Synthesis and Characteristic Study on Complexes of Europium(Ⅲ) and Maleic Acid Doped with Non-Fluorescent Ions

Complex of europium （Ⅲ） with maleic acid, and binuclear complexes of europium（Ⅲ）with maleic acid doped with non-fluorescent ions gadolinium, lanthanum and yttrium, were synthesized. The compositions and structures of complexes were characterized with elemental analysis, single crystal X-ray diffraction, IR and DSC-TG. Fluorescent properties were studied with fluorescence spectrum. The results indicated that the strongest fluorescent complexes were obtained when the ratio of europium and non-fluorescent ion was 8：2. The order of Eu^3＋ fluorescence strengthened by three doped rare earths was Gd^3＋ 〉La^3＋ 〉Y^3＋

Synthesis, Crystal Structure and Luminescence of a New Europium(Ⅲ) Coordination Polymer with Imidazole Carboxylic Ligand

A new luminescent compound, {[Eu3（L）4（H2 O）8]·（NO3）·4 H2 O}n（1, H2 L = 2-（pyridine-3-yl）-imidazole-4,5-dicarboxylic acid） has been solvothermally synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction. 1 crystallizes in monoclinic, space group C2/c with a = 21.0183（19）, b = 9.5227（6）, c = 28.227（3） ?, β = 106.885（5）o, V = 5406.1（8） ?3, Dc = 2.038 g/cm3, μ = 3.358 mm-1, Mr = 1658.76, F（000） = 3247, Z = 4, the final R = 0.0488, wR = 0.1195 and S = 1.075. The deprotonated L ligand employs a μ4-bridge to coordinate with three Eu（Ⅲ） ion, forming a wave-like（3,4）-connected 2 D structure. The existence of π···π interaction between the pyridine rings of L ligands leads to an infinite 3 D network. Furthermore, the thermal analysis, powder diffraction and solid-state photoluminescent properties of compound 1 have also been investigated.

离子色谱法测定复方聚乙二醇电解质散(Ⅲ)中氯离子、硫酸根和碳酸氢根的含量

目的建立同时测定复方聚乙二醇电解质散(Ⅲ)中氯离子、硫酸根和碳酸氢根含量的离子色谱法。方法色谱柱为Dionex Ionpac^(TM) AS11-HC阴离子分析柱,保护柱为Dionex IonPac^(TM) AG11-HC,以10 mmol/L氢氧化钾为淋洗液进行等度洗脱,流速为1.2 mL/min,检测器为电导检测器,抑制器为Dionex AERS,抑制电流为30 mA,柱温为30℃,进样体积为10μL;按外标法计算氯离子和硫酸根的含量,按双对数拟合的标准曲线法计算碳酸氢根的含量。结果该色谱条件下,氯离子、硫酸根、碳酸氢根能有效分离,其线性范围分别为0.055~0.219 mg/mL(r为0.9999)、0.155~0.618 mg/mL(r为1.0000)、0.065~0.121 mg/mL(r为0.9999);回收率分别为98.06%~101.34%、97.37%~101.25%、97.16%~99.81%,RSD分别为1.1%、1.3%、1.0%(n=9);精密度、准确度、稳定性、耐用性考察的RSD均小于2%。结论建立的离子色谱法简单快速,准确度、精密度和耐用性良好,可同时测定复方聚乙二醇电解质散(Ⅲ)中氯离子、硫酸根、碳酸氢根的含量,适用于该药品的质量控制。

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.

Effect of cerium ion(Ⅲ) on corrosion resistance of organic-inorganic hybrid coating on surface of aluminum-tube used in refrigeration equipment

Organic?inorganic hybrid coating on the surface of aluminum-tube used in refrigeration equipment using cerium ion (III) as the additive was fabricated by sol?gel method, and the structure of the coating was confirmed by FT-IR. The results of the characterization show that the corrosion resistance of the coating with 1.5 mmol/L cerium ion (III) gains significant improvement, in which the colour retention time of CuSO4 extends to 500 s, the anti-acid and alkali corrosion rates reduce by 67% and 70% compared with the blank one, respectively, and the salt spray tests also show good corrosion resistance. The electrochemical tests demonstrate that the self-corrosion current density and potential of the sample with hybrid coating are about 2.877×10?7 A/cm2 and?0.550 V, respectively. The metallographic and SEM images show that the hybrid coating is uniform and dense, and the EDS analysis confirms that the coating is mainly composed of Al, Si and Ce elements.

Adsorption behavior and mechanism of Bi(Ⅲ) ions on rutile-water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ)Complex Eu(C14H9O3)2(C12H8N2)2(NO3)

A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.

Crystal Structure and Fluorescent Study of a Binuclear Europium(Ⅲ) Complex

A novel binuclear Eu（Ⅲ） complex [Eu2（dpa dioxide）2（NO3）4（bpdioxide）-（EtOH）] （dpa dioxide = di-2-pyridylamine N,N＇-dioxide, bpdioxide = 2,2＇-bipyridine N,N＇-dioxide） has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu（Ⅲ） ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089（7）, b = 11.4670（8）, c = 17.1440（12） A, α = 92.834（2）, β = 93.854（3）, γ = 95.433（2）°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3（2） A3, F（000） = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ（I）.

Synthesis and Fluorescent, Magnetic and Thermal Stability Properties of a New Europium（Ⅲ） Complex Eu2(C15H11O3)6(C12H8N2)2

A new europium（Ⅲ） complex Eu2(C15H11O3)6(C12H8N2)2 has been synthesized with 2-（4-Methylbenzoyl）benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 15.1238（5）, b = 13.5928（4）, c = 22.9840（7） ?, β = 104.132（3）o, V = 4582.0（2） ?3, Dc = 1.522 g/cm3, Z = 4, μ（Mo Kα） = 1.433 mm-1, F（000） = 2128, the final R = 0.0447 and wR = 0.0826. The Eu（Ⅲ） ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+: 5 D0 → 7 F1（594 nm） and 5 D0 → 7 F2（617 nm）. The complex is an antiferromagnetism system in the range of 150～300 K. Also reported in the paper is the thermal stability property of the title complex.

Adsorption behavior of Sb(Ⅲ) in single and binary Sb(Ⅲ)-Fe(Ⅱ) systems on cationic ion exchange resin: Adsorption equilibrium, kinetic and thermodynamic aspects

The present study dealt with the mechanism of competitive adsorption of Sb(Ⅲ)and Fe(Ⅱ)ions from a copper-containing aqueous solution on Purolite S957,a commercially available cationic ion-exchange adsorbent.Experiments were conducted using aqueous copper sulfate solutions containing either single or conjoint ions,using both sedentary and batch adsorption techniques to ascertain the sensitivity of the adsorption process to variation in p H,mass of resin,contact time,and temperature as well as establishing the optimal range of variables for maximum ion removal.The data from single ion adsorption tests were fitted by non-linear regression techniques to Henry,Langmuir,Freundlich,Temkin,and Dubinin–Radushkevich isotherm models.Freundlich isotherm for Sb(Ⅲ)and Freundlich and Henry models for Fe(Ⅱ)solutions best express the adsorption equilibrium data;while for binary ion electrolytes,the extended Freundlich model fitted the data satisfactorily.The kinetic model adequately describing adsorption was shown to be the pseudo-first-order,underscoring the dominant role of physical adsorption playing in the process.Thermodynamic parameters for the adsorption process reveal differences in the Sb(Ⅲ)adsorption mechanism from single ion and Sb(Ⅲ)-Fe(Ⅱ)containing electrolytes.The adsorption of Sb(Ⅲ)alone is endothermic,whereas the process becomes exothermic in the Sb(Ⅲ)-Fe(Ⅱ)system.

Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

Cr(Ⅲ)离子印迹聚合物的制备及性能研究

以Cr(Ⅲ)为模板离子,采用表面印迹法,将氨基化多壁碳纳米管改性为乙烯化多壁碳纳米管作为固体基质,通过印迹体系的优化,制备了一系列Cr(Ⅲ)离子印迹聚合物[Cr(Ⅲ)-IIPs]及相应的非印迹聚合物[Cr(Ⅲ)-NIPs].在较优实验条件下制备的Cr(Ⅲ)-IIP1,吸附量为3.82 mmol·g^(−1),印迹因子为1.65.通过扫描电子显微镜(SEM)、氮气吸附/脱附(BET)、红外光谱(FIR)、热重分析(TG)等对Cr(Ⅲ)-IIP1及相应的Cr(Ⅲ)-NIP1,进行结构表征和性能评价.研究结果表明,Cr(Ⅲ)-IIP1属于热稳定性良好的吸附材料,吸附行为符合准二级动力学模型和Freundlich等温吸附模型,以化学吸附和多分子层吸附为主;在“竞争离子”Co(Ⅱ)、Ni(Ⅱ)和Pb(Ⅱ)共存条件下,对Cr(Ⅲ)离子具有较强的吸附能力和良好的选择性.说明在较优实验条件下制备的Cr(Ⅲ)-IIP1,有望作为一种新型的Cr(Ⅲ)离子吸附材料,去除和回收废水中的Cr(Ⅲ)离子.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)3(Phen)2

A new europium（III） complex Eu（L）3（Phen）2（1） with 2-benzoylbenzoic acid（HL） and 1,10-phenanthroline（Phen） as ligands has been synthesized. Crystal data for the complex are as follows： monoclinic, space group P21/c, a = 2.2577（4）, b = 1.23484（19）, c = 1.8789（3） nm, β = 94.918（3）o, V = 5.2189（14） nm^3, Dc = 1.512 g/cm^3, Z = 4, μ（Mo Kα） = 1.269 mm^-1, F（000） = 2408, the final R = 0.0433 and w R = 0.1038. The Eu（III） ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu^3＋： ^5D0→^7F1（597 nm） and ^5D0→^7F2（615 nm） with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.

Effect of fluoride addition on electrochemical behaviors of V(Ⅲ) in molten LiCl-KCl

X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine with V(Ⅲ)to form VF_(6)^(3-).The electrochemical behavior of V(Ⅲ)was evaluated under condition of the molar concentration ratio of F−to Vn+(α)equal to 0:1,1:1,2:1,5:1,20:1 and 50:1,respectively.The results showed that a new reduction step appeared:VF_(6)^(3-)→V^(2+),and the reduction mechanism of vanadium ions became more complicated.The metallic vanadium was deposited on the tungsten electrode at−2.90 V in the LiCl−KCl melts for 6 h,and the products were characterized by SEM−EDS.It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF_(6)^(3-).

聚合物改性膨润土对钢渣渗滤液及其Cr(Ⅲ)离子的阻隔与吸附特性研究

【目的】针对传统膨润土防渗衬垫在侵蚀性环境中防渗性能会大幅劣化的难题,自主研发了一种聚合物改性膨润土。【方法】通过渗透实验研究了聚合物改性膨润土对高盐溶液、强碱溶液和实际钢渣渗滤液的渗透系数,并采用Batch吸附实验探究了吸附时间、溶液pH值和溶液浓度对聚合物改性膨润土吸附钢渣渗滤液中Cr(Ⅲ)离子的影响。【结果】实验结果表明:未改性的钠化钙基膨润土对侵蚀性溶液的刚性壁渗透系数高达1×10^(-8)m/s,而聚合物改性膨润土对高盐、强碱和钢渣渗滤液的柔性壁渗透系数均小于1×10^(-11)m/s,且刚性壁渗透系数约为3×10^(-11)m/s,在高盐、强碱等侵蚀性环境中表现出更优越的防渗性能。【结论】聚合物改性膨润土对Cr(Ⅲ)的吸附量随着吸附时间、溶液pH值和溶液浓度的增加而增加。钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)吸附符合准二阶吸附动力学模型;Langmuir等温吸附模型更好地描述了钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)的吸附特性。

Fabrication and adsorption property of novel adsorbent for potential application to wastewater with Fe(Ⅲ) ions

The spherical macroporous cellulose(SMC) was fabricated using medical absorbent cotton as raw material and nano CaCO3 as porogenic agents.And then,the phenylglycine was grafted onto the SMC to obtain the novel spherical macroporous cellulose derivative adsorbent(PSMC).FT-IR and scanning electron microscope(SEM) were employed to characterize the adsorbents and Fe3+ ions served as model solute to evaluate the adsorption property of the adsorbents.The experimental results show that the amount of porogenic agents and the value of pH have obvious influence on adsorption capacity of the adsorbents.The data of adsorption kinetic and isotherm display that the adsorbents possess excellent equilibrium adsorption capacity(348.94 mg/g) and have a bright prospect and considerable potential in the treatment of Fe3+ ions in wastewater.

Separation of indium(Ⅲ), gallium(Ⅲ), and zinc(Ⅱ) with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204): Part Ⅱ. Mechanism and kinetics of adsorbing indium(Ⅲ)

The mechanism of adsorbing indium(Ⅲ) from sulfate solutions with CL-P204Levextrel resin containing di(-2-ethylhexyl) phosphoric acid was examined by batch operation andinfrared spectra. The results showed that the P204 adsorbed on the resin behaved in the similar wayto solvent extraction except that it was as a monomer in resin adsorbing but in dimeric form insolvent extraction. Three factors including temperature, indium(Ⅲ) concentration of solution, andthe size of resin particles which influence the In^(3+)/H^+ exchange on CL-P204 Levextrel resin wereinvestigated by the modified limited batch technique in order to determine the kinetics ofIn^(3+)/H^+ exchange. It was found that the rate of ion exchange increased with the temperature andthe concentration of solution increasing and with the size of the resin particles decreasing.According to the expression developed by Boyd et al., the controlling factor of In^(3+)/H^+ exchangeon CL-P204 Levextrel resin was the diffusion through the resin particles. The effective diffusioncoefficient, activation energy, and entropy of activation in the particle-diffusion were determinedas 1.57 x 10^(-10) m^2/s, 11.9 kJ/mol, -84.1 J/(mol·K), respectively.

Electroreduction of Co(Ⅱ) and La(Ⅲ)in UreaMelt

Electroreduction of Co(Ⅱ)to metallic cohalt in urea melt is irrevsible in one step.The transfer coeffi-cient of electrode reaction of Co(Ⅱ)+2e=Co(O)and the diffusion coefficient of Co(Ⅱ)were determined.The lanthanum can be inductively codeposited with cobalt. The contents of lanthanum in cobalt-lanthanum de-posts increase with the shift of electrode potential to the negative direction and the raise of La(Ⅲ)/Co(Ⅱ)mo-lar ratio in the melt. The cyclic voltammetry,open circuit potential-time curve after potentiostatic electrolysisand electron probe analyas were used.

Adsorption of Rare Earth Ion La(Ⅲ) on Yunnan Bowl Tea Surface from Aqueous Solution

The adsorption characteristics of rare earth ion La(Ⅲ) on Yunnan bowl tea surface from aqueous solution and effects of various surfactants on the adsorption were studied. It was found that Yunnan bowl tea can adsorb strongly La(Ⅲ) and pH may affect drastically the adsorption amount of La(Ⅲ). The adsorption law of La(Ⅲ) on Yunnan bowl tea surface follows the Langmuir equation. The maximum adsorption amount of La(Ⅲ) can reach 15 mg·g (-1). A comprehensive adsorption model is suggested according to the experimental results.