镨和镱掺杂Ba2SiO4∶Eu^2＋荧光材料的合成与发光性能

采用高温固相反应法分别合成了变价稀土镨和镱离子掺杂的绿色荧光粉[Ba（2-n-1.5x）REx]SiO4∶nEu^2＋（n=0.03,RE=Pr,Yb;x=0,0.02,0.05,0.10）。结果表明：所有合成荧光粉的激发峰均为250-400 nm的宽峰,与近紫外LED的发射光波长相匹配。发射峰位于450-550 nm之间,是Eu2＋的5d-4f跃迁的典型发射。Pr^3＋和Yb3＋的掺入并未改变Ba2SiO4∶Eu^2＋的相组成,但对荧光强度的影响大,且与掺杂元素、掺杂量和煅烧温度相关。当掺杂Pr^3＋和Yb3＋的量为x=0.02时,经1150℃煅烧所得荧光粉的发光强度分别是未掺杂时的595%和168%。证明三价稀土离子掺杂可以导致基质中的电荷缺陷而敏化Eu^2＋离子的发光,而变价稀土离子的掺杂可以大大提高电荷缺陷,导致荧光强度的进一步提高。     

镨和镱掺杂Ba2 SiO4:Eu2+荧光材料的合成与发光性能

采用高温固相反应法分别合成了变价稀土镨和镱离子掺杂的绿色荧光粉[Ba(2-n-1.5x)REx]SiO4:nEu2+ (n=0.03, RE=Pr, Yb;x=0, 0.02,0.05,0.10).结果表明: 所有合成荧光粉的激发峰均为250～400 nm的宽峰, 与近紫外LED的发射光波长相匹配.发射峰位于450～550 nm之间, 是Eu2+的5d-4f跃迁的典型发射.Pr3+和Yb3+的掺入并未改变Ba2SiO4:Eu2+的相组成, 但对荧光强度的影响大, 且与掺杂元素、掺杂量和煅烧温度相关.当掺杂Pr3+和Yb3+的量为x=0.02时, 经1150 ℃煅烧所得荧光粉的发光强度分别是未掺杂时的595%和168%.证明三价稀土离子掺杂可以导致基质中的电荷缺陷而敏化Eu2+离子的发光, 而变价稀土离子的掺杂可以大大提高电荷缺陷, 导致荧光强度的进一步提高.     

碳酸镨的结晶活性、外观形貌及结晶生长机制

采用原位pH值测定法确定了碳酸镨的结晶活性区域,并用扫描电镜观测了不同结晶区域结晶碳酸镨的外观形貌.结果表明在低配比区域(NH4HCO3/PrCl3的摩尔比小于3)为碳酸镨的易结晶区域,结晶产物为交叉层叠的花瓣形颗粒;在高配比区域(NH4HCO3/PrCl3的摩尔比大于3)为碳酸镨的可结晶区域,延长陈化时间可以得到鱼鳞片状的亮晶产物;所有结晶碳酸镨都具有镧石型结构,其基本构筑单元为片状结晶,这与镧石的层状结构相关.影响结晶的主要因素是加料比,其它因素象温度,加料方式和搅拌强度等对结晶过程也有影响.     

Characterization and DNA Interaction of Lanthanide Complexes Based on Thiourea Ligand

Three isostructural lanthanide complexes,namely[Ln(L)₃·CH₃ OH](Ln=Tb(1),Dy(2),Ho(3),HL=N-(pyridin-2-ylcarbamothioyl)benzamide),were successfully synthesized and characterized by IR,UV,elemental analysis,single-crystal X-ray diffraction and DNA-biding analysis.X-ray single-crystal diffractions show that the family of lanthanide complexes crystallizes in monoclinic C2/c space group.Each lanthanide atom is coordinated with three carbonyl-O atoms,three pyridyl-N atoms and three imine-N atoms from three distinct L^-1 ligands,forming a distorted tricapped trigonal prism.The binding properties of complexes with ct-DNA were studied by simulating the physiological environment of human body.The results suggest that compounds could bind with ct-DNA through interaction under a spontaneous process.     

配位诱导的硝酸铜与水杨酸甲酯的高选择性自由基硝基化反应

硝酸铜与水杨酸酯的硝基化反应得到了高收率的对位产物。电子吸收光谱、循环伏安、电喷雾质谱的研究表明该反应经历的是一个自由基硝基化机理。硝酸铜与水杨酸甲酯的配位促使硝酸根断裂氮氧键产生硝基自由基、氧自由基和配合物自由基。硝基自由基与水杨酸甲酯或配合物反应得到硝基水杨酸甲酯或硝基化配合物。硝基化配合物经过水解将铜离子转化成氧化铜沉淀而生成硝基水杨酸甲酯。     

镧石型碳酸镨钕向碱式碳酸镨钕的相转变反应特征及其应用

本文研究了镧石型碳酸镨钕[（PrNd）₂（CO₃）₃·8H₂O,LPN]在95℃的不同起始pH值的溶液中陈化不同时间所得样品的XRD衍射图,证明所得样品为碱式碳酸镨钕[（PrNd）（OH）（CO₃）,BPN]。为此,详细研究了这一相态转变的反应条件以及粒子特征变化。结果表明：LPN是由片状或条状结晶连生而成的聚集体,具有大的粒度和小的堆密度。当在热的水溶液中陈化时,由于水解反应而发生由LPN向BPN的相转变。这一相转变可以在95℃下pH=7以上的溶液中发生,其转化率随起始溶液pH值的升高和陈化时间的延长而增大。随着相转变的进行,溶液的pH值开始下降明显,而后趋于平缓。相应地,大的团聚体颗粒解散成小的单个粒子,导致粒度减小,分布变窄,氯根含量降低和堆密度的增大。而且,这些变化直接与溶液pH值和陈化时间相关。据此,发展了一种新的制备具有高堆密度、低氯根含量、细粒度和窄分布的新方法,而且通过改变相转变条件可以方便地调谐颗粒特征。     

伯胺N_(1923)从离子吸附型稀土浸出液中萃取分离稀土与铝

离子吸附型稀土浸出液中共存杂质铝的含量随矿床产地和浸取条件而变化,其浓度有时与稀土属于同一数量级,而铝对稀土的分离纯化过程影响严重。因此,稀土与铝的分离具有重要意义。本文研究了伯胺N_(1923)萃取分离稀土与铝的性能,结果表明:N_(1923)-煤油-异辛醇有机相可以从离子吸附型稀土浸出液中直接萃取稀土,而铝及其他低价金属离子留在水相;其分离系数可以达到10~5。少量进入有机相的铝继续用(NH_4)_2SO_4溶液反洗(O/A=1∶1),使负载有机相中稀土与铝的比值大大增加,其分离系数随(NH_4)_2SO_4浓度的升高和溶液pH的下降而增大。确定的最佳浓度和pH分别为2%和1。有机相中的稀土经3 mol·L~(-1) NH_4Cl溶液反萃(O/A=2∶1),可以得到浓度大纯度高的稀土溶液;采用c_(Al)/c_(RE)=8.443的含铝稀土浸出液,经萃取、洗涤和反萃,可以得到浓度为4.3～13.34 g·L~(-1)的c_(Al)/c_(RE)=0.0023～0.0027的稀土溶液,稀土回收率大于96%。     

一种2-甲基-3-羟基喹啉-4-甲酸单核铜(Ⅱ)配合物的合成、晶体结构、理论计算与性质

以2-甲基-3-羟基喹啉-4-甲酸和1,10-菲咯啉为原料,经溶剂热法合成了一种新颖的Cu(Ⅱ)配合物,[Cu(L)(Phen)(H_2O)]·CH_3OH(1,HL=2-甲基-3-羟基喹啉-4-甲酸,Phen=1,10-菲咯啉),并通过红外光谱、元素分析、单晶衍射、固态漫反射、光致发光及理论计算对其结构和性质进行了研究。单晶结构分析表明配合物1的晶体属于单斜晶系,P2_1/c空间群,是一种零维(0D)结构的单核体。固态光致发光表明其为蓝紫色光发射体。时间密度泛函理论(TDDFT)计算表明其发射归属于配体-配体电荷转移(LLCT)。固态漫反射测量显示该化合物存在1.91 eV的窄带能隙。     

具有缓慢磁弛豫行为的单核Dy（III）和Ho（III）配合物

以席夫碱配体N,N''-双（3-甲氧基亚水杨基）乙烯-1,2-二胺（H₂salen）为原料,合成了2个新的镧系配合物,即[Dy（salen）₂]₃·3C₂H₉N₂·2CH₃OH（1）,[Ho（salen）₂]₃·3C₂H₉N₂·1.5CH₃OH（2）,并对其进行了基本表征。X射线单晶衍射结果表明,配合物1和2结晶于单斜晶系C2空间群,其金属配位环境类似。配合物1和2在零场和外加磁场下均具有单分子磁体（SMMs）行为。     

碳酸氢铵与氯化钇反应及结晶产物的组成和晶相类型

The relationships of crystal type, crystallization speed, purity, grain size and shape of rare earth carbonate with precipitation and crystallization conditions are very important for the production of rare earth carbonate with high efficiency, high quality and low cost. It is necessary for us for further understand the crystallization process mechanism and the factors effect on the crystallization. In the present paper, the crystallization characteristic, composition and crystal phase type of yttrium carbonates or ammonium yttrium carbonates precipitated from yttrium chloride solution using ammonium bicarbonate as precipitant were determined by chemical analysis, X-ray powder diffraction and the pH situ-determination. It was found that the crystal phase type was dominated by the feed molar ratio of ammonium bicarbonate to yttrium chloride, and the crystallization speed and the crystal composition were also influenced by temperature, feed manner and aging period etc. When precipitating and aging under lower temperature, crystallization is easy to take place in the high feed molar ratio zone, and when increasing tempera-ture, crystallization will take place both in lower and higher feed molar ratio zones. The results show that spherical yttrium carbonate with tengerite type crystal phase can be formed within the temperature 30～70℃ when feed molar ratio of ammonium bicarbonate to yttrium chloride is less than 4, and that a rhombus flake crystal, which possesses the composition of ammonium yttrium quasi-double carbonate and a new XRD pattern, is formed when the feed molar ratio is over 4. Their compositions can be represented as (NH₄)_aY(CO₃)_b(OH)_c·nH₂O, a< 1, 1< b< 2, c=3+a-2b. A fine crystal of ammonium yttrium double carbonate with the formula of (NH₄)Y(CO₃)₂·H₂O can also be obtained as using an enough amount of ammonium bicarbonate and aging enough time.