稀土配合物[REL3(4-picNO)H2O]的合成与表征

合成了2,3-二氯异丁酸根和4-甲基吡啶氮氧化物稀土三元配合物(RE=La、Ce、Pr、Nd、Sm、Eu).通过元素分析、红外、紫外、荧光、X射线粉末衍射、XPS、热分析以及摩尔电导等分析手段,确定了配合物的组成为[REL3(4-picNO)H2O](L= CH3C2H2Cl2COO -),并对它们的性质进行了讨论.     

Preparing Process of Cerium Acetate and Rare Earth Acetate

Preparing process was presented and the influences of concentration of acetic acid, reaction temperature, the ratio of cerium carbonate and acetic acid, heat preservation time to the yield of cerium acetate were discussed.The crystalline cerium acetate and rare earth acetate such as ( La, Ce, Pr, Nd) (Ac) 3, ( Ce, Pr, Nd) (Ac) 3, ( Pr, Nd, Er,Y) (Ac) 3 and yttrium acetate were prepared under this condition.The shape, structure and composition of the crystals were determined by the methods of SEM, TG-DTA, X-ray diffraction and chemical analysis.The optimum prepared conditions of cerium acetate were described.This prepared process has characteristics such as simple process route, low cost, high yield, good quality, no pollution to environment, etc.     

Spectroscopy of Pr^3＋4f5d Configuration in LaF3 Nanocrystals／Oxyfluoride Glass Ceramics

Theinterestofinvestigatingthe 4fn -15delectronicconfigurationofthetrivalentrareearth (RE)ionsisbasedonavarietyofapplicationsinthevacuumultra violet (VUV)regionofthespectrum ,suchasthede velopmentofplasmadisplaypanelsandmercury freefluorescenttubes[1] .Amo…     

Synthesis, characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic acid and α-Picolinic acid

Five novel ternary complexes were synthesized by the rare earth with 2,6-pyridine dicarboxylic acid andα-picolinic acid.These complexes were characterized by elemental analysis,molar conductivity,FT-IR,UV-Vis,Raman,TG-DTA and XRD.The general formula of the complexes was[RE(DPA)(L α )(H2O)]·2H2O(RE=Pr 3+ ,Nd 3+ ,Sm 3+ ,Eu,Er 3+ ;DPA=2,6-pyridine dicarboxylic acid;L α =α-picolinic acid). The investigation of fluorescence properties of the Eu-complex showed that the Eu(III)ion could be sensitized efficiently by the ligand to some extent.The antibacterial activity test indicated that all the five complexes exhibited antibacterial ability against Escherichia coli and Staphylococcus aureus with broad antimicrobial spectrums.     

含N_2O_2四齿希夫碱配体的稀土有机配合物的合成和表征

室温下 ,采用 Schlenk操作技术 ,用 Cp3L n和对称的希夫碱双水杨醛缩邻苯二胺 ( H2 SAL OPHEN)为原料 ,物质的量之比为 1∶ 1,在四氢呋喃介质中反应 ,合成了六个新型配合物 Cp L n SAL OPHEN( L n=Y,Pr,Sm,Ho,Er,Tm)。所有这些配合物都经过了元素分析、IR和 Ms表征     

稀土氧化物复合ZrO2陶瓷的制备及应用研究进展

稀土氧化物可作为稳定剂、烧结助剂、掺杂改性剂加入到ZrO₂陶瓷材料中,能极大地提高和改善陶瓷材料的强度、韧性,降低其烧结温度,减少生产成本.文中简要综述了稀土氧化物ZrO₂陶瓷材料的制备及应用研究状况,包括Y₂O₃复合ZrO₂陶瓷粉体、富铈稀土氧化物复合ZrO₂陶瓷粉末、Nd₂O₃复合ZrO₂陶瓷材料、Pr₂O₃\Pr₆O₁₁复合ZrO₂陶瓷、La₂O₃复合ZrO₂陶瓷、Yb₂O₃复合ZrO₂陶瓷、Sm₂O₃复合ZrO₂陶瓷材料及氧化锆中掺杂多种稀土氧化物陶瓷粉体的制备和应用,分析讨论了一些需要解决的问题,并展望了稀土复合ZrO₂陶瓷制备技术及未来研究发展趋势.      

La0.65RE0.10Mg0.25Ni3.5Si0.15(RE=La,Ce,Pr,Nd,Sm)储氢合金的电化学性能及EIS分析

通过感应熔炼制备La0.65RE0.10Mg0.25Ni3.55i0.15(RE =La,Ce,Pr,Nd,Sm)合金.采用X射线衍射方法分析了合金的相结构,研究了其电化学性能,并采用电化学阻抗谱分析了合金电极的放氢动力学特性.研究结果表明,合金是以LaNi5、LaNi3为主相的多相结构,同时合金中少量的Si元素与Mg和Ni元素形成了少量的Mg2 Si相和Ni2Si相.Ce,Pr,Nd,Sm部分替代La以后,合金的放电容量下降,Ce的替代使合金容量大幅度降低.对于本系列合金,La被其他稀土元素部分替代后,合金经过100次循环后的容量保持率略有下降,但除了Pr元素以外,变化值均较小.合金电极的电化学阻抗谱分析表明,中低频区的容抗弧半径依次为Ce ＞La＞ Nd ＞Sm ＞Pr,这表明采用Nd、Sm、Pr替代La后合金电极在碱液中放电过程电荷传递电阻Rct减小,即合金表面活性增加,但Ce替代却导致Ret急剧增大,这可能与Ce在碱液中易形成氧化物降低了合金的表面活性有关.     

Synthesis, Catalysis of Rare Earth Complexes with Aliphatic Noncyclic Polyether-Amino Acid Schiff Base

Coordination chemistry of rare earth with Schiffbase has developed rapidly in the last fewyears ,butthe majority of the complexes studied are derivedfromaromatic Schiff base .So far less papers of rare earthcomplex with aliphatic Schiff base have been rep…     

双水杨醛1,6-己二胺希夫碱轻稀土配合物的合成和表征

合成并表征了双水杨醛缩 1,6 己二胺希夫碱配体 (C2 0 H2 4 N2 O2 ,以L表示 )与轻稀土Ln3 的 7种新的固体配合物 [LnL2 ](NO3) 3(Ln =La、Ce、Pr、Nd、Sm、Eu、Gd)。利用元素分析、摩尔电导、红外光谱、电子光谱、X射线衍射物相分析、热分析方法进行表征。中心金属离子Ln3 与希夫碱配体中的亚胺氮和酚羟基中的氧发生配位 ,配位数为 8。     

Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction

Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or Pr6O11） as raw materials. The samples were characterized by X-ray diffraction （XRD）, temperature-programmed reduction （TPR）, temperature-programmed reduc-tion of oxidized surfaces （s-TPR）, and temperature-programmed desorption （TPD）. Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.     

(Zn, Ca) Solid-Solution Behavior and Its Effect on Luminescence Properties in Ca1- xZnx TiO3: 0.002Pr3+ Phosphors

Nominal composition of Ca1 - xZnxTiO3: 0. 002Pr3 ( x = 0. 000 ～ 0. 200) phosphors were prepared by conventional solid reaction route. XRD and PL measurements were used to investigate the solid-solution structure and luminescence properties of Zn-doped Ca1- xZnxTiO3:0. 002Pr3 phosphors. The effect of solid-solution structure formed by substitution between Ca2 and Zn2 ions on the luminescent properties was analyzed. The results reveal that, with the increase of Zn substitution content below 0.010, lattice parameters and the intensity of excitation peak at both 260 and 330 nm as well as the corresponding 610 nm emission intensity are monotonously decreased quickly in a similar tendency. Also, the evolution of luminescence intensity and crystal cell parameters against Zn doping concentration are in good agreement.Above results are closely related with the structure change within Ca1- xZnxTiO3:0. 002Pr3 solid-solution phase formed by the Zn ions substitution for the Ca sites. Present study reveals that the solid-solution structure formed by substitution between Ca2 and Zn2 ions has significant effect on the luminescence properties of single phase Ca1- xZnxTiO3:0.002Pr3 phosphors.     

微波消解-电感耦合等离子体原子发射光谱法测定稀土合金渣中主要稀土氧化物

提出了微波消解-电感耦合等离子体原子发射光谱(ICP-AES)同时测定稀土合金渣中氧化镧、氧化铈、氧化镨、氧化钕、氧化钐和氧化镝等主要稀土氧化物的分析方法。考察4种不同的消解试剂体系,优化了消解参数并选择了合适的分析线。结果表明,在以下条件下样品的消解效果最好：以HNO₃-HCl-HF-H₂O₂（V(HNO₃)∶V(HCl)∶V(HF)∶V(H₂O₂)=4∶2∶2∶1）作为消解试剂,采用四段升温的消解程序,设定的最低温度为160 ℃,最低压力为1.5 MPa,最高温度为225 ℃,最高压力为3.5 MPa,每段的最大温差不超过25 ℃,最大压差不超过1 MPa。在选定的仪器参数下,以408.671,413.765,390.843,401.255,359.260,353.171 nm 波长的谱线分别作为La,Ce,Pr,Nd,Sm,Dy的分析线,用稀土氧化物绘制校准曲线,ICP-AES法测定消解液中上述氧化物。测定结果的相对标准偏差在0.44%～0.98% 范围,加标回收率在94%～106%之间。     

Synthesis, characterization, and biological properties of nano-rare earth complexes with L-glutamic acid and imidazole

Four nano-rare earth ternary complexes of L-glutamic acid and imidazole RE（Glu）3ImCl3·3H2O （RE=Ce^3＋, Pr^3＋, Sm^3＋, Dy^3＋, Glu= L-glutamic acid, and Im=imidazole） were synthesized. Their composition was characterized with elemental analysis, IR, and molar conductance. The TEM image indicated that the complexes were regular shaped and the length was about 30-60 nm. The antibacterial activity test showed that all these complexes exhibited better antibacterial ability against Escherichia coli, Staphylociccus aureus, and Candida albican （MIC were about 180, 100, and 310 μg/mi, respectively） and could be considered as broad-spectral antimicrobial. Their antitumor activity in vitro against leukemia K562 cells was measured using the MTr method. The results indicate that the four complexes possess strong inhibi- tion effect on leukemia K562 cells. An approximately linear relationship is discovered between the relative inhibition rate and concentration, with the correlation coefficients R〉0.7 and P〈0.05, which is considered statistically significant.     

轻稀土萃取分离中稀土总量和分量的同时在线测定

用放射性同位素源Am-241激发萃取分离过程的轻稀土样品La、Ce、Pr和Nd,样品经放射源激发后产生特征KX-射线和康普顿散射线,由固体探测器接收,多道能谱仪分析和处理特征KX-射线和康普顿散射线,确定总稀土浓度和各稀土元素含量,实现轻稀土分量和总量的在线同时测定。     

新型(Fe,Co)-Zr-RE-B非晶合金的热稳定性和磁性

利用旋铸技术制备了一种新型的含稀土元素的铁基非晶合金。研究了Nd含量对Fe70Co8Zr7-xNdxB15(x=0～6%原子数分数)合金的非晶形成能力、热稳定性和磁性能的影响。当该合金系的Nd含量在0～6%(原子数分数)变化时,其饱和磁感应强度(Js)在1.10T～1.37T范围内变化,矫顽力(Hc)在2.28A/m～8.15A/m范围内变化。Js随Nd含量的增加而增加,当Nd含量为2%和3%时,其Hc值均在3A/m以下,且在Nd含量为2%时,具有最高的非晶形成能力(glassformationability简称GFA)即大的ΔTx(达61K);同时又有良好的软磁性能,其Js和Hc值分别为1.25T和2.28A/m。经对比得出,Fe70Co8Zr5RE2B15(RE=Ce、Pr、Gd和Tb)合金与Fe70Co8Zr5Nd2B15具有相近的非晶形成能力和磁性能。     

Phase structure and hydrogen storage properties of REMg8.35Ni2.18Al0.21 （RE=La, Ce, Pr, and Nd） hydrogen storage alloys

REMg 8.35Ni2.18Al0.21 (RE=La, Ce, Pr, and Nd) alloys were prepared by induction melting and following annealing. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results showed that the alloys were composed of Mg2Ni, (La, Pr, Nd)Mg2Ni, (La, Ce)2Mg17 , (Ce, Pr, Nd)Mg12 and Ce2Ni7 phases. The above phases were disproportioned into Mg2NiH4 , MgH2 and REH x (x=2.51 or 3) phases in hydriding. CeH2.51 phase transformed into CeH2.29 phase in dehydriding, whereas LaH3 , PrH3 and NdH3 phases remained unchanged. The PrMg8.41Ni2.14Al0.20 alloy had the fastest hydriding kinetics and the highest dehydriding plateau pressure while the CeMg8.35Ni2.18Al0.21 alloy presented the best hydriding/dehydriding reversibility. The onset hydrogen desorption temperature of the CeMg8.35Ni2.18Al0.21 hydride decreased remarkably owing to the phase transformation between the CeH2.51 and the CeH2.29 .     

Microstructure and Properties of Mg-10%Al-(0～3%)Di Alloys

The effects of didymium(Nd:Pr=3:1)on the microstructure and mechanical properties of Mg-10%Al alloy were studied with the additions of 0～3%Di. The small block-like Al2(Nd,Pr) phase appears in 1%Di alloy, the block-like Al2(Nd,Pr) and needle-like Al11(Nd,Pr)3 phases appear synchronously in 2%Di and 3%Di alloys, while the network of (Mg17Al12) β phase is broken up. The tensile properties can be improved with the addition of didymium. When the addition of didymium in Mg-10%Al alloy reaches 2%, the alloy exhibits the best combination of strength and ductility, but the strength and ductility drop at the addition of 3%Di due to the obvious increase of the size and quantity of the needle-like Al11(Nd,Pr)3 phase.     

稀土金属基准晶形成规律研究及预测

研究了原子尺寸因数和电子因素对准晶形成的影响。利用原子尺寸因数和电子因素构成键参数坐标系统，对稀土族13个金属（La，Ce，Pr，Nd，Sm，Eu，Gd，Tb，Dy，Ho，Er，Yb，Ln）基，已有实验结果的55个准晶进行了系统的研究。研究结果表明：在键参数图中，准晶合金形成区与非形成区明显区分开，准确率为92．73％，并且区分边界可用一条椭圆函数曲线描述，椭圆曲线方程为：（x-m）^2/c^2＋（y-n）^2/d^2=1,椭圆曲线参数m，n，c，d可由基体元素的相关参数确定，同时对可能存在的新的二元准晶进行了预测。该方法为定性研究及寻找新型稀土金属基准晶合金开辟了一条新的途径，在材料研究领域具有理论指导意义。     

氮,氮,氮′,氮′-四辛基-3-氧戊二酰胺色谱柱分离-电感耦合等离子体质谱法测定混合稀土氧化物中重稀土

电感耦合等离子体质谱法(ICP-MS)测定稀土元素时,轻稀土元素Ce、Nd、Sm的氧化物等复合离子严重干扰重稀土元素Tb、Dy、Ho、Er的测定,因此对混合稀土中重稀土元素进行测定前一般需要先对其分离富集。实验在样品溶解后,将N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)用硅藻土吸附后装柱,以0.1 mol/L HNO₃为样品溶液介质上柱,通过控制洗脱液的种类、酸度以及洗脱液流速,实现了轻稀土元素La、Ce、Pr、Nd与重稀土元素Tb、Dy、Ho、Er、Tm、Yb、Lu的分离和富集,建立了ICP-MS测定混合稀土氧化物中重稀土元素的方法。实验表明:控制洗脱流速为2.0 mL/min,用pH 2.0的HNO₃淋洗至淋洗体积约为500 mL,继续收集洗脱液,并用ICP-MS检测其中Nd₂O₃含量,直至洗脱液中Nd₂O₃的质量浓度小于200 ng/mL,可将轻稀土元素La、Ce、Pr、Nd及少量Y、Sm、Gd洗脱;再改用350 mL 1 mol/L HCl洗脱重稀土元素,可实现重稀土元素与La、Ce、Pr、Nd及部分Y、Sm、Gd的分离;通过选择¹⁵⁹Tb、¹⁶³Dy、¹⁶⁵Ho、¹⁶⁷Er、¹⁶⁹Tm、¹⁷²Yb、¹⁷⁵Lu为测定同位素可消除质谱干扰。将实验方法应用于混合稀土氧化物中重稀土元素的测定,加标回收率在93%～110%之间,相对标准偏差(RSD,n=8)在1.1%～10%之间。     

电池级稀土氧化物制备工艺的研究

南方中钇富铕混合稀土先后经Ｎｄ／Ｓｍ分组、Ｌａ／ＣｅＰｒ／Ｎｄ分离,分别得到镧铈镨钕、镧、铈镨富集物、钕;北方富铈氯化然土原料经Ｃｅ／Ｐｒ分组得到镧富休物;除去稀土中非稀土杂质,经沉淀、灼烧后制备多种优质稀土氧化物,混样调配,为火法电解生产电池级稀土金属提供原料。