含膦,氮配体的混合膦酸锆—钯催化剂的研制

用氯化二苯基膦为膦化试剂,首次对多乙烯多胺乙基膦酸－磷酸氢锆Ｚｒ（ＨＰＯ４）１．３５（Ｏ２ＰＣＨ２ＣＨ２（ＮＨＣＨ２ＣＨ２）ｍＮＨ２）０．６５·Ｈ２Ｏ（ＺＰ－ＰＥＰＡＥＰＡ,ｎ＝０,１,２,３,４）载体表面进行二苯基膦化,合成了一类含膦氮配体的新型混合膦酸锆载体及负载钯催化剂。研究了有机膦酸侧链不同链长和Ｐｈ２ＰＣｌ用量对配体载体制备的影响,并用ＩＲ,ＴＧ,ＤＴＧ,ＤＴＡ对这类载体及催化剂进行表征     

二溴苯羟基荧光酮荧光光度法测定微量锆

本文提出了一个锆－二溴苯羟基荧光酮（ＤＢＨＰＦ）－乳化剂ＯＰ荧光光度法测定微量锆的新体系，在０．５～１．２ｍｏｌ／Ｌ的ＨＣｌ介质中，锆与ＤＢＨＰＦ生成组化比为１：４的红色荧光性络合物，荧光强度与锆（Ⅳ）的浓度在０～１００μｇ／Ｌ呈线性关系，检出限为２．０μｇ／Ｌ。灵敏度高，高选择性好，用于瓷釉等样品中ＺｒＯ２的测定，获得满意的结果。     

CO／H2合成甲醇CuO—ZnO—ZrO2催化剂的研究

通过活性测定，ＸＲＤ、ＴＧ－ＤＴＡ表征，考察了共沉淀法制备的铜锌锆合成甲醇催化剂中ＺｒＯ２对物相结构、催化活性及热稳定性的影响。结果表明，ＺｒＯ２能显著提高ＣＯ／Ｈ２合成甲醇的催化活性和热稳定性。催化剂母体、氧化态和还原态的物相并未发生变化，仍分别为：Ｃｕ２（ＯＨ）３ＮＯ３，（Ｃｕ，Ｚｎ）５（ＣＯ３）２（ＯＨ）６，（Ｃｕ，Ｚｎ）２ＣＯ３（ＯＨ）２，Ｚｎ５（ＣＯ３）２（ＯＨ）６；ＣｕＯ、ＺｎＯ；Ｃｕ     

无定形（磷酸氢—二苯基次膦酸）锆—氯化铁复合物催化烷基化反应

制得无定形（磷酸氢－二苯基次膦酸）锆－氯化铁复合物Ｚｒ（ＨＰＯ４）１．５（Ｏ２Ｐ（Ｃ６Ｈ５）２）．（ＦｅＣｌ２（ＯＨ）。该复合不易吸潮，不冒烟，在空气中稳定，对代烷与芳得在液相的烷基化应有较好的催化活性，反应条件温和，产物收率高，操作方便，后处理简单，并可多次重复使用。     

溶胶—凝胶合成（Mg,Ca）O—SiO2：Eu^3＋,Bi^3＋发光体及其发光行为

以Ｍｇ（ＮＯ３）２，Ｃａ（ＮＯ３）２，Ｅｕ（ＮＯ３）３，Ｂｉ（ＮＯ３）３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度，首次合成０．７０１ｍｏｌＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏｌＳｉＯ２：０．０６ｍｏｌＥｕ＾３＋，０．００２ｍｏｌＢｉ＾３＋（加入Ｌｉ＾＋作为电荷补偿剂）发光体，得到了最佳合成条件，研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程，探讨了发光体在不同激光     

秦油2号油菜高产栽培中喷肥优化配方研究

采用二次饱和－Ｄ最优设计的方法，研究Ｓｒ（ＮＯ３）２（ｘ１）、ＫＨ２ＰＯ４（ｘ２）和Ｎａ２Ｂ４Ｏ７·１０Ｈ２Ｏ（ｘ３）叶面喷施对秦油２号油菜的产量效应，获得回归方程：ｙ＝２４７．４８５＋７．００４８ｘ１＋２．２９２４４ｘ２—９．８２６４６ｘ３—０．２５３５ｘ１ｘ２—１３．８５２４ｘ１ｘ３：—３．３７４７５ｘ２ｘ３＋２７．０５７５Ｘ２１—１６．３０３６ｘ２２—８．７６７８ｘ２３结果表明Ｓｔ（ＮＯ３）２。有明显的增产作用．ｘ１ｘ３的交互作用（效应）最大．通过计算机模拟．其最佳因子组合为Ｓｒ（ＮＯ３），０．１％、ＫＨ２ＰＯ４０．３％和硼砂０．０１％，预计产量可达２９６．４６ｋｇ／６６７ｍ２．     

α-磷酸锆层柱材料的制备、表征及其催化羰基化性能

采用配体４－ＣＨ３ＳＣ６Ｈ４ＮＨ２插层的α－磷酸锆为插层主体,将Ｒｈ６３＋引入层状材料的层析之间制备了新型层柱催化材料Ｚｒ（ＨＰＯ４）１．７０（ＣＨ３ＳＣ６Ｈ４ＮＨ２）１．０９（ＰＯ４）０．３０Ｒｈ０．１０．５．５２Ｈ２Ｏ,其是距为２．３６变为１．５６ｎｍ,结晶度有所下降。     

三（3－苯基－4－苯甲酰基异噁唑酮－5）－乙醇－水合铕三元配合物的合成、表征及晶体结构

合成了三（３－苯基－４－苯甲酰基异唑酮－５）－乙醇－水合铕的配合物。有关鉴定和元素分析结果表明：该配合物的分子式为［Ｅｕ（ＰＢＩ）３（Ｃ２Ｈ５ＯＨ）（Ｈ２Ｏ）］·Ｈ２Ｏ，其中３－苯基－４－苯甲酰基异唑酮－５简记为ＨＰＢＩ，是一种新型高酸度的β－双酮。用Ｘ射线单晶衍射法测定了［Ｅｕ（ＰＢＩ）３（Ｃ２Ｈ５ＯＨ）（Ｈ２Ｏ）］·Ｈ２Ｏ的晶体结构，结果表明，该晶体属单斜晶系，Ｐ２１／ａ空间群，晶胞参数：ａ＝１．５５８６（９）ｎｍ，ｂ＝２．１２９７（７）ｎｍ，ｃ＝１．６０４（１）ｎｍ，β＝１１７．９７（５）°，Ｖ＝４．７０３（９）ｎｍ３，Ｚ＝４．中心离子铕为八配位，其配位多面体为畸变的双帽三棱柱。配位的８个氧原子分别来自３个ＰＢＩ配体中的６个氧、１个溶剂化乙醇分子中的氧和１个水分子中的氧，Ｅｕ—Ｏ配位键平均键长０．２３９１（４）ｎｍ。晶体结构中还存在１个未配位的水分子。该水分子、配位水分子、乙醇分子与配体ＰＢＩ中的Ｎ原子之间均存在强的氢键作用。同一ＰＢＩ基团内配位氧之间的平均距离为０．２８０８ｎｍ。     

溶胶－凝胶法合成（Mg，Ca）O－SiO_2∶Eu~（3＋），Bi~（3＋）发

以Ｍｇ（ＮＯ３）２、Ｃａ（ＮＯ３）２、Ｅｕ（ＮＯ３）３、Ｂｉ（ＮＯ３）３、ＬｉＮＯ３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度下，首次合成０．７０１ｍｏＩＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏＩＳｉＯ２∶０．０６ｍｏｌＥｕ（３＋），０．００２ｍｏＩＢｉ（３＋）（加入Ｌｉ＋作为电荷补偿剂）发光体。得到了最佳合成条件。研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程。探讨了发光体在不同激发波长激发下的发光特性以及在激活剂、敏化剂不同掺杂量下的发光行为。讨论了在（Ｍｇ（ａ）Ｏ－ＳｉＯ２基质中Ｂｉ（３＋）对Ｅｕ（３＋）的能量传递和敏化作用。     

CO在YBa2Cu3Ox薄膜上吸附与加氢的研究

ＹＢａ２Ｃｕ３Ｏｘ（ｘ＝６－７）薄膜被合成在ＹＳＺ基底上，用ＦＴＩＲ，ＸＰＳ，ＸＲＤ等手段原位研究ＣＯ在薄膜上的吸附及加氢行为。ＣＯ吸附在Ｃｕ位置上，与ＹＢＣＯ体相中的Ｏ作用，生成表面ＣＯ２或－ＣＯＯ基团，导致ＹＢＣＯ中生产氧空位，使ＹＢＣＯ发生昌型转变，Ｃｕ＾２＋被还原为Ｃｕ＾＋或Ｃｕ＾０．ＹＢＣＯ中的氧空位有利于ＣＯ、ＣＯ２及Ｈ２的吸附。ＣＯ、ＣＯ２在ＹＢＣＯ膜上的加氢产物为ＣＨ３ＯＨ、ＣＨ３     

锆元素概念的形成和发展

1789年,普鲁士分析化学家克拉普罗特提出黄锆石中含有一种新土质,并将其命名为“锆土”,锆元素假说正式形成。随后,锆的原子重量的测定以及锆元素在元素表中位置的确定,促进了锆元素假说的发展。1914年,荷兰工程师勒利和汉布格首次制得纯度较高的金属锆,这使得锆元素假说得以证实,锆元素概念正式形成。从1924年至2020年,锆同位素的发现使人们对锆元素有了新认识,促使了现代锆元素概念的形成。锆元素概念的形成和发展的过程既是元素的发现史,也是化学思想和化学方法的演进史。     

Thermal Decomposition of Several Layered Zirconium Salts

The thermal decomposition of zirconium molybdate, tungstate and arsenate were investigated. The total mass losses of the investigated materials were 12.5, 11 and 8.5%, respectively. Despite having different crystal dimensions and structure the thermal decomposition of the samples takes place in a similar way. During heating two main endothermic processes with mass loss were observed. At the end of the thermal decomposition, oxides of the original materials were observed. The mentioned mass losses originate partly from the crystal water loss of the materials. The calculated crystal water content in the original molecule was 1.3 and 1 mole/molecule unit, respectively. Furthermore, for zirconium arsenate, a sublimation process was recorded above 960 K.This revised version was published online in November 2005 with corrections to the Cover Date.     

Changes in the zirconium local surrounding on ligand substitution in solutions

EXAFS and SAXS methods have been used to examine zirconium hydroxide and oxychloride aqueous solutions in the presence of sulfuric acid in a wide range of concentrations, as well as a zirconium sulfate aqueous solution. The structure of the complexes and their transformation regularities were determined. Structures of the given complexes and structures of zirconium hydroxide and zirconium oxychloride and hydroxide complexes in aqueous solutions were compared. Complexes in zirconium hydroxide and oxychloride aqueous solutions have identical structures in the presence of sulfuric acid. When the concentration ratio of sulfuric acid and the initial compound is low (20–30), the complex is an open trimer with zirconium atoms bonded by sulfate groups. Bridge sulfate groups form Zr-O-S-O-Zr bonds. Apart from the bridge sulfate groups, there are three terminal sulfate groups and three terminal hydroxyl groups for each zirconium atom. When the concentration of sulfuric acid is increased (up to a ratio of 40–100), closed trimers are observed in the solution.     

Structure of zirconium butoxide complexes in n-butanol solutions

EXAFS and SAXS were used for structure elucidation of zirconium butoxide complexes in n-butanol at concentrations from 0.3 g to 0.015 g ZrO₂ in 1 ml. The basic structural unit of the complex is a tetramer. It has two equal sides with zirconium atoms linked by double oxygen bridges and with zirconium-zirconium distances of 3.5 Å. The other sides in the tetramer are 3.3 Å and 3.9 Å. This difference in bond lengths is explained by the different numbers of double or single ligand bridges between zirconium atoms. The tetramers are apt to undergo oligomerization to form particles with a diameter of 80 Å in solution.     

Seeding and the Non-Hydrolytic Sol-Gel Synthesis of ZrW2O8 and ZrMo2O8

The unseeded non-hydrolytic sol-gel synthesis of ZrW₂O₈ and ZrMo₂O₈ produces trigonal ZrM₂O₈ (M = W, Mo) at 740 and 300–400°C, respectively. Cubic ZrW₂O₈ can be prepared using non-hydrolytic sol-gel methods by seeding with small amounts of preprepared cubic material, and the formation of the trigonal polymorph can be suppressed completely. Seeds with a small particle size are necessary for the preparation of cubic ZrW₂O₈. In contrast, seeding of ZrMo₂O₈ gels with either cubic ZrMo₂O₈ or cubic ZrW₂O₈ only lowers the temperature at which the trigonal phase crystallizes.     

The thermal decomposition of zirconium oxyhydroxide

The thermal decomposition of zirconium oxyhydroxides prepared by the mixture of aqueous zirconium oxychloride solutions and aqueous solutions of sodium hydroxide or ammonium hydroxide under various conditions has been examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectrophotometry. As a result, it is seen that the thermal decomposition of zirconium oxyhydroxide, in which the composition is ZrO_2-x(OH)_2xyH₂O where x2 and 1y<2, proceeds according to the following process:

锆氧杂环络合物合成方法探索

邻甲氧基苯基锂和 6,6-二甲基富烯 (或 6,6-二乙基富烯 )反应得配体锂盐 ( Cp′ Li) ,Cp′ Li直接和 Cp Zr Cl3· DME反应生成 2个新的锆络合物 Cp′ Cp Zr Cl2 。 BBr3和 Li Br分别用来使 Cp′ Cp Zr Cl2 环化 ,发现在相同条件下 BBr3比 Li Br3更有效。Cp′ Cp Zr Cl2 通过和 BBr3反应得到 2个新的锆氧杂环络合物。 4个新的锆络合物经元素分析、1 H NMR和 MS确证     

Thermoanalytical Investigation of Several Layered Zirconium Salts and their Derivatives Part II

The comparison of data of thermal analysis partly with XRD and/or analytical results permits determination of the exact quantity of crystal water of the investigated samples having quite different behaviour. The compositions of the samples were determined from the results of thermal analysis. Furthermore, the data help elucidate the behaviour of various crystalline materials and also their intercalates during heat treatment. This revised version was published online in July 2006 with corrections to the Cover Date.     

二(三甲硅基环戊二烯基)二氯合锆的合成和晶体结构

在 THF中 ,通过三甲硅基环戊二烯基锂与四氯化锆反应合成了标题化合物 ,经元素分析 ,IR和 1 H NMR谱表征了其结构 ,并用 X-射线衍射测定了晶体结构 ,该晶体属于三斜晶系 ,空间群为 P1 ,晶体学参数 :a=0 .6787(6) ,b=1 .2 92 4 (2 ) ,c=1 .30 34(2 ) nm,α=67.83(1 ) ,β=82 .50 (3) ,γ=75.64 (3)°,V=1 .0 2 5nm3 ,Z=2 ,Dx=1 .41 5 g· cm-3 ,μ=8.989cm-1 ,F (0 0 0 ) =448,R=0 .0 32。质谱研究表明 ,化合物在质谱过程中发生二聚 C*p2 ZrClZr C*P2Cl(C*P=C5H4Si Me3 )。