H2BPMPBD和PMTFP协同萃取Ln(Ⅲ)的研究

研究了1,4-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)丁二酮(H2BPMPBD,简写为H2A)和1-苯基-3-甲基-4-三氟乙酰基吡唑酮-5(PMTFP)的氯仿溶液从硝酸介质中对Ln(Ⅲ)的协同萃取.用斜率法确定了萃合物的组成为LaA·HA·PMTFP,考察了萃取剂浓度和溶液酸度对萃取机理的影响,测定了半萃取pH1/2值和萃取反应平衡常数Ks.c.,求得了反应的焓变和熵变.     

H2BPMPBD和HOx协同萃取部分Ln(Ⅲ)

研究了1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](H2BPMPBD,简为H2A)和8-羟基喹啉(HOx)的氯仿溶液从硝酸介质中对Ln( )(Ln=La,Pr,Nd,Gd,Dy)的协同萃取。用斜率法确定了萃合物的组成为LaA·HA·HOx,考察了萃取剂浓度和溶液酸度对萃取机理的影响,测定了半萃取pH1/2值和萃取反应平衡常数Ks.e.,求得了反应的焓变和熵变。     

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.。     

H2BPMPBD和AP协同萃取Ln(Ⅲ)的研究

研究了1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](H2BPMPBD,简为H2A)和氨基比林(AP)的氯仿溶液从硝酸介质中对Ln( )的协同萃取。用斜率法确定了萃合物的组成为LaA·HA·(AP)2,考察了萃取剂浓度和溶液酸度对萃取机理的影响,测定了半萃取pH1/2值和萃取反应平衡常数Ks.e.,求得了反应的焓变和熵变。     

H2BPMOPP和Phen协同萃取Ln3+的研究

研究了 1,2 -双 (1′-苯基 - 3′-甲基 - 5′-氧代吡唑 - 4′-基 )邻苯二酮 (H2 BPMOPP,简为 H2 A)和邻菲 口罗啉 (Phen)的氯仿溶液从硝酸介质中对 L n3 (L n=L a,Pr,Nd,Gd,Dy)的协同萃取。用斜率法确定了萃合物的组成为 L n A· HA· Phen,考察了萃取剂浓度和溶液酸度对萃取机理的影响 ,测定了半萃取 p H1 /2 值和萃取反应平衡常数 Ks.e.,求得了反应的焓变和熵变。     

D_2EHDTPA萃取铟的热力学研究

报道了用二 (2 乙基己基 )二硫代磷酸为萃取剂 ,以正庚烷为稀释剂萃取铟的热力学研究。在In2 (SO4 ) 3+Na2 SO4 +D2 EHDTPA +n C7H1 6 +H2 O体系中 ,在温度 2 78.15～ 3 0 3 .15K和离子强度 0 .1～ 2 .0mol·kg- 1 范围内 ,以Na2 SO4 为支持电解质 ,测定了萃取平衡水相中In3+浓度和pH值。计算了萃取反应的标准平衡常数K0 ,并得到经验公式logK0 =43 .93 -5 3 68.5 4 T -0 .0 699T ,同时计算了萃取反应的其他热力学量 ,并指出了焓和熵都是此萃取过程的推动力     

用双(2-乙基己基)膦酸(PIA-8)的甲苯溶液萃取分离Co(Ⅱ)和Ni(Ⅱ)

D.V.Koladkar等研究了用双 (2 -乙基己基 )膦酸 (PIA-8)的甲苯溶液从硫酸盐溶液中萃取钴 ( )和镍 ( )。试验表明 ,用浓度为 0 .0 3 mol/L的 PIA-8甲苯溶液萃取时 ,钴 ( )在 p H为 5 .0～ 5 .9范围内被定量萃取 ,而镍 ( )则在 p H为 6.8～ 7.0范围内被定量萃取。钴 ( )和镍 ( )的 p H0 .5值相差 1.9。用斜率分析法确定的萃合物的化学式为 Co· R2 (HR) 2 和 Ni· R2 · 2 (HR) 2 。萃取反应属阳离子交换机理。该方法可用于分离钴 ( )和镍 ( ) ,当溶液中镍的浓度是钴浓度的 2 0倍时 ,也能很好地将钴 ( )与镍 ( )分开。温度对钴 ( )萃…     

1,9-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)壬二酮-〔1,9〕与三辛基氧膦,三苯基氧膦对铕(Ⅲ)的协同萃取

研究了1,9 - 双(1′- 苯基- 3′- 甲基-5′- 氧代吡唑-4′- 基) 壬二酮- 〔1 ,9〕(BPMPND, H2A) 与三辛基氧膦(TOPO) 或三苯基氧膦(TPPO) 的氯仿溶液从硝酸介质中对铕( Ⅲ) 的协同萃取行为。用斜率法测定了BPMPND单独和协同萃取铕(Ⅲ) 的萃合物组成分别为EuA·HA 和EuA·HA·B(B为TOPO 或TPPO) , 计算了相应的萃取平衡常数。用萃取法制得了固态协萃合物, 并对其组成和IR进行了研究。     

La(C7H5O3)2·(C9H6NO)的合成及热化学研究

研究由七水氯化镧与水杨酸、8-羟基喹啉反应合成镧与水杨酸、8-羟基喹啉多元混合配合物,并对该配合物进行表征.测定该合成反应的标准摩尔反应焓以及配合物的标准摩尔生成焓.通过红外光谱、元素分析、摩尔电导率、差热热重分析以及化学分析等方法来确定配合物的组成.应用溶解量热法分别测定了七水氯化镧、水杨酸、8-羟基喹啉和配合物在298.15 K、混合量热溶剂(VDMFVEtOHVHClO4=110.5)中的标准摩尔溶解焓.通过设计热化学循环,根据盖斯定律计算了合成反应的标准摩尔反应焓以及配合物的标准摩尔生成焓.该配合物的分子式是La(C7H5O3)2·(C9H6NO).各物质的溶解焓分别为△sH(I○)mLaCl3·7H2O(s),298.15 K]=-96.45±0.18 kJ·mol-1,△sH(I○)m[2 C7H6O3(s),298.15 K]=14.99±0.17 kJ·ml-1,△SH(I○)m[C9H7NO(s),298.15 K]=-3.86±0.06kJ·mdl-1及△S(I○)m[La(C7H5O3)2·(C9H6NO)(s),298.15K]=-117.78±0.11kJ·mol-1.反应LaCl3·7H2O(s)+2C7H6O3(s)+C9H7NO(s)=La(C7H5O3)2·(C9H6NO)(s)+3HCl(g)+7H2O(1)的标准摩尔反应焓为91.57±0.33 kJ·mol-1.La(C7H5O3)2·(C9H7NO)(s)的标准摩尔生成焓为△sH(I○)m[La(C7H5O3)2·(C9H6NO)(s),298.15 K]=-2076.5±3.9 kJ·mol-1.     

稀土和2, 3-二氯异丁酸及2, 2''-联吡啶混配配合物的合成与表征

以先制得 2 ,3-二氯异丁酸根 (L )稀土二元配合物再加入 2 ,2 '-联吡啶 (dipy)的方法 ,在丙酮溶液中合成了钕、钆、镱的 2 ,3-二氯异丁酸根 (L )和 2 ,2 '-联吡啶 (dipy)稀土混配配合物。通过元素分析、红外、紫外、X-射线粉末衍射、XPS、热分析以及摩尔电导等分析手段 ,确定了标题配合物的组成为 [REL3dipy]· H2 O。并对它们的性质进行了表征和讨论     

稀土离子与钙调素相互作用的研究进展

稀土离子由于配位环境与钙离子具有相似性,能够取代钙离子与钙调素发生作用,对钙调素的结构、构象及生物功能产生影响。各种光谱及生物化学实验研究表明,不同稀土离子与钙调素作用时,在作用力的强弱程度、结合位点、结合序及结合位点的相互作用具有各自的特殊性,本文概述了稀土离子La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Ho3+、Er3+和Lu3+等与钙调素的相互作用及对钙调素生物功能产生的影响。     

Study of Adsorption Properties and Enriching RE on Clay Minerals by Ouantum Chemical Calculation

The order of adsorbability of three kinds of clay minerals and their selectivity of adsorption tocommon cations and RE ions have been studied by quantum chemical calculation.They are as follows:montmorilionite>halloysite>kaolinite,RE~(3+)>Al~(3+)>Ca~(2+)>Mg~(2+)>K~+>NH_4~+>Na~+,Sc~(3+)>La~(3+)>Ce~(3+)>Pr~(3+)>Nd~(3+)>Sm~(3+)>Eu~(3+)>Gd~(3+)>Tb~(3+)>Dy~(3+)>Ho~(3+)>Y~(3+)>Er~(3+)>Tm~(3+)>Yb~(3+)>Lu~(3+).Based onthese orders,the facts that RE is preferentially adsorbed in weathered residual type of clay mineral and lightRE and heavy RE are enriched at the upper layer and at the lower layer respectively in ore body have beenexplained.     

A single-phased white-emitting Ca_2Ga_2GeO_7:Dy~(3+) phosphor with different charge compensation ions

A novel white-emitting Ca_2Ga_2GeO_7:Dy~(3+) phosphor was synthesized via a high-temperature solid-state reaction.The crystal phase was analyzed by X-ray diffraction(XRD),and the photoluminescence(PL) properties were studied by luminescence spectra and fluorescence decay curves.Under the excitation of 347 nm,the obtained phosphor exhibited strong emission in the blue region peaked at 478 nm,yellow at 574 nm and a weak red emission band at 665 nm,corresponding to the characteristic transitions of ~4F_(9/2)to ~6H_(15/2),~6H_(13/2) and ~6H_(11/2) of Dy~(3+),respectively.By varying the doping concentration of Dy~(3+),tunable colors from blue-white to yellow-white were obtained in the phosphors.Besides,by codoping charge compensators(Li~+,Na~+,K~+ and Ga~(3+)) in Ca_2Ga_2GeO_7:Dy~(3+),the optimum CE color coordinate and PL intensity were obtained in Ca_2Ga_2GeO_7:Dy~(3+),K~+.Accordingly,the PL mechanism of Ca_2Ga_2GeO_7:Dy~(3+) was discussed briefly.     

Effect of RE~(3+) electronegativities on luminescence property of Ba_5Si_8O_(21):Eu~(2+) persistent phosphor

A series of Ba_5Si_8O_(21):0.02Eu~(2+),0.09RE~(3+) persistent phosphors were synthesized by the solid-state reaction method.The measurement results of photoluminescence(PL),phosphorescence and thermoluminescence(TL)were analysed and discussed.The XRD results showed that samples codoped with different RE~(3+) were Ba_5Si_8O_(21) single pure phase.Under the excitation,all samples exhibited a broad Eu~(2+) characteristic emission,and the La~(3+) co-doped sample emitted the brightest photoluminescence even though its persistent luminescence property was the worst because of the weakest electronegativity.However,Nd~(3+) electronegativity was suitable,thus after activation,the Ba_5Si_8O_(21):Eu~(2+),Nd~(3+) sample had the best persistent luminescence performance with the highest phosphorescence intensity and the persistent luminescence decay time beyond 8 h.The Nd~(3+) co-doped sample also had the largest thermoluminescence integral area which proved effectively it had longer persistent luminescence time.The luminescence mechanism was also proposed to study the photoluminescence and persistent luminescence process.These results showed that RE~(3+) electronegativities were distinctly important for persistent phosphors and choosing suitable electronegativity codopant was conducive to enhancing the phosphorescent performance.     

Crystal-field analyses for trivalent lanthanide ions in LiYF_4

Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln~(3+) in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce~(3+), Nd~(3+), Sm~(3+), Dy~(3+) and Yb~(3+) were in good agreement with experiment, while those of Er~(3+) deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm~(-1) led to g factors agreeing well with the experimental values.     

Significant enhancement of blue photoluminescence intensity of Dy~(3+) modified Sr_6Ca_4(PO_4)_6F_2:Eu~(2+) phosphors

Blue-emitting phosphors Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+)(SCPF:Eu~(2+)),Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+),Dy~(3+)(SCPF:Eu~(2+),Dy~(3+))and Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+),Dy~(3+),Si~(4+)(SCPF:Eu~(2+),Dy~(3+),Si~(4+)) with apatite structure were successfully synthesized by traditional solid-state reaction under reducing atmosphere.Eu~(2+),Dy~(3+) and Si4+ions occupy the corresponding sites of Sr~(2+),Ca~(2+) and P~(5+).Strong broad blue photo luminescence band is exhibited in SCPF:Eu~(2+),Dy~(3+) phosphor ranging from 400 to 550 nm centered at 455 nm and Dy~(3+) ions are vital in creating traps.Emission intensity of Eu~(2+),Dy~(3+) co-doped SCPF:0.02 Eu~(2+),0.02 Dy~(3+) is about 1.8 times that of SCPF:0.02 Eu~(2+) and electron trap centers serve as energy transporting media.To further elucidate the formation and effect of the specific defect on the luminescence of SCPF:0.02 Eu~(2+),0.02 Dy~(3+) phosphor,the thermoluminescence properties,decay curves and thermal stability studies were performed while the Si~(4+)-P~(5+) charge compensated pho sphor SCPF:0.02 Eu~(2+),0.02 Dy~(3+),0.02 Si~(4+) was prepared as a contrast.All the results of present work indicate that Dy~(3+) co-doping can obviously enhance photoluminescence intensity of SCPF:0.02 Eu~(2+) by the electron traps generated by non-equivalence replacement of Dy~(3+)-Ca~(2+).     

Microcapsules containing ionic liquid [A336][P507] for La~(3+)/Sm~(3+)/Er~(3+)recovery from dilute aqueous solution

The efficacy of polysulfone microcapsules encapsulating ionic liquid [trialkylmethylammonium][di(2-ethylhelxyl) orthophosphinate]([A336][P507]) for the extraction of La~(3+), Sm~(3+) and Er~(3+) from dilute aqueous solutions was investigated. Microcapsules were synthesized using coaxial microfluidic method, and subsequently encapsulated with extractant [A336][P507]. The kinetics data were fitted well by pseudo-second-order equation and Crank model, and the kinetics parameters were evaluated. The extraction rate had the order of Er~(3+)Sm~(3+)La~(3+). The isotherm data were analyzed by Langmuir model and shifted Langmuir model. The extraction capacities of La~(3+), Sm~(3+) and Er~(3+) were 58.4, 56.6 and 81.7 mg/g, respectively. The dependency of stripping performance on HNO3 concentration was measured. The regeneration of microcapsules was evaluated using cycling extraction experiments.     

Presence of neodymium and gadolinium in cobalt ferrite lattice:Structural,magnetic and microwave features for electromagnetic wave absorbing

In this work,neodymium substituted gadolinium-cobalt ferrite nanoparticles were synthesized by hydrothermal method.The significant role of doping both the Nd~(3+)and Gd~(3+) ions to cobalt ferrite in manipulating the cation distribution and further in influencing structural and magnetic properties was experimentally studied and reported.The influence of Nd~(3+) substitution was investigated with step of 0.02-0.1 into the optimized Gd-Co compound.The crystal structure formation and crystallite size were explored by X-ray diffraction analysis in which the crystallite size and lattice constant decrease with increasing the Nd~(3+) substitution.The microstructural properties were studied by field emission scanning electron microscopy and atomic force microscopy studies.The obtained structural and morphological results reveal that the substitution of Nd~(3+) with more than 0.06 into the Gd-Co ferrites will change the material be havior and trends.The saturation magnetization and coercivity values were measured using a vibration sample magnetometer at room temperature.Comparative microwave absorption experiments demonstrate that the reflection loss properties enhance with increasing substitution of Nd~(3+) cations in Gd-Co ferrite spinel structure.This research reports that the as-prepared Nd~(3+) substituted Gd-Co ferrite compound stands as promising candidate for absorbing electromagnetic wave with a wider absorbing bandwidth of X-band.     

Optical performance study of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+) ternary luminous fiber

In this study, down-conversion fluorescent powder of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+), which were the common three primary colors materials with long afterglow, were synthesized by high temperature solid state method. The blends of rare earth(RE) luminescent materials have been of interest to reinvest the luminescent characteristics of polyethylene terephtahalate(PET) luminous fiber. The scanning electron microscopy(SEM) and an inversion fluorescence microscope were used to characterize the surface morphology and the dispersion of inclusion. Through analysis of microcosmic morphology, three typical dispersions of luminescent particles were summarized. The X-ray diffraction indicated that the phase structure of fiber samples and crystal structure of luminescence materials kept complete after prilling and spinning. From the fluorescence spectra and CIE 1931 coordinates, it could be found that different combinations of luminous fibers were desired to obtain divers colors emission luminous fiber. And the fiber samples were a light sensation which could induct different excitation wavelengths and convert it down to different colors. The afterglow decay curve and its differential curve were summarized indicating the three decay stages. The decay curve and decay rate curve showed that the contents of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+) had obvious influence on the afterglow of fiber samples.     

Ultraviolet to near-infrared energy transfer in NaYF_4:Nd~(3+),Yb~(3+) crystals

To convert ultraviolet(UV) light into near-infrared(NIR) light in phosphors is demanded for the development of solar cells.A series of NaYF_4:Nd~(3+),Yb~(3+) white powder samples were prepared via the hydrothermal method.The crystal structure and photoluminescence properties of the samples were carefully studied using X-ray diffractometry(XRD) and photoluminescence spectra.The excitation and emission spectra of NaYF_4:Nd~(3+),Yb~(3+) samples and the luminescence decay curves of Nd~(3+) and Yb~(3+) revealed an efficient energy transfer process from Nd~(3+) to Yb~(3+).This process resulted in the Yb~(3+) NIR fluorescent emission at 980 nm.Moreover,the lifetime of the Nd~(3+4)F_(3/2) level decreased with the increase of Yb~(3+) doping concentration.The build-up time of the decay curves of the Yb~(3+2)F_(5/2) level further verified the energy transfer process.Meanwhile,energy transfer efficiency based on different Yb~(3+) doping concentrations was achieved.