A novel one-dimensional manganese phosphomolybdate with rectangular cavities: [H3N(CH2)(4)NH3] (H3O)(2){[Mn(phen)(2)](4) [(MnMo12O30)-O-v(HPO4)(6)(H2PO4)2} center dot 4H(2)O

A novel manganese phosphomolybdate, [H3N(CH2)(4)NH3](H3O)(2){[Mn(phen)(2)](4)[(MnMovO30)-O-12(HPO4)(6)(H2PO4)(2)]} . 4H(2)O 1, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The crystal data: triclinic, P (1) over bar, a = 14.172(7) Angstrom, b = 16.547(2) Angstrom, c = 16.679(3) Angstrom, alpha = 62.881(12)degrees, beta = 73.83(3)degrees, gamma = 88.81(3)degrees. X-ray crystallography shows that the [Mn(phen)(2)] fragments are covalently bonded to the [Mn(Mo6P4)(2)] dimers leading to a one-dimensional chain with rectangular cavities occupied by tetramethylene-diamine cations and water molecules. (C) 2002 Elsevier Science B.V. All rights reserved.

Assembly of the transition metal substituted polyoxometalates ZnW11M(H2O)O-39(n-) (M = Mn, Cu, Fe, Co, Cr, Ni, Zn) on 4-aminobenzoic acid modified glassy carbon electrode and their electrochemical study

Through layer-by-layer assembly, a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M=Cr, Mn, Fe, Co, Ni, Cu. or Zn) were first successfully immobilized on a 4-aminobenzoic acid modified glassy carbon electrode surface. The electrochemical behaviors of these polyoxometalates were investigated. They exhibit some special properties in the films different from those in homogeneous aqueous solution. The Cu-centered reaction mechanism in the ZnW11Cu multilayer film was described. The electrocatalytic behaviors of these multilayer film electrodes to the reduction of H2O2 and BrO3- were comparatively studied.

Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

柠檬酸-凝胶法合成ZnGa_2O_4∶Mn~(2+)/Eu~(3+)及其发光性能的研究

采用柠檬酸 凝胶法合成了纯的ZnGa2 O4粉末以及ZnGa2 O4∶Mn2 + /Eu3 + 粉末 ,利用X射线衍射(XRD)、热重及差热分析 (TG DTA)、发光光谱等测试手段对ZnGa2 O4和ZnGa2 O4∶Mn2 + /Eu3 + 的结晶过程、发光性质进行了研究。XRD结果表明 ,柠檬酸 凝胶法合成的样品在 5 0 0℃时已开始结晶 ,在 70 0℃时可得到纯相的ZnGa2 O4多晶粉末 ,这比传统固相法的烧结温度低 5 0 0℃。发光光谱测试表明ZnGa2 O4∶Mn2 + 在4 5 0nm和 5 0 6nm处出现两个发射带 ,前者属于ZnGa2 O4基质的发射 ,后者属于Mn2 + 的4T1→6A1的跃迁发射。ZnGa2 O4∶Eu3 + 则呈现Eu3 + 的特征红光发射 ,最强峰位于 6 13nm ,属于Eu3 + 的5D0 →7F2 超灵敏跃迁。通过光谱分析进一步证实了ZnGa2 O4∶Mn2 + /Eu3 + 的发光机理是基质敏化 ,吸收能量并向激活离子传递能量

Preparation, structure and luminescence of BaMAl10O17 : Eu2+ (M = Be, Mg, Ca, Zn, Cd, Mn, Co, Li) system

The BaMA(10)O(17) (M = Be, Mg, Ca, Zn, Cd, Mn, Co, Li) system has been synthesized by solid state method and characterized by XRD. The results show that when M is Mg, Zn, Mn, Co, Li, there exists the structure of beta-Al2O3 for BaMAl10O17 system, and when M indicates Cd, beta-Al2O3 structure is formed accompanying alpha-Al2O3 phase, and when M represents Be and Ca, beta-Al2O3 structure cannot be formed. This demonstrates that the condition forming beta-Al2O3 structure compounds for the system BaMAl10O17 is 0.05nm < R-M < 0.09nm (R-M represents the radius of M). The thought that if a M ion can form a stable spinel structure there exsits a corresponding magnetoplumbite and beta-alumina structure is proposed for BaMAl10O17 system according to the experimental results. When M is Li, Be, Zn, Eu2+ activator produces an emission of nearly 450 nm with half height width about 50 nm, when M is Mn, there are simultaneously the emissions of Eu2+ and Mn2+ and the excitation energy of Eu2+ can transfer to Mn2+ in the host, when M is Cd, Eu2+ displays a double-emission band, which can be explained by the Jahn-Teller's effect. It is possible for the system BaMAl10O17 with M being Li, Be, Zn to become blue-emitting component in three colour lamp through further study.

Zn_2SiO_4∶Mn的VUV和UV光谱特性

采用高温固相反应法以硅酸为原料合成了等离子显示用荧光体Zn2 SiO4 ∶Mn ,研究了Zn2 SiO4 ∶Mn的VUV和UV光谱特性 ,表明波长小于 2 0 0nm的部分的基质吸收带主要是氧的 2 p轨道到锌的 3d轨道跃迁产生的 ,波长大于 2 0 0nm的部分的基质吸收带是氧的 2 p轨道到硅的 3p轨道跃迁吸收。在VUV和UV激发下 ,Mn2 +的浓度与发射强度的相关性研究表明 ,在不同区域激发时荧光体的发射强度随着Mn2 +的浓度的变化存在明显不同

BaMAl_(10)O_(17)(M=Be,Mg,Ca,Zn,Cd,Mn,Co,Li)体系的合成、结构和Eu~(2+)在其中的发光

在BaMAl10O17 体系中 ,将M扩大到除镁以外的其它离子 ,研究和讨论了离子半径与基质结构的形成关系 ,提出能稳定(形成)尖晶石结构的M离子有相应的磁铅矿或β Al2O3 结构的化合物存在的思想 ,并研究了Eu2 +在体系中的发光性能。结果表明 ,M=Zn,Cd,Mn,Co,Li时可形成 β Al2O3 结构化合物 ,M=Ca,Be时不能形成这类结构 ,Ca形成多相共存 ,Be形成一未知相 ;Eu2 +在M=Li,Be,Zn体系中具有良好的发光性能 ,发射波长450nm ,半高宽在50nm附近 ,将是一类很有前途的新的蓝色发光材料 ,Eu2 +在M=Mn的体系中存在Eu2 +和Mn2 +的同时发射 ,在M=Cd体系中 ,Eu2 +产生一双重宽带发射。对实验结果进行了合理的解释

Multilayer assembly of Mn-substituted Keggin-type [ZnW11O39Mn(H2O)](8-) on chemically modified glassy carbon electrode and its electrocatalytic properties

Through layer-by-layer assembly, undecatungstozincates monosubstituted by transition metals Mn, ZnW11 Mn (H2O) O-39(8-) was successfully immobilized on a glassy carbon electrode surface grafted covalently by 4-aminobenzoic acid. The electrochemical behavior of these polyoxometalates was investigated. Cyclic voltammetry proves the uniform growth of the film. They exhibit some special electrochemical properties in the films, different from those in homogeneous aqueous solution. The effect of pH on the redox behavior of ZnW11Mn(H2O)O-39(8-) in the film was discussed in detail. The multilayer film electrodes have an excellent electrocatalytic response to the reduction of H2O2 and BrO3-, and to the oxidation of ascorbic acid.

Catalytic reduction of NO, by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

Electrochemical behavior of a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M = Cr, Mn, Fe, Co, Ni, Cu or Zn)

The electrochemical behavior of a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M=Cr, Mn, Fe, Co, Ni, Cu or Zn), was investigated systematically and comparably in aqueous solutions by electrochemical and in situ UV-visible-near-IR spectroelectrochemical methods. These compounds exhibit not only successive reduction processes of the addenda atoms (W) in a negative potential range, but some of them also involve redox reactions originating from the substituted transition metals (M) such as the reduction of Fe-III and Cu-II at less negative potentials and the oxidation of Mn-II at a more positive potential. Some interesting results and phenomena, especially of the transition metals, were found for the first time. Moreover, possible reaction mechanisms are proposed based on the experimental results.