掺Ce~（3＋）、Tb~（3＋）的四硼酸铝钇的发光特性

本文采用固相反应法合成了一系列掺Ｃｅ￣（３＋）、Ｔｂ￣（３＋）的四硼酸铝钇（Ｙ＿（１－ｘ－ｙ）Ｃｅ＿ｘＴｂ＿ｙＡｌ（ＢＯ＿３）＿４）磷光体。测定了它们的结构、属于三方晶系、空间群Ｒ＿（３２）、Ｌｎ￣（３＋）离子处于六个氧形成的三棱柱中。测定了磷光体中Ｃｅ￣（３＋）、Ｔｂ￣（３＋）和Ｃｅ￣（３＋）－Ｔｂ￣（３＋）共掺时的光谱，观察到Ｃｅ￣（３＋）、的Ｓｔｏｋｅｓ位移相当小（～１７００ｃｍ￣（－１））、Ｔｂ￣（３＋）的能级劈裂较明显和Ｃｅ￣（３＋）能将能量传递给Ｔｂ￣（３＋），测定了磷光体中Ｃｅ￣（３＋）、的荧光寿命，探讨了Ｃｅ￣（３＋）－Ｃｅ￣（３＋）之间的能量传递。

YAG∶Er~(3+),Ce~(3+)激光晶体的光谱特性

本文采用在YAG晶体中共掺铒铈离子,利用Ce~(3+)离子具有f—d宽带吸收跃迁,提高Er~(3+)离子对泵浦能量的吸收,以降低YAG:Er,Ce晶体的激光阈值。并测定了晶体在室温下的吸收光谱和荧光光谱。讨论了YAG:Er~(3+),Ce~(3+)晶体的光谱特性。用Judd—Ofelt理论计算了晶体中Er~(3+)离子振子强度,并与单掺铒离子YAG:Er~(3+)晶体中的数值进行了比较。

La_4(P_2O_7)_3:Ce,Gd,Tb磷光体的合成与光谱性质

本文首次采用溶液沉淀法合成了一系列La_4(P_2O_7)_3;Ce,Gd,Tb磷光体.经X射线分析表明,它们属于纯的La_4(P_2O_7)_3相。测定了这些化合物的激发和发射光谱、相对亮度及Ce~(3+)的发光寿命,观察到在此基质中Ce~(3+)与Gd~(3+)的光谱重叠,它们之间存在着一定的相互作用,使(La_(0.64)Ce_(0.3)Gd_(0.06)_4(P_2O_7)_3的亮度比(La_(0.7)Ce_(0.3)_4(P_2O_7)3和(La_(0.94)Gd_(0.06)_4(P_2O_7)_3有少许增加.此外,Ce~(3+)能有效地敏化Tb~(3+)~9,从而大大增强Tb~(3+)的发射.然而,Gd~(3+)与Tb~(3+)共存时存在着竞争吸收和独自发射,使(La_(0.80)Gd_(0.06)Tb_(0.14)_4(P_2O_7)_3的亮度与单掺的(La_(0.86)Tb_(0.14)_4(P_2O_7)3相比有少许降低.相应地在Ce,Gd和Tb共掺时,由于Gd~(3+)的影响,使Tb~(3+)的发射减弱,从而总的发光相对亮度有所降低。

Sm~(3+)在玻璃中的发光以及Sb~(6+)、Ce~(6+)、Gd~(3+)对Sm~(3+)发光性质的影响

本文研究了单掺(Sm~(3+),Ce~(3+)、Gd~(3+).Sb~(3+)、双掺(Sm~(3+)+Ce~(3+)、Sm~(3+)+Gd~(3+),Sm~(3+)+Sb~(3+))和兰掺(Sm~(3+)+Gd~(3+)+Ce~(3+))约四十余种不同玻璃的发射谱和激发谱.探讨了玻璃成份和掺杂离子浓度对Sm~(3+)发光性质的影响以及Ce~(3+),Gd~(3+)、Sb~(3+)、Ce~(3+)+Gd~(3+)对Sm~(3+)的敏化作用。

LaP_3O_9:Ce,Tb磷光体的合成与光谱特性

Ce~(3+)离子有宽而强的4f-5d吸收带,能有效地吸收能量,并形成强的宽带发射。Ce~(3+)的5d-4f跃迁是允许的电偶极子跃迁,其5d态的寿命非常短。为此Ce~(3+)可将能量有效地传递给其它离子,而成为良好的敏化剂。通常Ce~(3+)对Tb~(3+)的敏化十分有效,已有许多Ce~(3+)敏化Tb~(3+)的绿色发光材料。稀土磷酸盐是发光和激光材料的良好基质,LaPO_4:Ce,Tb已用作灯用三基色荧光粉,对不同类型稀土磷酸盐中Ce~(3+)、Tb~(3+)的发光已有不少报道,为探索新的高效

Ce~(3+)的敏化作用及其在发光材料中的应用

Ce~(3+)具有与其他三价稀土离子不同的发光性质已引起国内外的重视,不仅开展了许多研究,并已在各种发光材料中获得应用。然而,Ce~(3+)的发光特征表明,它不仅是一个好的激活剂,而且更是一个好的敏化剂。Ce~(3+)离子具有强而宽的4f—5d吸收带,其能有效地吸收能量、或本身发射或将能量传递给其他离子起敏化作用;Ce~(3+)具有宽的发射带,且随基质不同而异、则有利于与激活离子的吸收带匹配,能有高的能量传递效率;Ce~(3+)的5d—4f跃迁是容许的电偶子跃迁,其中5d组态的电子寿命非常短(一般为30—100ns),具有较高的能量传递几率;Ce~(3+)的含氧化合物的吸收带大多在紫外或兰区,因此在灯用发光材料中作为敏化离子较为普遍;铈提取容易、价格便宜作为敏化剂、减少价格较贵的其它稀土元素的用量更有其实际意义。本文在近年来工作的基础上作一定的总结与归纳,将有助于推动新型高效发光材料的发展。

CaF_2:Ce~(3+)中的电荷补偿问题的探讨

在不同的反应条件下,运用固相反应的方法合成了CaF_2∶Ce~(3+)多种粉末磷光体,测定了它们的荧光光谱,发现了3种不同的发光中心,并探讨了3种发光中心的转化规律;研究了不同阳离子电荷补偿剂对CaF_2∶Ce~(3+)光谱性质的影响;指出了不同发光中心的产生是电荷补偿途径不同所致。

CaF_2:Ce~(3+)晶体的光谱性质及γ线辐照效应

Ce~(3+)只有一个4f电子,基态能级为~2F_(5/2)和~2F(7/2),两能级差约为2200cm~(-1),Ce~(3+)不同于其它三价稀土离子,一般是d→f跃迁,特征发射为d→~2F_(5/2)和d→~2F_(7/2)跃迁引起的两宽带。CaF_2∶Ce~(3+)晶体中,当Ce~(3+)取代Ca~(2+)时,存在电荷补偿问题。Manthey讨论了CaF_2∶Ce~(3+)中间隙F~-充当电荷剂问题,Feofilov探讨了CaF_2∶Ce~(3+)的氧补偿问题,指出当有氧存在时,它

KMgF_3中Ce~(3+)的发射中心及取代格位的研究

本文用高温固相扩散反应方法及坩埚下降法制备了KMgF_(3~-)Ce~(3+)及KMg_(1-x)M_xF_(3~-)Ce~(3+)(M=Be~(2+),Ca~(2+))的粉末样品及KMgF_(3~-)Ce~(3+)单晶,测定了它们的激发光谱和发射光谱,发现KMgF_(3~-)Ce~(3+)中存在两种不同的发射中心,且证明了这是不同的电荷补偿途径所致,而不是Ge~(3+)占据了不同的阳离子格位所致.通过X射线四圆衍射仪的检测及Be~(2+)和Ca~(2+)对KMgF_(3~-)Ce~(3+)中Mg~(2+)取代后的光谱变化,推断Ce~(3+)占据KMgF_3中K~+的格位.

THE CATALYTIC BEHAVIOR AND REACTION-MECHANISM OF THE BI-CE-O SYSTEM CATALYSTS IN THE OXIDATIVE DEHYDROAROMATIZATION OF PROPYLENE

Oxidative dehydroaromatization of propylene was investigated by the pulse technique over two kinds of single oxide catalysts. With the Bi2O3 catalyst, the main dimer product was 1,5-hexadiene, and the dimerization activity was stable to pulse number even if the catalyst was partly reduced to the bulk. With the CeO2 catalyst, benzene was mainly formed instead of 1,5-hexadiene, but the activity decreased rapidly with increasing pulse number, indicating that only the lattice oxygen near the catalyst surface could be used for oxidative dimerization and the further aromatization. The Bi-Ce-O system catalyst was found in this study to give higher aromatization activity and showed better stability, compared to the Bi-Sn-O catalyst. Although the Bi-Ce-O catalyst was only a mixture of the two component oxides from X-ray diffraction analysis, there was a significant combination effect on the selectivity to benzene. The highest and the most stable selectivity of benzene was obtained at Bi/Ce = 1. In the TPD spectrum of Bi-Ce-O catalyst, there are not only the lattice oxygen (beta-oxygen) over 620-degrees-C due to the reduction of Bi2O3, but also a great deal of the alpha-oxygen desorbed about 400-degrees-C, which is considered the absorbed oxygen in the bulk. This absorbed oxygen could probably be a compensation of the lattice oxygen through the route of gaseous --> absorbed --> lattice oxygen in the binary catalyst system. By the kinetic study on the Bi-Ce-O catalyst, the dimer formation rate was the first-order with respect to the partial pressure of propylene and zero-order of oxygen. Although detail investigation would be made further, it was considered that the complete oxidation of propylene would mainly take place parallelly on some different sites, and the rate-determining step of propylene dimerization occurred probably between an adosrbed propylene and a gaseous one by an Eley-Rideal type mechanism.

氨氧化La-Ce-Co氧化物催化剂氧的性能研究

用X射线衍射和程序升温脱附方法研究了八个La-Ce-Co氧化物催化剂的结构及其氧的性能,试验了不同催化剂氨氧化反应前后氧的程脱并比较了其脱出氧的变化。测定了催化剂活性、组成及元素价态。发现催化剂的活性与三价钴离子的浓度成正比。催化剂中晶格氧的再生能力强,即氧化还原性能好,催化活性就高。结果表明,氨在La-Ce-Co氧化物体系催化剂上的氧化可能遵循Redox机理。Co~(3+)是活性中心。在催化剂中以少量Ce~(4+)取代La~(3+),可在催化剂中产生阳离子空位La_(1-x)CoO_(3+λ),有利于Co~(3+)的稳定加速体相中氧和电子的传递,促进催化剂的再氧化速度。从而提高催化剂的活性。

K_2NaAlF_6:Ce~(3+)和KAlF_4:Ce~(3+)磷光体的光谱特性

采用高温固相反应法,在Ar气氛中,合成了K_2NaAlF_6和KAlF_4基质化合物.分别测定了它们的结构,并计算了晶胞参数.测定了K_2NaAlF_6:Ce~(3+)和KAlF_4:Ce~(3+)磷光体的激发光谱和荧光光谱,根据Ce~(3+)的光谱结构的特点,讨论了Ce~(3+)的取代格位.

Ce~(3+)-Gd~(3+)在某些稀土硼酸盐体系中的能量传递

Ce~(3+)离子有一个宽而强的4f-5d吸收带,它能有效地吸收能量。Ce~(3+)离子的荧光寿命非常短,能将能量有效地传递给其它离子起敏化作用。对于Ce~(3+)→Tb~3+),Ce~(3+)→EU~(3+)和Ce~(2+)→Mn~(3+)的敏化作用已有许多报导,并在灯用发光材料上获得应用。Blasse等提出在Ce~(3+)敏化Tb~(3+)时。用Gd~(3+)作中间体能获得高效发光材料。由于Ce~(3+)的5d能级强烈地依赖于基质,其发射波长可以从紫外到红区,而Gd~(3+)的4f-4f跃迁的激发和发射峰值随基质的变化改变不大,因此将有可能呈现不同的Ce~(3+)-Gd~(3+)的能量转移过程。

CaS:Ce~(3+)磷光体的合成及发光性质

本文研究了不同合成条件对CaS:Ce~(3+)磷光体发光性质的影响。CaS:Ce~(3+)的发光强度随Ce~(3+)离子的浓度发生变化,最佳浓度为1.001×10~(-3)mol。对应于新的单一热释发光峰(426K)的陷阱参数为,陷阱深度E=1.01eV,逃逸频率因素S=1.2×10~(11)s~(-1),磷光体的热释发光满足二级动力学过程。

GENERAL ALPHA-N INDEX AND ITS APPLICATION .1. GENERAL ALPHA-N INDEX AND ITS APPLICATION IN THE EXTRACTION OF Y, CE, U, AND TH BY NEUTRAL PHOSPHORUS EXTRACTANCTS

The general a(N) index is established for molecules containing heteroatoms, rings, and multiple bonds. The general a(N) index is able to describe molecules with minute differences in structure and can also reveal the properties of molecules. This theory is successfully applied to the case of neutral phosphorus extractants. Both the molecular polarity and steric effect are characterized by the general a(N) index. The relationships between these properties and the distribution ratios for extracting Y, Ce, U, and Th are also shown by the general a(N) index.