Preparation，Structural Characterization and Thermal Decomposition Mechanism of Rare Earth Salts of 3－Nitro－1，2，4－Triazol－5－One

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Luminescence Properties of Rare Earth Ions in Cadmium Metasilicate

The luminescence properties of CdSiO3:RE^3 phosphors doped with various rare earth ions are reported. The series of rare earth ions doped CdSiO3 phosphors are prepared by the conventional high-temperature solid-state method, and characterized by XRD and photoluminescence (PL) spectra. The results of XRD measurement indicate that the products fired under 1050 ~C for 3 h have a good crystallization without any detectable amount of impure phase. The PL spectra measurement results show that CdSiO3 is a novel self-activated luminescent matrix. When rare earth ions such as Y^3 ,La^3 , Gd^3 , Lu^3 , Ce^3 , Nd^3 , Ho^3 , Er^3 , Tm^3 and Yb^3 are introduced into the CdSiO3 host, one broadband centered at about 420 nm resulted from traps can be observed. In the case of other earth ions which show emissions at the visible spectrum region, such as Pr^3 , Sm^3 , Eu^3 , Tb^3 and Dy3 , the mixture of their characteristic line emissions with the ～420 nm strong broadband luminescence results in various emitting colors. As a consequence, different emitting colors can be attairied via introducing certain appropriate active ions into the CdSiO3 matrix. In additional, this kind of phosphors shows good long-lasting properties when excited by UV light. All the results show that CdSiO3 is a potential luminance matrix.     

Analysis of Response Surface in the Study of RE(NO_3)_3-HNO_3-P507-Kerosene Extraction System

RE(NO_3)_3-HNO_3-P507-kerosene extraction system(RE=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y)was studied by the response surface technique.14 models for extracting single rare earth ele-ment in a broad range of acidity and initial rare earth concentration were obtained by using the stepwiseregression method.Three-dimensional display of the response surface of the model of extracting Er~(3 )wasshowed as an example,which reveals clearly the dependence of distribution ratio upon both initial acidity and ini-tial rare earth concentration.     

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。     

共沉淀分离-电感耦合等离子体原子发射光谱法测定含难熔金属岩石中12种稀土元素

准确测定稀土元素含量,对是否开采含难熔金属岩石的矿山中稀土元素具有重要指导意义。实验采用Na₂O₂在750℃马弗炉中熔融样品,熔融体冷却后用盐酸(1+4)转入烧杯中,往溶液中加入氨水,以样品做载体,共沉淀分离除去钠盐及能与氨水形成络氨离子的金属元素,沉淀物用稀氨水洗涤、热稀盐酸溶解,以电感耦合等离子体原子发射光谱法(ICP-AES)测定试液中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y,建立了含难熔金属岩石中12种稀土元素的测定方法。各元素校准曲线的线性范围为0.10~25μg/mL,方法的检出限0.20~1.0μg/g。按照实验方法测定含难熔金属岩石物料中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y等12种稀土元素,结果的相对标准偏差(RSD,n=9)为3.2%~6.2%,加标回收率为90%~110%。实验方法可用于含难溶金属岩石中稀土元素含量为0.001%~0.50%(质量分数)的测定。     

电感耦合等离子体原子发射光谱法测定La、Ce、Yb基体中痕量稀土杂质的多元光谱拟合校正限度

考察了La、Ce和Yb等基体元素对稀土杂质元素测定的光谱干扰。在杂质元素谱线窗口内,La、Ce和Yb所产生的干扰线总数量比文献报导的少,且当基体元素浓度增大时,在杂质元素谱线窗口内出现一些未曾报道过的谱线。经多元光谱拟合（MSF）法校正,基体元素的光谱干扰得到有效消除,杂质元素的检出限明显降低,但仍达不到没有La、Ce和Yb时的水平。当测定质量浓度为0100 μg/mL杂质元素时允许质量浓度为1 000～2 000 μg/mL基体元素存在,当被测的杂质浓度进一步降低时允许基体元素的最高浓度也随之降低。建立MSF模型时,应使建模溶液中杂质元素浓度是这些元素检出限的100倍,基体元素浓度接近实际样品中基体的存在量,MSF建模数据与样品测定数据还须在同一实验条件下完成。     

电感耦合等离子体原子发射光谱法测定磷矿中微量稀土元素

样品经碱熔,溶液提取,沉淀富集后得到只含稀土元素的溶液,采用电感耦合等离子体原子发射光谱(ICP-AES)法测定磷矿中15种稀土元素La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y。主要考察了共存元素间的干扰情况,选择无干扰或干扰量对分析结果可以忽略不计的谱线为最佳分析线,标准曲线法直接测定磷矿中稀土元素。本法测定结果与ICP-MS测定结果相符合,可满足日常分析要求。     

电感耦合等离子体质谱法分析粉煤灰漂珠中稀土元素

为研究粉煤灰漂珠中稀土元素对环境的影响,减少二次污染,建立了一种压力密闭消解-电感耦合等离子体质谱法测定粉煤灰漂珠中Sc,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu等15种稀土元素的方法。方法用于分析国家标准物质(GBW07103)中稀土元素,结果与认定值一致;用于分析粉煤灰样品中稀土元素并做加标回收实验,加标回收率在93.9%~104.2%之间。     

First-principles prediction of the magnetism of 4f rare-earth-metal-doped wurtzite zinc oxide

Electronic structure and magnetic properties of wurtzite ZnO semiconductor doped with rare earth （RE=La, Ce, Pr, Pm, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb） atoms were studied using spin-polarized density functional theory based on the full-potential linear augmented plane wave （FP-LAPW） method as implemented in the Wien2k code. In this approach the generalized gradient approximation （GGA） was used for the exchange-correlation （XC） potential. Our results showed that the substitution of RE ions in ZnO induced spins polarized localized states in the band gap. Moreover, the studied DMSs compounds retained half metallicity at dopant concentration x=0.625%for most of the studied elements, with 100%spin polarization at the Fermi level （EF）. The total magnetic moments of these compounds existed due to RE 4f states present at EF, while small induced magnetic moments existed on other non-magnetic atoms as well. Finally, the energy difference between far and near configurations was investigated. It was found that the room temperature ferromagnetism was possible for RE-doped ZnO at near configuration. Since the RE-RE separation was long enough （far configuration） for magnetic coupling, the system became paramagnetic or antiferromagnetic ground state.     

Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins

The effects of rare earth（RE）on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE（RE=La,Ce,Pr,Nd,Sm,Eu or Gd）,were prepared by the impregnation of the ZSM-5 type zeolites（Si/Al=64：1）with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B（Lewis acid/Brnsted acid）,but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.     

贵州赫章铜厂沟铜矿稀土元素地球化学特征及成矿物源示踪

通过对赫章铜矿化带的野外地质调查、采样、室内显微镜下分析、化学分析、扫描电镜、X衍射成分分析,研究了铜矿的矿物组成、矿石类型特征(初步划分为砂岩型铜矿石和蚀变构造角砾岩型铜矿石),矿石铜品位为3.26%～3.88%。采用ICP-MS方法测定了赫章铜矿两类型矿石、赋矿围岩及峨眉山玄武岩的稀土元素及微量元素组成,并进行了稀土特征值等的对比研究;LREE/HREE比值为9.43～11.12,La/Yb比值为11.86～14.6,显示出各样品轻稀土明显富集;δCe值为0.75～0.84,显示出负异常。除HTC-3的δEu=1.11、显示出很弱正异常外,其余样品的δEu=0.94～1.06,Eu仅显示非常微弱的异常。铜厂沟铜矿岩矿样品微量元素分布模式图表明其分布特征具有同源性。通过研究各样品的稀土元素、微量元素地球化学特征、铜矿化蚀变过程中稀土元素的迁移规律及呈现继承性的特点,结合飞仙关组砂岩的形成环境,得出峨眉山玄武岩为铜矿成矿(矿化)的物质来源结论。     

电感耦合等离子体原子发射光谱法测定镝铁电解粉尘中15种稀土元素

用硝酸和氢氟酸溶解试样,高氯酸冒烟除氟,在硝酸介质中用电感耦合等离子体原子发射光谱法(ICP-AES)测定了镝铁电解粉尘中La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y 15种稀土元素。为了提高高含量元素的测定准确度,在测定基体元素Dy时,采用铟作内标;为了消除基体效应对稀土杂质元素测定的影响,采用基体匹配的校准曲线。镝铁电解粉尘中铁含量很低(铁的质量分数不超过1%),对测定没有影响。实验方法测定了一镝铁电解粉尘样品,结果表明,La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Ho、Er、Tm、Yb、Lu和Y 14个稀土杂质元素测定值与ICP-MS的测定值基本一致,镝和14个稀土元素的合量与重量法测得的稀土总量吻合。     

共沉淀分离-电感耦合等离子体原子发射光谱法测定含难熔金属岩石中12种稀土元素

准确测定稀土元素含量,对是否开采含难熔金属岩石的矿山中稀土元素具有重要指导意义。实验采用Na₂O₂在750℃马弗炉中熔融样品,熔融体冷却后用盐酸(1+4)转入烧杯中,往溶液中加入氨水,以样品做载体,共沉淀分离除去钠盐及能与氨水形成络氨离子的金属元素,沉淀物用稀氨水洗涤、热稀盐酸溶解,以电感耦合等离子体原子发射光谱法(ICP-AES)测定试液中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y,建立了含难熔金属岩石中12种稀土元素的测定方法。各元素校准曲线的线性范围为0.10~25μg/mL,方法的检出限0.20~1.0μg/g。按照实验方法测定含难熔金属岩石物料中La、Ce、Sm、Eu、Gd、Tb、Ho、Er、Dy、Tm、Yb、Y等12种稀土元素,结果的相对标准偏差(RSD,n=9)为3.2%~6.2%,加标回收率为90%~110%。实验方法可用于含难溶金属岩石中稀土元素含量为0.001%~0.50%(质量分数)的测定。     

Influence of Rare Earth Elements on Luminescent Properties of Y2SiO5:Tb

Photoluminescent(PL) and cathodoluminescent(CL) properties of rare earths (Sc3 , La3 , Gd3 and Lu3 ) doped (Y0.97Tb0.03)2SiO5 were studied. Rare earth doping clearly influences PL and CL properties of Y2SiO5:Tb. For La3 doped system, PL intensity increases nearly 10% at x=0.05 whereas for Lu3 doped system, the intensity increases about 20% at x=0.20. Gd3 doping and Sc3 doping reduce the intensity; at x=0.3, it is reduced about 30% for Gd3 doped system and about 15% for Sc3 doped system, respectively. Quenching concentration of activator became higher in rare earth doped samples, which may be understood by that the rare earth dopants might dilute the concentration of the activator. Additionally, doping also influences the color saturation of Y2SiO5:Tb. Sc3 , La3 , and Gd3 doping improve the color saturation, whereas Lu3 doping decreases the color saturation. CL measurements show that CL intensity increases for all rare earths doped systems. The energy transfer from Gd3 to Tb3 was discussed.     

ICP-AES法测定镝铁合金中稀土杂质

研究了以ICP-AES法测定镝铁合金中稀土杂质,采用基体匹配和光谱拟合技术消除基体光谱干扰,分析范围,La、Ce、Pr、Nd、Sm、Eu、Tm、Yb、Lu:0.0050％～0.50％,Gd、Tb、Ho、Er、Y:0.010％～0.50％,精密度RSD为0.40％～10.32％.对不同含量样品,经与等离子质谱法对照,结果吻合.     

Effects of Rare Earth Elements on Photocatalytic Antibacterial Properties of Nanometer TiO2 Powders

Nanometer Ce/TiO2 functional materials with photocatalystic antibacterial properties were prepared by dipping TiO2 nanometer powders into RE( NO3 )·nH2O solutions, filtrating, drying and heat treatment, and the enhancement mechanisms of Ce on the nanometer TiO2 were studied by electronic spin resonance(ESR) The results show that TiO2 for photocatalystic antibacterial properties is strengthened evidently by adding Ce, which has a high efficiency of photocatalystic antibacterial properties with the light extent of visible light and ultraviolet radiation. The basic reason for obtaining the strengthened result is that the effective wave length of photocatalystic properties of TiO2 can be expanded to visible light area with the induction of the rare earth elements, whether or not ultraviolet light exists, nanometer TiO2 can produce a great deal of hydroxylic radical(·OH) by treating with rare earth elements.     

大兴安岭玻乌勒山地区玛尼吐组火山岩地球化学特征及成矿预测

大兴安岭玻乌勒山地区玛尼吐组火山岩样品SiO2平均质量分数为59.93%,属中性岩,过铝质、富碱,为一套高钾钙碱性和钙碱性中性火山岩系列。稀土元素总量较高（∑REE=（144.06~212.88）×10-6）,铕异常不明显（δEu值介于0.75~0.99之间）,轻重稀土分馏明显,分馏系数（La/Yb）N介于10.49～13.47之间。富集大离子亲石元素K、La、Ce、Rb、Ba和LREE,亏损高场强元素Ta、Nb和Ti等,火山岩样品主要来源于受俯冲流体交代的地幔源区,火山活动与古亚洲洋或蒙古-鄂霍茨克洋俯冲有关。区内地、物、化、遥异常特征显著,综合预测圈出成矿有利地段2处,具有寻找岩浆热液型多金属矿床的潜力。     

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。     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

Element migration and phase distribution characteristics during crystallization of rare earth phase in rare earth slag

The crystallization experiment of molten rare earth (RE) slag under different cooling rates was carried out. The characteristics of element migration and phase distribution during RE phase crystallization were studied by using different equipment. The experimental results show that there are two RE phases in the RE slag, namely (Ca, Ce, La)₅(SiO₄)₆F and (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇. During the cooling crystallization process of molten RE slag, Ca and P elements in the RE phase of (Ca,Ce,La)₅(SiO₄)₆F migrate from inside to outside, and finally gather at the outer edge of the phase to form phase Ca₃(PO₄)₂. The RE phase (Ca,Ce,La)₅(SiO₄)₆F is distributed inside the furnace-cooled slag, and the RE phase (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇ is distributed in the surface layer of the furnace-cooled slag. And based on the phase distribution characteristics, the central hollowing method is proposed to realize the preliminary enrichment of valuable elements Ti, Nb and RE in RE slag.