Eu掺杂对γ-Ce2S3合成温度及抗氧化性能的影响

本文以CeCl_3·7H_2O、Eu_2O_3、C_2H_2O_4·2H_2O为原料,制备了铈铕草酸盐沉淀,该沉淀经高温煅烧获得铈铕氧化物前驱体;以Ar气为载气、CS_2为硫源对铈铕氧化物前驱体进行硫化合成了Eu~(2+)掺杂的γ-Ce_2S_3。Eu~(2+)掺杂能够明显降低γ-Ce2S3的合成温度,Eu~(2+)/Ce~(3+)为0. 03时,在900℃硫化150min即可获得纯相的γ-Ce_2S_3,与不掺杂时合成γ-Ce_2S_3的温度相比降低了300℃左右;同时,Eu~(2+)掺杂能够提升γ-Ce_2S_3的抗氧化能力,氧化气氛下,Eu~(2+)/Ce~(3+)比例为0. 03的样品其氧化放热峰温度由不掺杂时的490. 6℃提高至553. 3℃。     

沸石基质中Eu^3＋的还原及Eu^2＋的稳定性

低温弱还原条件下,在沸石基质中获得了稳定的Eu~(2+)。借助程序升温还原(TPR)技术考察了沸石中Eu~(3+)→Eu~(2+)还原温度及价态转换途径。通过穆斯堡尔谱讨论了价态转换过程中,铕离子在沸石笼结构中的配位环境及其与沸石骨架的相互作用。光电子能谱和荧光光谱数据表明,Eu~(2+)在沸石基质中价态是稳定的。     

氟氯化钡铕的合成、发光性能以及在X射线照像增感屏中的应用

铕激活的氟氯化钡是一种高效率的发光材料。Sommerdijk 等讨论过 MeFX:Eu~(2+)的发光。Tangue等报道过 MeFX:Eu~(2+)在低温下的发射光谱。Stevel等研究了 BaFX:Eu~(2+)在 X 射线激发下的发光性质。     

镧系元素光化学 III: 铕的光还原分离

本文报道了以低压汞灯做光源, HCO2H-HCO2Na做自由基清除剂, Na2SO4做光还原产物Eu(II)的沉淀剂, 在改变自由基清除剂、沉淀剂和稀土离子浓度、溶液的酸度和光强度的条件下, 研究了从铕和其它镧系元素氯化物的二元混合物中光还原分离提取铕的问题, 同时测定了沉淀的组成以及元素间的分离因数(β)。     

镧系元素光化学 III: 铕的光还原分离

本文报道了以低压汞灯做光源, HCO2H-HCO2Na做自由基清除剂, Na2SO4做光还原产物Eu(II)的沉淀剂, 在改变自由基清除剂、沉淀剂和稀土离子浓度、溶液的酸度和光强度的条件下, 研究了从铕和其它镧系元素氯化物的二元混合物中光还原分离提取铕的问题, 同时测定了沉淀的组成以及元素间的分离因数(β)。     

蓄光发光材料SrAl2O4:Eu2+,Dy3+及其常温磷光光谱分析

组成为SrAl_2O_4:Eu~(2+),Dy~(3+)的稀土铝酸锶系蓄光发光材料(也称为超长余辉发光材料)是目前已开始广泛应用的第三代产品。该材料基质中的二价稀土铕离子Eu~(2+)作为发光中心,能够吸收波长为480nm以下的可见光和紫外光,发出波长为520nm的     

碱土金属锡酸盐掺铕体系荧光粉合成和荧光性质研究

本文报道了MSnO_3∶Eu~(3+)和M_2SnO_4∶Eu~(3+)(M=Ca,Sr,Ba)体系荧光粉的合成和荧光性质。产品经X射线确证CaSnO_3∶Eu~(3+)和Ca_2SnO_4∶Eu~(3+)为正交晶系,SrSnO_3∶Eu~(3+)和BaSnO_2∶Eu~(3+)为立方晶系,而Sr_2SnO_4∶Eu~(3+)和Ba_2SnO_4∶Eu~(3+)为四方晶系。激发光谱表明,随Ba—Sr—Ca离子半径减小,Eu~(3+)的电荷迁移能量紫移,而Eu~(3+)的f-f跃迁红移。发射光谱表明,CaSnO_3∶Eu~(3+)和Ca_2SnO_4∶Eu~(3+)以电偶极跃迁为主,而其它4种化合物不存在电偶极跃迁。     

三辛基氧化膦修饰电极富集溶出机理的光谱表征

化学修饰电极表面的表征是修饰电极研究的重要方面,我们曾报道用三辛基氧化膦(TOPO)修饰电极进行铕(Ⅲ)的测定,发现在含有Eu~(3+)和噻吩甲酰三氟丙酮(HTTA)的HAc-NaAc溶液中,能得到一个十分灵敏的阴极溶出峰,而HTTA不存在时,则无明显的峰因此,HTTA对Eu~(3+)的富集过程一定起着某种重要的协同作用,我们认为,HTTA在溶液中存在酮式与烯醇式的平衡,其烯醇式与溶液中的Eu~(3+)和H_2O形成中性络合物[Eu(TTA)_3·(H_2O)],当其扩散至TOPO修饰电极表面时,电极表面的TOPO就将其水分子取代,生成更稳定的协同三元络合物,从而将Eu~(3+)富集在电极表面:     

铽-铕共掺杂的硅酸铝钠荧光体的光致发光性能及能量传递

采用温和的固相反应法合成了具有四方相结构的铽一铕共掺杂的硅酸铝钠(NaAlSiO_4:Tb~(3+),Eu~(3+))发光材料.利用粉末X射线衍射(XRD)、荧光光谱(PL)、时间分辨光谱(TRPL)以及荧光寿命等手段对合成的样品进行表征.研究结果表明:通过改变NaAlSiO_4:Tb~(3+),Eu~(3+)中Eu~(3+)离子的掺杂浓度,可实现其绿光及红光发射的调控;由于Tb~(3+),Eu~(3+)离子间的有效能量传递,Tb~(3+)离子的共掺杂可显著增强该基质中Eu~(3+)离子的发光性能;该能量传递现象可由TRPL光谱等手段进行证实,根据荧光寿命的数值计算可知,从Tb3~(3+)向Eu~(3+)离子的能量传递效率高达95%.     

用电子自旋共振波谱和荧光光谱研究BaFCl:Eu中铕的价态

BaFCl:Eu是一种优良的X射线发光材料,最近我们发现:虽然它的发光起源于Eu~(2+)离子的4f~65d→4f~7能级间的电子跃迁;但是晶体中同时存在的Eu~(3+)离子的电荷转移跃迁对发光有很明显的增强作用。因此在研究Eu~(2+)和Eu~(3+)离子在发光过程中的作用时,必须首先要知道它们在发光材料中的浓度。我们提出了一种准确测定BaFCl:Eu中Eu~(2+)和Eu~(3+)离子含量的方法。这种方法是依据Eu~(2+)离子的电子自旋共振(ESR)波谱以及Eu~(2+)和Eu~(3+)离子的发光光谱。我们合成了一系列含有不同Eu~(2+)/Eu~(3+)浓度比的BaFCl:Eu,并初步讨论了它们的发光现象。     

Determination of photoredox properties of individual kinetically labile complexes in equilibrium systems

The paper evaluates the possibilities and limitations in characterising photochemical properties of individual kinetically labile species being in mutual equilibrium. A model of calculating quantum yield values is elaborated and applied to azidokojic iron(III) complexes in aqueous solutions. Based on the known speciation of the complexes as a function of pH, Fe(III) and azidokojic acid concentrations, electronic absorption spectra of individual species, and the determined overall quantum yield of Fe(II) photoformation at irradiation with monochromatised radiation at 366 nm, the quantum yield of Fe(III) to Fe(II) photoreduction was obtained for each of the complexes present in the investigated systems.     

Flow-injection determination of europium after on-line reduction

A zinc reductor minicolumn is used in a flow-injection system for reduction of europium(III) to europium(II). Europium(II) is indirectly determined either spectrophotometrically by oxidation with iron(III) and reaction of the iron(II) formed with 1,10- phenanthroline, or spectrofluorimetrically by reaction with cerium(IV) and measurement of the cerium(III) produced. The reductor functions efficiently at flow rates up to 1 ml min^?1, which allows sample injection rates up to 100 h^?1. Linear calibration is achieved for 10–200 and 0.5–4 μg ml^?1 with detection limits of 2.5 and 0.25 μg ml^?1, by spectrophotometry and spectrofluorimetry, respectively.     

Titration of antimony(III) with cerium(IV) sulphate and diphenylamine and its derivatives as reversible indicators

Diphenylamine, barium diphenylamine sulphonate, N-phenylanthranilic acid and 2-nitrodiphenylamine have been investigated as reversible indicators for the titration of antimony(III) with cerium(IV) sulphate in 0.5–2 M sulphuric acid medium. Diphenylamine is the most satisfactory in titrations of antimony(III) in chloride-free solutions, e.g. of potassium antimonyl tartrate. Even low chloride concentrations affect the indicator action of N-phenyl-anthranilic acid or 2-nitrodiphenylamine, but diphenylamine is satisfactory in 1 M hydrochloric acid media. Iodine catalyst is necessary to accelerate the reduction of the oxidized indicator by antimony(III). The indicator colour change is vivid and the colour of the oxidized indicator is stable. Titrations of antimony(III) in mixtures with iron(II) and arsenic(III) are also considered.     

A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium--VII. Photometric titration of vanadium(IV) and of cerium(III) alone and in mixtures with iroN(II)

Vanadium(IV) can be accurately titrated with potassium dichromate in media containing phosphoric acid of 3-12M concentration: the change in absorption of vanadium(IV) is followed in the region 660 mmicro using a red filter. It is more convenient to carry out the titration in 3M phosphoric acid because at higher concentrations chloride, nitrate, cerium(III) and manganese(II) may interfere. Photoelcetric titration is more convenient than potentiometric because the former can be made in a 3M phosphoric acid medium, whereas the latter is possible only in 12M phosphoric acid. The simultaneous differential photometric titration of iron(II) and vanadium(IV) is also possible. Conditions have been found for the photometric titration of cerium(III) and of cerium(III) plus iron(II). The titration is carried out (at 450 mmicro or with a blue filter) in about 10.5M phosphoric acid. Application of the method to a cerium mineral is considered.     

2-Nitrodiphenylamine as a versatile high-potential reversible oxidation-reduction indicator

The use of 2-nitrodiphenylamine as a reversible indicator has been investigated in the titration of iron(II) with cerium(IV) sulphate, potassium dichromate and sodium vanadate in sulphuric acid media. Accurate results can be obtained with cerium(IV) sulphate in 0.5–5.0 M acid, with potassium dichromate in 5.0–7.0 M acid, and with sodium vanadate in 5.0–7.5 M acid. With cerium(IV) sulphate the titrations are preferably conducted in 2.0 M sulphuric acid or in a 1.0 M. sulphuric acid-1.0 M pechloric acid medium. Tungstic acid, acetic acid, arsenic(III) and manganese(II) do not interfere. In titrations of iron(II) with dichromate and vanadate, the colour changes at the end-point are much more vivid with 2-nitrodiphenylamine than with ferroin.     

Titration of cerium (IV) sulphate with sodium oxalate at the room temperature using ferroin as internal indicator

Summary A method has been developed for the titration of cerium(IV) sulphate with sodium oxalate at the room temperature, using ferroin as internal indicator. A new principle has been utilised for facilitating the indicator action at the equivalence point. This involves the use of a photochemical reaction between the oxalate and iron(III) which is deliberately added to the mixture containing cerium(IV) sulphate and ferriin. When the mixture is titrated with the sodium oxalate solution under exposure to the light from a Philips Repro lamp, the addition of a very slight excess of sodium oxalate solution, after all the cerium(IV) sulphate has reacted, produces a vivid red colour. The slight excess of sodium oxalate added reacts with the iron(III) salt photochemically producing a trace of iron(II) salt which reduces the ferriin to the red ferroin. In titrations with 0.1 and 0.05 N solutions of sodium oxalate, the error is negligible. In titrations with sodium oxalate solution of lower strengths, the error amounts to 0.02 ml of 0.01 N oxalate which has to be subtracted from the titre.     

Determination of cerium in minerals with sulphanilic acid

Cerium can be determined colorimetrically in minerals with sulphanilic acid. Cerium(III) ions are oxidized with silver(II) in 1-7% sulphuric acid. Sulphanilic acid is oxidized by cerium(IV) ions in 20% sulphuric acid. The absorbance is determined at 540 nm. In the presence of maganese or chromium, cerium can be separated by precipitation as the oxalate. Lanthanum can be used as a gathering agent if necessary.     

混合价黑色氧化铕的制备及其性质初步研究

用含肼甲酸铕在Ｎ２气氛中热分解的方法制得了混合价黑色氧化铕粉末。对它的有关物理化学性质进行了初步研究,得到了相应的结论。     

Dosage electrochimique du cobalt: I. Etude des Courbes Intensité— Potentiel du Système cobalt(III)/cobalt(II) en Milieu Picolique

Electrochemical determination of cobalt. Part I. Studies of current—voltage curves of the cobalt(III)/cobalt(II) system in picolinic acid mediaAs a preliminary to the development of electrochemical determinations of cobalt in steels, current—voltage curves at a platinum electrode were studied for the systems coblt(III)/cobalt(II) and iron(III)/iron(II) in media containing picolinic acid as complexing agent. Iron(III) oxidizes cobalt(II) in this complexmg medium, and the iron-(II) formed can be determined by an oxidant such as cerium(IV).     

Some observations on the redox behaviour of N-phenylanthranilic acid indicator in iron(II) titrations

The optimum conditions for the successful use of N-phenylanthranilic acid as indicator in titrations of iron(II) with dichromate, cerium(IV) sulphate and vanadate have been established. The influence of iron(III) on the indicator action, and the nature of a green compound formed from the indicator in iron(II) titrations, have been investigated spectrophotometrically.