-like crystals and continuous crystalline structure in the whole cement matrix. The properties and microstructure of magnesium oxychloride cement at a stirring rate of 280 rpm are better than those at 140 rpm.