碱土金属离子（Mg^2＋，Ca^2＋，Ba^2＋）掺杂对长余辉荧光粉SrAl2O4：Eu^2＋，Dy^2＋发光性能的影响

采用高温固相法制备了碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）掺杂的SrAl2O4：Eu^2＋,Dy^3＋长余辉荧光粉。XRD谱分析表明,随着基质中掺入的碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）浓度增加,基质晶格常数也随之发生变化。Mg^2＋,Ca^2＋和Ba^2＋ 3种碱土离子在SrAl2O4中的固溶范围分别为40％,15％和30％。光谱分析则表明在固溶范围内随着掺杂Mg^2＋,Ca^2＋和Ba^2＋浓度的增大,样品的发射峰值会在480～530nm范围出现规律性移动。适当浓度的Mg^2＋,Ba^2＋掺杂会不同程度地提高样品的发光强度,而Ca^2＋的掺杂则会降低发光强度。但是碱土金属离子（Mg^2＋,Ca^2＋,Ba^2＋）的掺杂并不能延长SrAl2O4：Eu^2＋,Dy^3＋荧光粉的余辉时间。     

SrAl2B2O7:Eu3+的发光性能和电子结构研究

采用固相法合成了SrAl2B2O7:Eu3+系列荧光粉,研究了它们在紫外和真空紫外激发下的发光性能.紫外激发下,SrAl2B2O7:Eu3+的最强发射峰位于610 nm附近,具有较高的发射镁度和较好的色纯度,但是在真空紫外激发下,其发光强度却比较弱.通过分析SrAl2B2O7:Eu3+的激发光谱与基质晶体的电子结构计算结果,对该现象进行了解释.第一原理的模拟计算表明,Ba2+的掺杂可以使SrAl2B2O7的带隙变宽,由此推论Ba2+的掺杂可以提高SrAl2B2O7:Eu3+样品在真空紫外激发下的发光强度.本研究的实验结果也证实了这一推论.     

杂质的添加对SrAl_2O_4∶Eu~(2 ),Dy~(3 )余辉发光特性的改善

采用溶胶 凝胶法制备SrAl2 O4 ∶Eu2 ,Dy3 磷光体 ,并在合成过程中添加硼或硅以探讨光致发光及长余辉发光性质。发现硼、硅添加物不仅是助熔剂 ,且能改良SrAl2 O4 ∶Eu2 ,Dy3 之长余辉的持续时间及余辉发光强度。基于不同磷光体样品的实验结果比较 ,综合材料表面微结构观察、X射线衍射图谱、热释发光光谱与余辉衰减曲线的测量等实验结果分析 ,推断在SrAl2 O4 ∶Eu2 ,Dy3 中添加硼、硅可导致磷光体缺陷增加并稳定活化剂Eu2 的价态。     

纳米SrAl2O4:Eu2+,Dy3+长余辉发光材料的制备与性能

采用水热-均匀共沉淀法制备了纳米SrAl2O4:Eu2+,Dy3+长余辉发光材料.通过XRD、TEM、荧光光谱、热释光谱对其结构和性能进行分析.XRD结果表明所制备的SrAl2O4:Eu2+Dy3+纳米发光材料为单相,属单斜晶系.TEM测试表明纳米SrAl2O4:Eu2+,Dy3+发光材料为规则的球状粒子,粒径为50～80 nm,且分散性良好.激发和发射光谱测试表明,样品的激发光谱是峰值在356 nm 的连续宽带谱,发射光谱是峰值位于512 nm的宽带谱,与SrAl2O4:Eu2+,Dy3+粗晶材料相比,激发和发射光谱都出现了"蓝移"现象.样品的热释光峰值位于358 K,适合于产生长余辉.     

高温固相法合成长余辉发光材料Sr_(0.96)Al_2O_4:Eu_(0.02)~(2+),Dy_(0.02)~(3+)

以高温固相法合成了Sr0.96Al2O4:Eu2+0.02,Dy3+0.02长余辉发光材料,其激发光谱和发射光谱均为宽带谱,激发光谱为300～480nm,具有从紫外到蓝绿光波段能量的吸收范围.随着稀土元素Eu2+掺杂量的增加,发光强度逐渐增强,当Eu2+掺杂量达到2(mol)%时,材料的发光强度最大.辅助激活剂Dy3+的添加能显著改善材料的余辉性能.Sr0.96Al2O4:Eu2+0.02,Dy3+0.02在25W日光灯激发30min后,黑暗环境中余辉长达3h.     

Dy3+,Eu3+双掺单基质Ca9Y(PO4)7白色荧光粉的合成与发光性能

以具有多种格位的Ca9Y(PO4)7作为基质, 以Dy3+和Eu3+作为共激活剂, 利用高温固相法合成了一种单基质白光荧光粉. X射线衍射证实样品属于三方晶系菱面体结构, Dy3+和Eu3+在Ca9Y(PO4)7晶体中占据了Y3+ 的格位. 样品在365 nm紫外线激发下, 荧光光谱同时出现了Dy3+和Eu3+的特征发射, 且发光强度以及色度坐标随着Dy3+和Eu3+掺杂比率的变化而有规律变化, 所有样品的发射均处于白光区域. 利用近紫外芯片作为激发源, 单一基质白色荧光粉Ca9Y1-x-y(PO4)7: xDy3+, yEu3+可应用于白光发光二极管等领域.     

喷雾热解法制备球形SrAl_2O_4:Eu,Dy长余辉发光材料

采用喷雾热解两段法制备了SrAl2O4:Eu,Dy长余辉发光材料,利用SEM、荧光长余辉亮度测试、F-4500荧光分光光度等方法分析了不同制备工艺条件下SrAl2O4:Eu,Dy发光材料的形貌、余辉性能以及光谱性能的变化。采用喷雾热解两段法可制备出余辉性能良好的球形SrAl2O4:Eu,Dy长余辉发光材料。前驱体溶液浓度、热解温度、添加剂对产物的形貌、粒度分布、发光性能有较大影响。较之高温固相法,喷雾热解法制备的SrAl2O4:Eu,Dy具有合成温度低、发光性能好、形貌好、粒度分布窄等优点。     

高温固相法合成长余辉发光材料Sr0.96Al2O4:Eu2+0.02,Dy3+0.02

以高温固相法合成了Sr0.96Al2O4:Eu2+0.02,Dy3+0.02长余辉发光材料,其激发光谱和发射光谱均为宽带谱,激发光谱为300～480nm,具有从紫外到蓝绿光波段能量的吸收范围.随着稀土元素Eu2+掺杂量的增加,发光强度逐渐增强,当Eu2+掺杂量达到2(mol)%时,材料的发光强度最大.辅助激活剂Dy3+...     

SrAl2O4:Eu,Dy发光粉的机械余辉与机械劣化研究

研究了SrAl2O4:Eu,Dy发光粉的机械余辉与机械劣化现象.结果表明,机械余辉强度与所施加的机械压力的大小及稀土掺杂离子的浓度有关.发光粉所受机械压力越大,掺杂Dy3+浓度越高,机械余辉强度越高;掺杂Eu2+浓度的变化,对机械余辉影响较小.从机械劣化研究结果可知,机械外力会导致荧光劣化和余辉劣化,而且后者总是先于前者发生.另外还对机械余辉与机械劣化机制进行了探讨,提出机械余辉是由机械能转化而来的热能将陷阱捕获的电子和空穴激发,二者复合导致发光;机械劣化是由于机械外力破坏了晶体结构,而且率先破坏晶格畸变严重的部分(包含Dy3+或空位的部分).     

Ba_3(PO_4)_2:Ce~(3+),Dy~(3+)荧光粉的组成与发光特性研究

在活性炭还原气氛下高温固相法合成了Ba3(PO4)2:Ce3+,Dy3+紫外发射荧光粉。XRD图谱表明,烧结温度为1100℃时保温处理3 h,样品为单相的Ba3(PO4)2型六方晶系结构。荧光光谱显示:单掺Ce3+样品中,Ce3+掺杂浓度为8%(摩尔分数)时样品的发光最强,发射峰的位置处在350 nm附近(Ce3+的2D→2F5/2和2D→2F7/2跃迁发射)。适量的Sr2+取代部分Ba2+离子,改变了基质晶格环境,使样品的发光强度得到提高且发射峰向长波方向红移。引入Dy3+作为敏化剂,样品发射峰红移到386 nm,亮度增强,主要是由于Dy3+和Ce3+之间发生了有效的能量传递过程。确定了Dy3+的最佳掺杂浓度为3%,发光强度提高了27%。     

啤酒酵母生理代谢过程中钠、钾、镁、钙离子含量变化的跟踪检测

采用空气-乙炔火焰原子吸收光谱法分别测定了啤酒酵母发酵液中的Na^ 、K^ 、Mg^2 、Ca^2 离子动态变化中的含量,用La^3 盐消除P对Ca^3 的干扰,以Sr^2 盐作为Na^ 、K^ 的消电离剂。本实验室采用配制培养基,通过对不同种类及不同发酵阶段培养的发酵液样品进行测定,以研究在啤酒酵母生长代谢过程中Na^ 、K^ 、Mg^2 、Ca^2 离子代谢动态变化。方法的Na^ 、K^ 、Mg^2 、Ca^2 相对标准偏差(RSD)分别为0．31％,0．73％。1．78％,0．28％;样品加标回收率为98％-107％;检出限：Na^ 为0．159mg／L,K^ 为0．789nag／L,Mg^2 为0．039mg／L,Ca^2 为0．029mg／L。该方法简便快速,具有很好的精密度。     

巯基树脂对金属离子的吸附性能(Ⅱ)

研究了自合成的巯基树脂对重金属离子Ag 、Hg2 、Cr3 的吸附容量、吸附动力学、等温吸附过程等静态吸附性能,影响吸附的因素和吸附机理.结果表明,该树脂对上述3种离子吸附能力强,吸附量分别达6.56mmol/g、3.25mmol/g、2.10mmol/g.树脂对各重金属离子等温吸附在实验浓度范围内符合Langmuir或Freundlich方程.吸附机理研究表明,巯基与金属离子发生了离子交换和配位反应,化学吸附起支配作用;另外树脂对Ag 、Hg2 吸附过程中存在一定的氧化还原现象.     

Effect of metal cations [Li+, Na+, K+, Be2+, Mg2+, and Ca2+] on the structure of 2‐(3′‐hydroxy‐2′‐pyridyl)benzoxazole: A theoretical investigation

Density functional theory calculations were performed at the B3LYP/6‐311++G(d,p) level to systematically explore the geometrical multiplicity and binding strength for the complexes formed by alkaline and alkaline earth metal cations, viz. Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ (Mⁿ⁺, hereinafter), with 2‐(3′‐hydroxy‐2′‐pyridyl)benzoxazole. A total of 60 initial structures were designed and optimized, of which 51 optimized structures were found, which could be divided into two different types: monodentate complexes and bidentate complexes. In the cation‐heteroatom complex, bidentate binding is generally stronger than monodentate binding, and of which the bidentate binding with five‐membered ring structure has the strongest interaction. Energy decomposition revealed that the total binding energies mainly come from electrostatic interaction for alkaline metal ion complexes and orbital interaction energy for alkaline earth metal ion complex. In addition, the electron localization function analysis show that only the Be? O and Be? N bond are covalent character, and others are ionic character. © 2012 Wiley Periodicals, Inc.     

Effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water coordination on the structure of glycine and zwitterionic glycine

Interactions between metal ions and amino acids are common both in solution and in the gas phase. Here, the effect of metal ions and water on the structure of glycine is examined. The effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water on structures of Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (m = 0, 2, 5) complexes have been determined theoretically by employing the hybrid B3LYP exchange-correlation functional and using extended basis sets. Selected calculations were carried out also by means of CBS-QB3 model chemistry. The interaction enthalpies, entropies, and Gibbs energies of eight complexes Gly.Mn+ (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) were determined at the B3LYP density functional level of theory. The computed Gibbs energies DeltaG degrees are negative and span a rather broad energy interval (from -90 to -1100 kJ mol(-1)), meaning that the ions studied form strong complexes. The largest interaction Gibbs energy (-1076 kJ mol(-1)) was computed for the NiGly2+ complex. Calculations of the molecular structure and relative stability of the Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+; m = 0, 2, and 5) systems indicate that in the complexes with monovalent metal cations the most stable species are the NO coordinated metal cations in non-zwitterionic glycine. Divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ prefer coordination via the OO bifurcated bonds of the zwitterionic glycine. Stepwise addition of two and five water molecules leads to considerable changes in the relative stability of the hydrated species. Addition of two water molecules at the metal ion in both Gly.Mn+ and GlyZwitt.Mn+ complexes reduces the relative stability of metallic complexes of glycine. For Mn+ = Li+ or Na+, the addition of five water molecules does not change the relative order of stability. In the Gly.K+ complex, the solvation shell of water molecules around K+ ion has, because of the larger size of the potassium cation, a different structure with a reduced number of hydrogen-bonded contacts. This results in a net preference (by 10.3 kJ mol(-1)) of the GlyZwitt.K+H2O5 system. Addition of five water molecules to the glycine complexes containing divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ results in a net preference for non-zwitterionic glycine species. The computed relative Gibbs energies are quite high (-10 to -38 kJ mol(-1)), and the NO coordination is preferred in the Gly.Mn+(H2O)5 (Mn+ = Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) complexes over the OO coordination.     

Separation of strontium from simulated waste in K2SO4/Nitrate medium containing Sr2+, Eu3+, Ce3+, Pd2+, Rh3+, Ru3+, UO 2 2+ , Fe3+, Cr3+, Ni2+, Al3+, Ca2+ and Cs+, by strongly basic anion exchanger

In this work Strontium was separated selectively form, Pd²⁺, Ni²⁺ and Ca³⁺ using anionic resins of Amberlite type IRA-900 and IRA-410 from nitrate medium. The Separation of strontium by strongly basic anion exchangers IRA-410 and IRA-900 from simulated waste containing, Sr²⁺, Eu³⁺, Ce³⁺, Pd²⁺, Rh³⁺, Ru³⁺, VO₂ ²⁺, Fe³⁺, Cr³⁺, Ni²⁺, Al³⁺, Ca²⁺, and Cs⁺, in K₂SO₄/nitrate medium which adsorbed as strontium sulphate complex was achieved through ligand- ligan exchange. The elution of strontium carried out via “loading” the column with a solution of 0.03N EDTA in presence of 0.1N NaNO₃ at pH7 where Sr²⁺ has low K_d value. An inductively Coubled Plasma — Optical Emission Spectrometry (ICP — OES) of ARL type model 3520, was used for elemental analysis.     

Theoretical study of interaction of 2,6-dithiopurine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cations

The geometries of the complexes of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with different possible 2,6-dithiopurine anions (DTP) were studied. The complexes were optimized at the B3LYP level and the 6-311++G(d, p) basis set. The interactions of the metal cations at different nucleophilic sites of various possible 2,6-dithiopurine anions were considered. It was revealed that metal cations would interact with 2,6-dithiopurine anions in a bicoordinate manner. In the gas phase, the most preferred position for the interaction of Li⁺, Na⁺, and K⁺ cations is between the N₃ and S₂ sites, while all divalent cations Be²⁺, Mg²⁺, and Ca²⁺ prefer binding between the N₇ and S₆ sites of the corresponding 2,6-dithiopurine. The influence of aqueous solvent on the relative stability of different complexes has been examined using the Tomasi’s polarized continuum model. The basis set superposition error (BSSE) corrected interaction energy was also computed for complexes. The AIM theory has been applied to analyze the properties of the bond critical points (electron densities and their Laplacians) involved in the coordination between 2,6-dithiopurine anions and the metal cations. It was revealed that aqueous solution would have significant effect on the relative stability of complexes obtained by the interaction of 2,6-dithiopurine anions with Mg²⁺ and Ca²⁺ cations. The effect of metal cations on different NH and CS stretching vibrational modes of 2,6-dithiopurine has also been discussed.     

Effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water coordination on the structure and properties of L-arginine and zwitterionic L-arginine

Interactions between metal ions and amino acids are common both in solution and in the gas phase. The effect of metal ions and water on the structure of L-arginine is examined. The effects of metal ions (Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ni(2+), Cu(2+), and Zn(2+)) and water on structures of Arg x M(H2O)m , m = 0, 1 complexes have been determined theoretically by employing the density functional theories (DFT) and using extended basis sets. Of the three stable complexes investigated, the relative stability of the gas-phase complexes computed with DFT methods (with the exception of K(+) systems) suggests metallic complexes of the neutral L-arginine to be the most stable species. The calculations of monohydrated systems show that even one water molecule has a profound effect on the relative stability of individual complexes. Proton dissociation enthalpies and Gibbs energies of arginine in the presence of the metal cations Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ni(2+), Cu(2+), and Zn(2+) were also computed. Its gas-phase acidity considerably increases upon chelation. Of the Lewis acids investigated, the strongest affinity to arginine is exhibited by the Cu(2+) cation. The computed Gibbs energies DeltaG(o) are negative, span a rather broad energy interval (from -150 to -1500 kJ/mol), and are appreciably lowered upon hydration.     

Study of Complex Formation Between Dicyclohexano-18-Crown-6 (DCH18C6) with Mg 2+, Ca2+, Sr 2+, and Ba2+ Cations in Methanol–Water Binary Mixtures Using Conductometric Method

The complexation reactions between Mg²⁺,Ca²⁺,Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H₂O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr ²⁺ and DCH18C6-Ba²⁺versus the composition of MeOH–H₂O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg²⁺ and DCH18C6-Ca²⁺ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔH_c°, ΔS_c°) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H₂O binary system is: Ba²⁺>Sr²⁺>Ca²⁺> Mg²⁺.