含稀土和过渡元素Keggin结构混配型杂多酸盐的热解性质研究

本文研究了通式为Ｋ１０Ｈ３〔Ｌｎ（ＳｉＭｏ９Ｗ２Ｏ３９）２〕·ｘＨ２Ｏ（简记为Ｌｎ（ＳｉＭｏ９Ｗ２）２，Ｌｎ＝Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｔｂ、Ｙｂ，以下相同），Ｋ１０Ｈ３〔Ｌｎ（ＳｉＭｏ６Ｗ５Ｏ３９）２〕·ｘＨ２Ｏ（简记为Ｌｎ（ＳｉＭｏ６Ｗ５）２）、Ｋ１０Ｈ３〔Ｌｎ（ＳｉＭｏ２Ｗ９Ｏ３９）２〕·ｘＨ２Ｏ（简记为Ｌｎ（ＳｉＭｏ２Ｗ９）２）和Ｍｍ＋Ｈ４－ｍＳｉＭｏ１０Ｗ２Ｏ４０·ｘＨ２Ｏ（简记为ＭＳｉＭｏ１０Ｗ２，Ｍ＝Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｃｄ）４个系列３８种化合物的热解性质，确定它们的分解温度分别为：Ｌｎ（ＳｉＭｏ９Ｗ２）２，２５０～３００℃；Ｌｎ（ＳｉＭｏ６Ｗ５）２，３００～３５０℃；Ｌｎ（ＳｉＭｏ２Ｗ９）２，３５０～４００℃；ＭＳｉＭｏ１０Ｗ２，３８０～４２０℃，详细研究了稀土和过渡元素取代钼对化合物热解性质的影响。     

含钒镧系元素杂多配合物的热解性质研究

利用差热与热重分析、变温红外光谱、Ｘ射线粉末衍射以及溶解性实验等手段详细地研究了未见报道的Ｋ＿７Ｈ＿６［Ｌｎ（Ｗ＿（１０）Ｖ＿２Ｏ＿（３９））＿２］·ｍＨ＿２Ｏ（简记为Ｌｎ（Ｗ＿（１０）Ｖ＿２），Ｌｎ＝Ｌａ￣（３＋）、Ｃｅ￣（３＋）、Ｐｒ￣（３＋）、Ｎｄ￣（３＋）、Ｓｍ￣（３－）、Ｅｕ￣（３－）、Ｇｄ￣（３－）、Ｄｙ￣（３－）、Ｙｂ￣（３－），以下同）、Ｋ＿（１０）Ｈ＿５［Ｌｎ（Ｗ＿（１０）ＶＯ＿（３７））＿２］·ｍＨ＿２Ｏ［简记Ｌｎ（Ｗ＿（１０）Ｖ）＿（２２）、Ｋ＿（１０）Ｈ＿７［Ｌｎ（Ｗ＿９Ｖ＿２Ｏ＿（３９））＿２］·ｍＨ＿２Ｏ［Ｌｎ（Ｗ＿９Ｖ＿２）＿２］、Ｋ＿９ＬｎＭｏ＿６Ｖ＿６Ｏ＿（３９）·ｍＨ＿２Ｏ［ＬｎＭｏ＿６Ｖ＿６］、Ｋ＿（１０）ＬｎＭｏ＿５Ｖ＿７Ｏ＿（３９）·ｍＨ＿２Ｏ［ＬｎＭｏ＿５Ｖ＿７］和ｋ＿（１３）Ｈ＿２［Ｌｎ（ＳｉＷ＿（１０）ＶＯ＿（３９））＿２］·ｍＨ＿２Ｏ［Ｌｎ（ＳｉＷ＿（１０）Ｖ）＿２］＿６个系列５０多种含钒镧系元素杂多配合物的热解性质，确定它们的分解温度分别为：Ｌｎ（ＳｉＷ＿（１０）Ｖ）＿２，４５０～５００℃；Ｌｎ（Ｗ＿（１０）Ｖ＿２）＿２、Ｌｎ（Ｗ＿（１０）Ｖ）＿２、Ｌｎ（     

镧系元素的双(九钨二钒)杂多酸钾的合成与表征

报道了镧系元素钨钒杂多配合物的合成方法。元素分析和热重分析确定其通式为：Ｋ１０Ｈ７〔Ｌｎ（Ｖ２Ｗ９Ｏ３７）２〕·ｘＨ２Ｏ（Ｌｎ＝Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋）。利用红外（ＩＲ）、紫外（ＵＶ）和Ｘ射线衍射谱对其进行了表征。配合物的热解性质研究表明，其分解温度范围为４００～４５０℃。     

轻稀土元素钨钒杂多配合物的合成与表征

本文首次报道了轻稀土元素钨钒杂多配合物的合成方法，经元素组成和ＴＧ分析确定其分子通式为Ｋ_（１０）Ｈ_７［Ｌｎ（Ｖ_２Ｗ_９Ｏ_（３７））_２］·ｘＨ_２Ｏ（Ｌｎ＝Ｌａ~（３＋）、Ｃｅ~（３＋）、Ｐｒ~（３＋）、Ｎｄ~（３＋））。利用ＩＲ、ＵＶ、ＸＲＤ和ＥＳＲ对配合物进行了表征。     

镧系元素钼钒杂多配合物的合成与表征

本文报道了镧系元素的钼钒杂多配合物Ｋ５ＨＬｎＭｏ６Ｖ７Ｏ（４０）·ｘＨ２Ｏ（Ｌｎ＝Ｌａ、Ｃｅ、Ｐｒ）的合成方法。通过元素分析、红外光谱、紫外光谱、顺磁共振谱、Ｘ射线粉末衍射及差热—热重分析等手段，对配合物进行表征，推断出此类杂多配合物具有Ｋｅｇｇｉｎ结构的基本骨架。     

65～150μm的（NH4）2WS4在氮气中的热分解行为研究

用ＤＴＡ法和ＸＲＤ法研究了粒度为６５～１５０μｍ的（ＮＨ４）２ＷＳ４在氮气中的热分解机理，得出热分解反应是由（ＮＨ４）２ＷＳ４＝２ＮＨ３＋Ｈ２＋２Ｓ＋ＷＳ２和Ｈ２＋Ｓ＝Ｈ２Ｓ两个反应构成的。用Ｄｏｌｙｅ—Ｏｚａｗａ法和Ｋｉｓｉｎｇｅｒ法计算了（ＮＨ４）２ＷＳ４热分解中两个反应的活化能分别为２７００±１０ｋＪ／ｍｏｌ、５９０３±１０ｋＪ／ｍｏｌ，反应级数分别为０６、１５，分解产物为ＷＳ２。     

硅锑钼蓝光度法测定分子筛中的硅

在ｐＨ０．８～１．５、ＨＣｌ－Ｃ２Ｈ５ＯＨ－ＣＨ３ＣＯＣＨ３－Ｈ２Ｏ体系中，Ｓｉ（Ⅳ）、Ｓｂ（Ⅲ）、Ｍｏ（Ⅵ）形成三元杂多酸，用抗坏血酸还原三元杂多酸形成杂多蓝。方法的表观摩尔吸光系数ε７８０ｎｍ＝１．６７×１０４Ｌ／ｍｏｌｃｍ，硅量在０～１．２μｇ／ｍＬ范围内符合比尔定律。本法用于分子筛中硅的测定，获得了令人满意的结果。     

非平衡萃取体系研究：2—乙基已基膦酸单2—乙基已基酯萃锌

以正辛烷为稀释剂，采用上升液滴法研究了在硝酸盐体系中Ｐ５０７萃取锌（Ⅱ）的动力学。条件试验表明，该萃取过程受反应Ｚｎ（Ⅱ）Ａ．ＨＡ（＋）ｉ＋２Ｈ２Ａ２（α）＝Ｚｎ（Ⅱ）Ａ２．２ＨＡ（ｏ）＋２ＨＡ（１）＋Ｈ＾＋控制，萃取速率可表示为：Ｒ＝ｋ＇［Ｚｎ（Ⅱ）］［Ｈ２Ａ２］＾２（Ｏ）／ｋ２［Ｈ＾＋］＋ｋ３［Ｈ２Ａ２］＾２（ｏ），在２９８Ｋ时测得表观速率常数Ｋ值为１０＾－＾６．６７ｄｍ＾－＾２ｓ－＾－＾１ｍ     

脱硫的现状

１　前　言本文简要地介绍联合钢铁厂铁水脱硫的几种基本方法。有效的方法很多,一些最常用的反应剂如下：石　灰———Ｃａ＋２Ｏ－２＋Ｓ０＝Ｃａ＋２Ｓ－２＋Ｏ０（１）苏　打———Ｎａ＋１２Ｃ＋４Ｏ－２３＋Ｓ０＝Ｎａ＋１２Ｓ－２＋Ｃ＋４Ｏ－２２＋Ｏ０（２）碳化钙———Ｃａ＋２Ｃ－１２＋Ｓ０＝Ｃａ＋２Ｓ－２＋２Ｃ０（３）镁　Ｍｇ———Ｍｇ０＋Ｓ０＝Ｍｇ＋２Ｓ－２（４）硅化钙———Ｃａ＋２Ｓｉ－２＋Ｓ０＝Ｃａ＋２Ｓ－２＋Ｓｉ０（５）一般来说,脱硫反应可表示如下：Ｓ＋２ｅ→Ｓ２－（６）反应式（１）和（２）中,反…     

铬铁矿的快速溶解方法及用分光光度法测定铬

Ｃｒ２Ｏ３和铬铁矿能溶于Ｈ２ＳＯ４－Ｌｉ２ＳＯ４Ｃｅ（ＳＯ４）２（２０／１０／１Ｖ／Ｗ／Ｖ），Ｈ２ＳＯ４－Ｌｉ２ＳＯ４－ＭｎＯ２（２０／１０／１Ｖ／Ｗ／Ｗ）或Ｈ２ＳＯ４－Ｌｉ２ＳＯ４－ＫＩＯ４（２０／１０／２／Ｖ／Ｗ／Ｗ）中，生成的混浊溶解可用Ｈ２Ｏ２处理或溶剂萃取使之变得清亮，而后用分光光度法在６１４ｎｍ处测定铬。     

Synthesis and Characterization of Rare Earth Complexes of Ferrocenylcarbonylhydrazine

Ｔｈｅｍｅｔａｌｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅａｔｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｏｗｉｎｇｔｏｔｈｅｉｒａｎｔｉｆｕｎｇａｌａｎｄａｎｔｉｂａｃｔｅｒｉａｌａｃｔｉｖｉｔｉｅｓ[1 ,2 ] .Ｔｈｅｙｃａｎａｌｓｏｂｅｕｓｅｄａｓａｎａｌｙｔｉｃａｌｒｅａｇｅｎｔｓ[3 ]ａｎｄｅｘｔｒａｃｔｉｎｇａｇｅｎｔｓｆｏｒｍｅｔａｌｓａｌｔｓ[4 ] .Ｍａｎｙｃｏｍｐｌｅｘｅｓｏｆｈｙｄｒａｚｉｄｅｓｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄａｎｄｃｈａｒａｃｔｅｒｉｚｅｄ[5]…     

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…     

共沉淀法制备稀土石榴石Ln3Al5O12(Ln=Y, Ce, Yb)

以Y2O3、Yb2O3、Al(NO3)3.9H2O和Ce(NO3)3.6H2O为原料,NH4HCO3、NH3.H2O做复合沉淀剂,用共沉淀法制备纳米稀土石榴石Ln3Al5O12(LnAG,Ln=Y,Ce,Yb)粉体。用TG/DTA、XRD、SEM、TEM等手段对LnAG前驱体及煅烧后的粉体进行表征。结果表明,用上述方法在1 000℃煅烧3h可得到分散性好、形状规则且粒径为50nm左右的Y3Al5O12、Yb3Al5O12、Y2.9Ce0.1Al5O12石榴石粉体,但不能得到Ce3Al5O12石榴石,合成石榴石粉体的最佳煅烧温度为1 050℃以上。     

Synthesis and Properties of Heteropoly Tungstovanadogermanic Complexes with Rare Earths

Ｈｅｔｅｒｏｐｏｌｙｃｏｍｐｏｕｎｄｉｓａｎｅｗｃａｔａｌｙｓｔｗｉｔｈｍａｎｙｆｕｎｃｔｉｏｎｓｉｎｃｈｅｍｉｓｔｒｙｉｎｄｕｓｔｒｙ .Ｉｔｓｅｘｃｅｌｌｅｎｔｃａｔａｌｙｔｉｃｐｅｒｆｏｒｍａｎｃｅｉｓｄｅｔｅｒｍｉｎｅｄｂｙｉｔｓｃｏｍｐｏｓｉｔｉｏｎａｎｄｓｔｒｕｃｔｕｒｅ .Ｉｔｈａｓｓｉｍｐｌｅｃｏｍｐｏｓｉｔｉｏｎａｎｄｆｉｘｅｄｓｔｒｕｃｔｕｒｅ ,ａｌｔｈｏｕｇｈｉｔｍａｙｃｏｎｓｉｓｔｏｆｍａｎｙｅｌｅｍｅｎｔｓ .Ｉｔｓｓｔｒｕｃｔｕｒｅａｎｄｐｒｏｐｅｒｔｙｃａｎｂｅｃｈａｎｇ…     

Synthesis and photoluminescent properties of doped ternary Eu_(1-x)Ln_x(NPPD)_3·DPQ complexes

Rare earth (RE) ternary complexes of Eu0.5Ln0.5(NPPD)3·(DPQ) (HNPPD=1-(naphthalen-2-yl)-3-phenylpropane-1,3-dione; DPQ= dipyridobenzoquinone) and Eu1-xLax(NPPD)3·(DPQ) (Ln3+=La3+, Gd3+, Sm3+, Pr3+; x=0.0, 0.1, 0.3, 0.5, 0.7, 0.9) were synthesized by the reaction of RECl3·6H2O with HNPPD and DPQ in stoichiometry. The complexes were characterized with IR, elemental analysis, TGA-DSC and wide-angle X-ray diffraction. The UV-Vis absorption spectra and fluorescence properties of the complexes were also investigated. The experimental results showed that the luminescence efficiency of Eu3+ complexes was enhanced by doping some other lanthanide ions. Eu0.7La0.3(NPPD)3·(DPQ) showed the highest luminescence efficiency.     

Photoluminescence and electrochemiluminescence studies of chosen rare earths systems

Eu（Ⅲ） complexes with chosen Keggin polyoxomatalates, POM, containing organic counter cations （tetrabutylarnmonium, tetrabutylphosphonium, triphenylethylphosphonium）, were synthesized, and their photophysical properties were studied. The synthesized complexes had the general formula of XnH5-n[EuSiW11O39], formulated based on the results of elemental and thermogravimetric analysis and FTIR spectroscopy. The photophysical properties of the obtained compounds were investigated using photoluminescence and electrochemiluminescence, ECL, methods in solutions and solids. The most intense luminescence of Eu（Ⅲ） was observed for the complexes with tetrabutylarnmonium cations. After the addition of phenanthroline to the XnH5-n[EuSiW11O39] solutions, a large increase in the Eu（Ⅲ） luminescence intensity and a lengthening of its luminescence lifetime were observed as a result of the formation of ternary complexes. Attempts to apply ECL as a method of light emission by generating species capable of forming excited states in Ln/POMs, i.e., Tb（Ⅲ） and Eu（Ⅲ） in the Na9EuW10O36 and Na9TbW10O36 complexes, were made. The influence of the POM complexes on the ECL was also tested using the Tb/EDDHA （EDDA=ethylenediamine di（o-hydroxyphenylacetic acid）） complex, which is effective in generating ECL.     

Syntheses, characterization, and luminescence of two lanthanide complexes [Ln2(acetate)6(H2O)4]·4H2O (Ln=Tb(1), Sm(2))

Two dinuclear compounds [Ln2(acetate)6(H2O)4]·4H2O (Ln=Tb(1), Sm(2)) were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P(-1). The coordination geometry around Ln(III) ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb(III) in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.     

Preparation and characterization of Y3Al5O12:Ln（Ln=Eu,Ce） phosphor powders by ultrasonic atomization and co-precipitation process

A novel technique for YAG:Ln(Ln=Eu,Ce) phosphor powder synthesis with a nanocrystalline structure was developed.Nanocrystalline YAG:Ln powder was prepared by an ultrasonic atomization and co-precipitation method using a mixture solution of ammonium hydroxide(NH3·H2O) and ammonium hydrogen carbonate(NH4HCO3) as precipitant.The as-prepared nano-powders were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),and fluorescence spectrometer.The obtained phosphor powders were homogenous and in size of 50-70 nm.The results demonstrated that by using ultrasonic atomization and co-precipitation process,we could synthesize a good quality YAG:Ln(Ln=Eu,Ce) phosphor powder that had many potential applications.     

Hydrothermal syntheses and characterization of three lanthanide coordination complexes constructed by 2,2’:6’,2’’-terpyridine and 2,2’-biphenyldicarboxylic acid

Two 1D coordination polymers [Ln2(dpdc)3(tpy)2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2’-biphenyldicarboxylic acid and tpy= 2,2’:6’,2’’-terpyridine] and one dinuclear complex Er2(dpdc)2(Hdpdc)2(tpy)2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln(III) centers. In the asymmetric unit, the two Er(III) ions in 3 were both nine-coordinated and had similar coordination environments. The Er(III) ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.     

Synthesis and spectral characteristics of La2MoO6：Ln3＋ （Ln=Eu, Sm, Dy, Pr, Tb） polycrystals

The novel phosphors of La 2 MoO 6 activated with the trivalent rare earth Ln 3+ (Ln=Eu, Sm, Dy, Pr, Tb) ions were synthesized by solid state reactions at high temperature in air atmosphere, and their phase impurities and luminescent properties were studied. The photoluminescence (PL) excitation and emission spectra, and decay curves were employed to study their luminescence properties. The lifetimes of the characteristic emissions from Ln 3+ ions were in the order of millisecond except Pr 3+ ions. (LaEu 1-x ) 2 MoO 6 was a promising phosphor for practical application and the optimum concentration was x=0.075. The concentration quenching mechanism of Eu 3+ was also discussed by theoretical fitting using Burshtein model.