Synthesis of sulfonated poly(arylene-co-naphthalimide)s as novel polymers for proton exchange membranes

A series of novel sulfonated poly(arylene-co-binaphthalimide)s (SPPIs) were successfully synthesized via Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and bis(chloronaphthalimide)s. Bis(chloronaphthalimide)s were conveniently prepared from 5-chloro-1,8-naphthalic anhydride and various diamines. Tough and transparent SPPI membranes were prepared and the electrolyte properties of the copolymers were intensively investigated as were the effects of different diamine structures on the copolymer characterisitics. The copolymer membrane Ia-80, with an ion exchange capacity (IEC) of 2.50 meq g(-1), displayed a higher proton conductivity, i.e. 0.135 S cm(-1) at 20 degrees C, as compared to Nafion 117 (0.09 S cm(-1), 20 degrees C).

Effect of Single- and co-Dopant on TL of Sr2Mg(BO3)(2) Phosphor

Sr2Mg(BO3)(2) thermoluminescence (TL) phosphor was synthesized by a high temperature solid state reaction and the effect of Li+, Bi3+, Gd3+ or Ti4+ as a codopant on TL of Sr2Mg(BO3)(2) : Dy was investigated. The results show that Li+ as a codopant improves the emission intensity of high temperature TL peak of Sr2Mg(BO3)(2) : Dy phosphor whereas the addition of Bi3+, Gd3+ or Ti3+ leads to the decrease of TL intensity. The TL emission bands of Sr2Mg(BO3)(2) : Dy phosphors with Li+, Bi3+, Gd3+ or Ti4+ as a codopant are situated at 480, 579, 662 and 755 nm, which were attributed to the characteristic F-4(9/2)-> H-6(15/2), F-4(9/2)-> H-6(13/2), F-4(9/2)-> H-6(11/2) and F-4(9/2)-> H-6(9/2) transitions of Dy3+ ion, consistent with the emission of Sr2Mg(BO3)(2) : Dy phosphors. The kinetics parameters of 234 degrees C TL peak of Sr2Mg(BO3)(2) Dy-0.04(3+), (Li-0.04(+)) phosphor with the values of trap depth E=1.1 eV, frequency factor s=6.3 x 10(9) s(-1) were estimated by a peak shape method, which obey the second order kinetics.

Effect of Single- and co-Dopant on TL of Sr2Mg(BO3)(2) Phosphor(单掺杂与共掺杂离子对Sr_2Mg(BO_3)_2磷光体热释发光的影响)

Sr2Mg(BO3)(2) thermoluminescence (TL) phosphor was synthesized by a high temperature solid state reaction and the effect of Li+, Bi3+, Gd3+ or Ti4+ as a codopant on TL of Sr2Mg(BO3)(2) : Dy was investigated. The results show that Li+ as a codopant improves the emission intensity of high temperature TL peak of Sr2Mg(BO3)(2) : Dy phosphor whereas the addition of Bi3+, Gd3+ or Ti3+ leads to the decrease of TL intensity. The TL emission bands of Sr2Mg(BO3)(2) : Dy phosphors with Li+, Bi3+, Gd3+ or Ti4+ as a codopant are situated at 480, 579, 662 and 755 nm, which were attributed to the characteristic F-4(9/2)-> H-6(15/2), F-4(9/2)-> H-6(13/2), F-4(9/2)-> H-6(11/2) and F-4(9/2)-> H-6(9/2) transitions of Dy3+ ion, consistent with the emission of Sr2Mg(BO3)(2) : Dy phosphors. The kinetics parameters of 234 degrees C TL peak of Sr2Mg(BO3)(2) Dy-0.04(3+), (Li-0.04(+)) phosphor with the values of trap depth E=1.1 eV, frequency factor s=6.3 x 10(9) s(-1) were estimated by a peak shape method, which obey the second order kinetics.

High-dimensional assembly depending on polyoxoanion templates, metal ion coordination geometries, and a flexible bis(imidazole) ligand

By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As8V14O42](4-) and [V16O38Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As8V14O42(H2O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As8V14O42(H2O)] (4), and [Cu(bbi)](6)[V16O38Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schlafli symbol (3(4)center dot 4(2))(3(4)center dot 4(4)center dot 5(4)center dot 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M-4(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As8V14O42](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M-8(bbi)(6)O-2 circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V16O38Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M-24(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process.

Up-conversion spectrum properties of the oxy-fluoride glass co-doped with Er3+ and Yb3+

Up-conversion of 45PbF(2)-45GeO(2)-10WO(3) oxy-fluoride glasses co-doped with Yb3+ and Er3+ ions were prepared by fusion method through melting at 1223 K and then annealing at 653 K for 4 h. Transmittance of the undoped host glass was beyond 73% in a range of 0.6-2.5 mu m and the co-doped glasses still provided good transmittance beyond 50%. Refractive indices of the host and co-doped glasses were 1.517 and 1.650, respectively. Blue, green and red fluorescence spectra were observed in a range of 400-700 nm under 980 nm diode laser excitation. Up-conversion spectra at about 410, 518, 530and 650 nm were assigned to the 4f electron transitions of H-2(9/2) -> I-4(15)/(2), H-2(15/2) -> I-4(15/2) S-4(3/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2) of Er3+ ion, respectively. The mechanism of energy transfer between Yb3+ and Er3+ ions in the glass was analyzed. Raman shift shows the non-radiative relaxation of the glass sample is low.

Synthesis, characterization, crystal structure and magnetic property of asymmetrical double Schiff base heterotrinuclear complex: Cu(II)-Co(II)-Cu(II)

An asymmetrical double Schiff-base Cu(II) mononuclear complex, HCuLp (H(3)Lp is N-3-carboxylsalicylidene-N'-5-chlorosalicylaldehyde-1,3-diaminopropane) and a heterometal trinuclear complex with double molecular structure (CuLp)(2)Co center dot 5H(2)O have been synthesized and characterized by means of elemental analyses, IR and electronic spectra. The crystal structure of the heterotrinucler complex was determined by X-ray analysis. Each asymmetric unit within the unit cell of the complex contains two heterotrinuclear neutral molecules (a) [CuLpCoCuLp], (b) [(CuLpH(2)O) CoCuLp] and four uncoordinated water molecules. In the two neutral molecules, the central Co2+ ions are located at the site of O-6 with a distorted octahedral geometry, one terminal Cu2+ ion (Cu(3)) at the square-pyramidal environment of N2O3, and the other three at the square planar coordination geometry with N2O2 donor atoms. Magnetic properties of the heterotrinucler complex have been determined in the temperature range 5-300 K, indicating that the interaction between the central Co2+ ion and the outer Co2+ ions is antiferromagnetic.

Two new coordination polymers of Co(II) with 1,1 '-(1,4-butanediyl)bis(benzimidazole)

Two new compounds, [CoL2(H2O)(2)](NO3)(2). 8H(2)O (1) and [CoL(H2O)(2)(CH3CO2)(2)]. H2O (2), were obtained from self-assembly of the corresponding metal salts with 1,1'-(1,4-butanediyl)bis(benzimidazole) (L). In 1, each cobalt ion is coordinated to four nitrogen atoms from four molecules of L, and to two water molecules. Metal ions are bridged by L ligands to form infinite (4, 4) networks that contain 44-membered rings. The (4, 4) networks of 1 stack in a parallel fashion, resulting in the formation of large channels in the material. In 2, each cobalt ion is coordinated to two N atoms from two L molecules, two water molecules and two carboxylate O atoms from two acetate anions. Each L molecule is coordinated to two cobalt ions, acting as a bridging ligand as in 1. The bridged cobalt ions form an infinite zigzag chain structure.

Networks with hexagonal circuits in co-ordination polymers of metal ions (Zn-II, Cd-II) with 1,1 '-(1,4-butanediyl)bis(imidazole)

Three new compounds, [ZnL1.5(H2O)(SO4)]. 6H(2)O 1, [ZnL1.5(H2O)(2)][NO3](2). 2H(2)O 2 and [CdL1.5(H2O)(2)(SO4)]. 4H(2)O 3 were obtained from self-assembly of the corresponding metal salts with 1,1'-(1,4-butanediyl)bis(imidazole) (L). In both 1 and 2 zinc ion is five-co-ordinated, showing a less-common trigonal bipyramidal co-ordination polyhedron, while cadmium ion of 3 is six-co-ordinated with a common octahedral arrangement. The sulfate ions of 1 and 3 are co-ordinated, however the nitrate ions of 2 are not. Each of the three compounds is composed of a (6, 3) network with the hexagonal smallest circuit containing six metal ions and six L; each L is co-ordinated to two metal ions, acting as a bridging ligand. In 1 the 2-D sheet of (6, 3) networks is interpenetrated in an inclined mode by symmetry related, identical sheets to give an interlocked 3-D structure, while the (6, 3) networks of both 2 and 3 stack in a parallel fashion to construct frameworks having channels.

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.

Preparation, characterization of solid solution La4BaCu5-xMnxO13+lambda (x=0-5) and its catalytic activity in the reduction of NO by CO

A series of layered mixed oxides La4BaCu5-xMnxO13+lambda(x = 0-5) was prepared, characterized and used as catalysts for NO+CO reaction. It was found that all the samples were single phase having a structure with five-layered-perovskite. La4BaCu2Mn3O13+lambda showed the highest activity in the title reaction, this could be attributed to the synergetic effect between Cu and Mn. The results of TPR, TPD and excess oxygen investigations confirmed that the Cu ion would be the active center. The displacement of the Cu ion by Mn caused the Cu ion to be more easily reducible and more content of excess oxygen, and it was beneficial to the activity of the catalyst. The reaction mechanism was also proposed.

Study of physicochemical properties and active oxygen in structures of layered mixed La4BaCu5-xMxO13+lambda (M = Mn, Co)

Two series of layered mixed oxides La4BaCu5-xMxO13+lambda(M = Mn, Co, x = 0 similar to 5) were prepared and characterized by means of XRD, XPS, O-2-TPD and chemical analysis. The results show that their structures are 5-layered ABO(3) perovskite, and the XPS and O-2-TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+lambda,, and the synergistic effect between Mn and Cu is stronger than that of Cu-Co.

Synthesis, characterization and catalytic behavior of layered mixed oxides La4BaCu5-xMnxO12 in NO reduction by CO

A series of sample having the stoichiometry La4BaCu5-xMnxO12 (x = 0 similar to 5) were prepared, characterized by XRD, IR and H-2 - TPR and used as catalyst for NO + CO reaction. It was found that they have 5 - layered ABO(3) - type structure. The results of H-2 - TPR showed that the Cu ion was more easily reduced while a part of them was replaced by Mn ions. Their catalytic behavior to NO + CO reaction was investigate, La4BaCu2Mn3O12 showed the highest catalyst activity for the reaction than the others. The reaction mechanism is discussed:the activity of the catalysts could be attributed to the Cu ions, but it was improved when Mn ions took the place of some Cu ions.

Gas phase derivations of endohedral metallofullerenes by ion-molecular reactions

Gas phase ion-molecular reactions of endohedral metallofullerenes with the self-chemical ionization ion system of vinyl acetate, benzene and acetone in the ion source of the mass spectrometer have been studied. Several derivatized endohedral metallofullerene cations [M@C-82-C2H3O](+), [M-2@C-80-C2H3O](+), [M@C-82-C6H6](+) and [M@C-82-CO-CH3](+) are observed as the major products. The experimental results indicate that endohedral metallofullerenes have active gas phase reactivities and can be efficiently derivatized by some small organic cations.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

Study on the Adsorption and Activation of NO and CO over Mixed Oxide Catalysts Containing Cu by Means of TPSR

Adsorption and activation of small molecules NO, CO and CO+ NO on LaSrCuO4, La2CuO4 and La1.7Th0.3CuO4 which are typical samples in the sence of nonstoichiometric oxygen(lambda) anrong the series of La2-x(SrTh)(x)CuO4 +/-lambda mixed oxide catalysts were studied by means of MS- TPD (TPSR ), XRD, chemical analysis and so on. It was shown that the adsorption amount of NO can be correlated with the content of oxygen vacancy while the types and strength of adsorption of NO could be related to the oxidation state of the metallic ion. It was also found that CO molecule was first converted into CO32- and then desorbed in the form of CO2 at high temperature during the adsorption and desorption of CO on the mixed oxide with oxygen vacancy. The fact that the profiles of TPD(TPSR) of NO in co-adsorption of NO+CO and in single NO adsorption are similar shows that the adsorption of NO molecule not only has some priority to that of CO but also is stronger than that of CO. It seems that the adsorption of NO plays a dominate role in the activation and decomposition of NO.