1,2-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)乙二酮-〔1,2〕与三正辛基氧化膦协同萃取RE(Ⅲ)的性能和机理研究

研究了 1,2 -双 ( 1′-苯基 - 3′-甲基 - 5′-氧代吡唑 - 4′-基 )乙二酮 -〔1,2〕( H2 A )与三正辛基氧化膦 ( TOPO )协同萃取 RE( ) ( RE=L a、Pr、Nd、Gd、Dy和 Y)的性能。通过考察萃取剂浓度、溶液酸度和温度对 RE( )萃取平衡的影响 ,确定了萃取机理和萃合物组成 ,求得了半萃取 p H1 /2 值和萃取反应平衡常数 Ks.e.。     

铕(Ⅲ)与2,2′-联吡啶配合物的合成与谱学研究

报道了铕离子 (Eu3+ )与 2 ,2′-联吡啶形成的配合物的制备 ,经过元素分析确定其化学组成为 [Eu(bipy) 2 (H2 O) 4]Cl3(bipy:2 ,2′-联吡啶 ) ,并用红外光谱 (IR)、紫外光谱 (U V)、荧光光谱、二维核磁同核相关谱 (1 H- 1 HCOSY)对上述配合物进行了研究 ,并提出了此配合物的可能的立体构型     

6,6″-二甲基-4′-苯基-2,2′∶6′,2″-三联吡啶与铅显色反应的分光光度研究

用作者合成的新显色剂 6,6″-二甲基 - 4′-苯基 - 2 ,2′∶6′ ,2″ -三联吡啶 (TPY)分光光度法测定痕量铅 ,在 pH5.0～ 6.0的HAc -NaAc介质中 ,该试剂与铅形成稳定络合物 ,其最大吸收波长在 375nm处 ,Pb2 +∶TPY =3∶4,表观摩尔吸光系数ε=5.71× 1 0 4 ,铅量在 0～ 2 5μg/2 5mL范围内服从比尔定律 ,用于纯铜试样的分析 ,结果满意。     

4-(3,5-二溴-2-吡啶重氮氨基)-4′-硝基偶氮苯的合成及其与镉(Ⅱ)显色反应的研究

合成了新显色剂4-(3,5-二溴-2-吡啶重氮氨基)-4′-硝基偶氮苯(简称DBPNAB),研究了在非离子表面活性剂Triton X-100存在下其与Cd(Ⅱ)的显色反应。结果表明,在pH10.2的Na2B4O7-NaOH缓冲介质中,该试剂与Cd(Ⅱ)形成摩尔比为2∶1的红色络合物,最大吸收波长位于581 nm,表观摩尔吸光系数为1.61×105L.mol-1.cm-1,镉的质量浓度在0～0.7μg/mL范围内遵守比尔定律。所拟方法用于废水中微量镉(Ⅱ)的直接测定,相对标准偏差为2.0%～3.3%,回收率为97.4%～103.6%。     

1-(2-吡啶偶氮)-2-萘酚褪色光度法测定稀土氧化物中微量铈

利用Ce（Ⅳ）的强氧化性对1-（2-吡啶偶氮）-2-萘酚（PAN）的褪色作用，建立褪色分光光度法测定微量铈的新方法。试验选择了最佳测定条件，讨论了共存离子的干扰情况。结果表明，在0．06～0．12mol／L H2 SO4介质中，有色溶液的最大吸收波长为440nm表观摩尔吸光系数ε=1．02×10^4L·mol^-1·cm^-1.铈量在0～8．0mg／L范围内与有色溶液褪色程度呈线性关系。方法用于稀土氧化物中微量铈的测定，相对标准偏差≤4．7％，回收率为94％～103％。     

SO4^2-／TiO2-WO3催化合成丁醛1，2-丙二醇缩醛

以固体超强酸SO4^2-／TiO2-WO3为催化剂，对以丁醛和1，2-丙二醇为原料合成丁醛1，2-丙二醇缩醛的反应条件进行了研究。实验表明：SO4^2-／TiO2-WO3是合成丁醛1，2-丙二醇缩醛的良好催化剂，研究了醛醇摩尔比、催化剂用量、反应时间诸因素对收率的影响。最佳反应条件为：n（丁醛），n（1，2-丙二醇）：1／1．4，催化剂用量为反应物料总质量的0．5％，环己烷为带水剂，反应时间50min。上述条件下，丁醛1，2-丙二醇缩醛的收率可达84．6％。     

1-(2-苯并噻唑偶氮)-2-羟基-3-萘甲酸与镍(Ⅱ)的显色反应研究及应用

用分光光度法研究了新试剂1-(2-苯并噻唑偶氮)-2-羟基-3-萘甲酸(BTAHN)与镍Ⅱ的显色反应性能。在pH4·6~10·4范围内,BTAHN与镍Ⅱ形成2∶1的蓝色络合物,该络合物的最大吸收波长λmax在612nm处,25mL溶液中镍的质量在0~34μg范围内服从比尔定律,测定的表观摩尔吸光系数ε612为3·52×104,所拟方法用于合金钢样品中微量镍的测定,结果满意。     

4-丙基-4′-氰基联苯的合成研究

以联苯为原料，经Friedel-Crafts反应、还原反应、碘代反应、氰化反应，合成4-丙基-4′-氰基联苯。此方法合成步骤少，操作简单，提纯方便，节省了费用。     

N,N′-双(2-水杨醛缩氨基苯基)-1,3-二丙二酰胺及其轻稀土配合物的合成

报道了N,N′-双(2-水杨醛缩氨基苯基)-1,3-二丙二酰胺(H4L)及其7种稀土配合物的合成,经NMR、IR,UV,摩尔电导,元素分析,TG-DTA等方法对配合物进行了表征,初步认证了配体及其配合物的结构,确认配合物组成为(Ⅰ)LRE2Cl2·6H2O(RE=La3+,Pr3+,Nd3+,Sm3+,Eu3+,Gd3+);(Ⅱ)LCe2(OH)2·(NO3)2·2H2O.并对其荧光性能进行测定,其中Eu,Sm,La配合物荧光性最好.     

1,6-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基) 己二酮与UO_2(Ⅱ),Th(Ⅳ)及Ce(Ⅳ)的配合物合成及性质

本文用电导滴定和pH滴定法研究了乙醇—水液溶中UO_2(Ⅱ),Th(Ⅳ)及Ce(Ⅳ)与1,6—双(1′苯基-3′-甲基-5′-氧代吡唑-4′-基)已二酮的配合反应。合成了固态配合物:UO_2L·H_2O,ThL_2·2H_2O和Ce_2L_3(NO_3)_2·4H_2O,研究了它们的UV,IR,~1HNMR,荧光光谱及热稳定性。     

Preparation of La0.9RE0.1MnO3 Ultra-fine Particles Used for CH4 Oxidation

Ｐｅｒｏｖｓｋｉｔｅ ｔｙｐｅｏｘｉｄｅｓ (ｇｅｎｅｒａｌｆｏｒｍｕｌａＡＢＯ3 )ｈａｖｅｂｅｅｎａｔｔｒａｃｔｉｎｇｍｕｃｈａｔｔｅｎｔｉｏｎｆｏｒｍｏｒｅｔｈａｎｔｗｏｄｅｃａｄｅｓｄｕｅｔｏｔｈｅｉｒｐｏｔｅｎｔｉａｌｃｏｍｍｅｒｃｉａｌａｐｐｌｉｃａｔｉｏｎｓａｓｃａｔａｌｙｓｔｓｆｏｒｖａｒｉｏｕｓｒｅａｃｔｉｏｎｓ :ｏｘｉｄａｔｉｏｎｏｆＣＯ[1～ 3 ] ａｎｄｌｉｇｈｔｈｙ ｄｒｏｃａｒｂｏｎｓ[4～ 7] ,ｃｏｍｂｕｓｔｉｏｎｏｆｎａｔｕｒａｌｇａｓｏｒＣＨ4 [8～ 1 1 ] (ｔｏｃｏｎｔｒｏｌＮ…     

Synergistic extraction of rare earths by mixture of HDEHP and HEH/EHP in sulfuric acid medium

The extraction of RE（Ⅲ） （RE=La, Nd, Sm, Gd） in sulfuric acid medium using the mixture of HDEHP（H2B2） and HEH/EHP（H2L2） was investigated. The synergistic enhancement coefficient（R） was calculated for La （1.96）, Nd（3.52）, Sm（5.96）, and Gd（5.71）, respectively, at pH=2.0, and it was seen that the R increased with the increase of aqueous quilibrium pH. The configuration of the extracted complexes was considered to be RE（SOa）xH2x（HB2）3 with HDEHP, RE（SOa）xH2x（HL2）3 with HEH/EHP, and RE（HB2）2（HL2） with their mixture as the extractant with the slope method. The equilibrium constants and stability constants were calculated. A cation exchange mechanism was proposed as well.     

Stability of Rare Earth Ion-N, N′-bis（2′-Pyridine）methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

1 ,10 Phenanthrolinehasbeenextensivelyusedasanazaheterocyclicchelateligandinbothanalyticalandpreparativecoordinationchemistry[1] .Asanim portantligand ,1,10 phenanthrolineunitplaysanim portantroleforthedevelopmentofthesupramolecularchemistry .Manynovelsupramolecularcompoundsin clude 1,10 phenanthrolineunit[2～ 4 ] .Furthermore ,consideringtheuniquecombinationofchemicalstabil ities ,redoxproperties ,luminescenceemissionandex citedstatelifetime ,derivativesof 1,10 phenanthrolinehaveplayedama…     

金属钕及氧化钕中稀土杂质光谱测定

在色散０．２５ｍｍ／ｍｍ光栅光谱仪上，以控制气氛直流电弧粉末地测定了金属钕及氧化钕中氧化镧、氧化铈、氧化镨、氧化钐、氧化钆、氧化镝和氧化钇。采用正交设计实验，确定了测定条件。测定的下限对氧化铈、氧化镨为０．０５％，氧化镧、氧化钐、氧化钆、氧化镝和氧化钇为０．０３％，相对标准偏差为６％￣１８％。     

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.     

Effect of trivalent rare earth ions doping on the fluorescence properties of electron trapping materials SrS：Eu~（2＋）

Trivalent rare-earth ions (La3+,Pr3+,Nd3+,Sm3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Tm3+,and Yb3+) were investigated as the codoped auxiliary sensitizer for the electron trapping materials SrS:Eu2+ in order to enhance the fluorescence properties.It was found that Sm3+ and Tb3+ had the best photoluminescence stimulated luminescence (PSL) effect among the selected trivalent rare-earth ions.All the SrS:Eu2+ samples doped by different trivalent rare-earth ions could be stimulated by 980 nm laser after being exposed to the conventional sunlight,and they emitted PSL with the peak located at 615 nm.The result also indicated that some co-doped rare earth ions could increase fluorescence intensities of the traditional electron trapping materials SrS:Eu2+.     

HPMBP和DAM协同萃取Ln~(3 )的研究

研究了１－苯基－３－甲基－４－苯甲酰基吡唑酮－５（ＨＰＭＢＰ）和二安替吡啉甲烷（ＤＡＭ）的氯仿溶液从硝酸介质中对Ｌｎ３＋（Ｌｎ＝Ｌａ，Ｐｒ，Ｎｄ，Ｇｄ）的协同萃取，测定了其半萃取ｐＨ值，结果分别为４．３８（Ｌａ３＋）、３．９７（Ｐｒ３＋）、３．９２（Ｎｄ３＋）和３．８２（Ｇｄ３＋）。通过斜率法确定了协萃合物的组成为Ｌａ（ＰＭＢＰ）３（ＤＡＭ），并合成了固态萃合物。     

铽在硫氧化镧基质中的光致发光

采用高温固相反应法制备了La2O2S∶Tb3+、La2O2S∶Tb3+,RE3+(RE=Dy,Gd,Ce,Sm)荧光粉样品并进行了相关表征。结果表明,合成样品的晶体结构与La2O2S相同,为六方晶系;荧光粉颗粒的形貌多为长方形片状;发射光谱由494 nm、545 nm、587 nm、622 nm的一系列锐发射峰组成。研究发现Tb3+的掺杂浓度对样品主发射峰545 nm的发光强度影响很大,且在摩尔分数x(Tb3+)=0.02时达到最强。稀土离子Dy3+、Gd3+对La2O2S∶Tb3+荧光粉的发光有明显的敏化作用。     

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…     

Raman spectra of RE2O3 （RE=Eu,Gd, Dy,Ho, Er,Tm, Yb,Lu, Sc and Y）：laser-excited luminescence and trace impurity analysis

Raman spectra of a series of cubic rare earth sesquioxides RE2O3 （RE=Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y） were investigated by Raman spectroscopy with both 532 and 785 nm laser lines. Abundant additional bands due to laser-excited lumines-cence were observed. For Eu2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3, the luminescence mainly came from the intrinsic trivalent lanthanide ions, while for Gd2O3, Lu2O3, Sc2O3 and Y2O3, their luminescence were attributed to the trace impurities of other lumines-cent lanthanide ions such as Eu3＋, Nd3＋and Er3＋. This investigation confirmed Raman spectroscopy as a useful tool for detecting trace luminescent lanthanide impurities.