Two new organic-inorganic compounds [（CH2）5NH2]3[PMo12O40]·3[（CH2）NH] 1 and [（CH2）5NH2]6[P2Mo18O62]·5H2O 2 have been synthesized using conventional and hydrothermal methods, respectively, and character...Two new organic-inorganic compounds [（CH2）5NH2]3[PMo12O40]·3[（CH2）NH] 1 and [（CH2）5NH2]6[P2Mo18O62]·5H2O 2 have been synthesized using conventional and hydrothermal methods, respectively, and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. X-ray analyses show that in these compounds heteropolymolybdates [PMo12O40]^3- and [P2Mo18O62]^6- are reserved their Keggin or Dawson structures and linked to piperidine through electrostatic and hydrogen-bonding interactions.展开更多
Nanoscale hybrid organic/inorganic Langmuir-Blodgett films of cerium-substituted heteropolymolybdates(Ce-HPMo) and π-conjugated macromolecule poly(1,2-dihydro-2,2,4-trimethyl)quinoline(PQ) were obtained with auxiliar...Nanoscale hybrid organic/inorganic Langmuir-Blodgett films of cerium-substituted heteropolymolybdates(Ce-HPMo) and π-conjugated macromolecule poly(1,2-dihydro-2,2,4-trimethyl)quinoline(PQ) were obtained with auxiliary film-forming material stearic acid(SA) or octadecylamine(ODA). The surface pressure-area isotherms illuminate the formation of the hybrid LB films of PQ/ODA/Ce-HPMo and PQ/SA/Ce-HPMo. The different film-forming mechanism was discussed when the different auxiliary film-forming materials were used in the system. The absorption spectra indicate that the molecules of PQ and Ce-HPMo are incorporated into the LB films. Tapping-mode AFM image reveals a granular surface texture of nanosized Ce-substituted heteropolymolybdate. STM image shows that the conductivity is greatly improved after Ce-substituted heteropolymolybdates are incorporated in the films.展开更多
A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H202 with high selectivity, was studied. In this system, heteropolymolybdate [C7H7N（CH3）3]3 {PO4[MoO（O2）2]4} was utilized as the...A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H202 with high selectivity, was studied. In this system, heteropolymolybdate [C7H7N（CH3）3]3 {PO4[MoO（O2）2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.展开更多
Single crystals of the title complex Na4 (NH4)10[Nd4Mo29O100(H2O)16]·34H2O obtained from the reaction of (NH4)6Mo7O24 and Nd (NO3)3, crystallize in themonoclinic, space group C2/c, with a= 19. 556(8), b= 43. 22 (...Single crystals of the title complex Na4 (NH4)10[Nd4Mo29O100(H2O)16]·34H2O obtained from the reaction of (NH4)6Mo7O24 and Nd (NO3)3, crystallize in themonoclinic, space group C2/c, with a= 19. 556(8), b= 43. 22 (2), c= 20. 389 (7) A,β= 117. 43(3)°, V= 15297(10) A3, Z=4, Dc= 1. 331g· cm-3, F(000) =5824, μ=1. 875 mm-1, final R(wR) = 0. 0816 (0. 2039) for 6128 unique intensity data [I≥2σ(I)]. In the molecule, each Nd heteroatom is coordinated by nine oxygen atoms with amono-capped square-antiprism configuration[1], while the Mo (VI) ions have severaldifferent coordination numbers (4, 5 and 6) with different configurations such as tetra-hedron, distorted square pyramid and octahedron respectively.展开更多
The title complex crystallizes in the triclinic system, space group P1 with a=16.9568(5), b=18.8631(6), c=24.1640(8), α=100.110(1), β=92\^330(1), γ=113.368(1)°, V=7602.54(4)~3, D_c=3.002 g/cm^3, F(000)=589...The title complex crystallizes in the triclinic system, space group P1 with a=16.9568(5), b=18.8631(6), c=24.1640(8), α=100.110(1), β=92\^330(1), γ=113.368(1)°, V=7602.54(4)~3, D_c=3.002 g/cm^3, F(000)=5893, M_r=6245.25, μ(Mo Kα)=5.010mm^-1, Z=2 and final R=0.0722 and wR=0\^1960 for 16015 observed reflections with I≥2σ(I). The Gd(Ⅲ) ion is coordinated by nine oxygen atoms, forming a distorted mono-capped square antiprism, while the Mo(Ⅵ) ions have their different coordination numbers such as 4,5 and 6 with different configurations such as tetrahedron, square pyramid and octahedron, respectively.展开更多
Al2O3-CeO2 supports containing 1-10 wt%Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH4HCO3.Heteropolymolybdate,（NH4）4NiMo6O（24）,was used as the precursor of the Ni and Mo to ...Al2O3-CeO2 supports containing 1-10 wt%Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH4HCO3.Heteropolymolybdate,（NH4）4NiMo6O（24）,was used as the precursor of the Ni and Mo to prepare NiMo6/Al2O3-CeO2 components in catalysts by impregnation method.The physicochemical properties of the catalysts were determined using chemical analysis,X-ray diffraction,temperature-programmed H2 reduction,temperature-programmed NH3 desorption,X-ray photoelectron spectroscopy（XPS）,and the Brunauer-Emmett-Teller method.The catalyst acidity decreased with increasing Ce concentration in the support.XPS showed that the NiS/MoS ratio decreased two-fold for the Ce-modified alumina support.NiMo6/Al2O3,which had the highest acidity,showed the highest activity in hydrodesulfurization of 1-benzothiophene（normalized per weight of catalyst）.The concentration of surface MoOxSy species（which is equal to the concentration of Mo^（5＋）） gradually decreased to zero for catalysts with Ce concentrations 10 wt%.However,the activities of all the catalysts prepared mechanochemically from Al2O3 and Al2O3-CeO2supports significantly exceeded that of a reference NiMo6/Al2O3 catalyst prepared by impregnation method using the same precursor and with the same composition.展开更多
A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4-bpy (4,4-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4-bpy)]2 [Mo8O26]4H2O 1. Si...A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4-bpy (4,4-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4-bpy)]2 [Mo8O26]4H2O 1. Single-crystal X-ray analysis has revealed that 1 (C68H56N12O30Cu4Mo8) crystallizes in the triclinic system, space group P with a = 11.270(3), b = 13.113(6), c = 13.906(3) ? = 103.33(4), b = 98.54(2), g = 101.29(2)? V = 1920.1(1) ?3, Mr = 2542.93, Z = 1, Dc = 2.199 g/cm3, m = 2.435 mm-1, F(000) = 1240, the final R = 0.0445, wR = 0.1082 and S = 1.021 for 5052 observed reflections with I >2s(I). It consists of copper (Ⅰ) tetramer units and -[Mo8O26]4- anions, which are further attached into a three-dimensional framework through hydrogen bonding and - stacking interactions.展开更多
The title complex crystallized in triclinic system with space group P1;Mr=5862. 35 a= 17.04(1), b= 18. 989(5), c= 24. 240(6) A ;a= 100. 18(2), β=92. 24(3), γ= 113. 04(3)°; V=7054(6) A3, Z=2, Dc= 2. 664 g. cm-3,...The title complex crystallized in triclinic system with space group P1;Mr=5862. 35 a= 17.04(1), b= 18. 989(5), c= 24. 240(6) A ;a= 100. 18(2), β=92. 24(3), γ= 113. 04(3)°; V=7054(6) A3, Z=2, Dc= 2. 664 g. cm-3, F(000) =5306, μ= 4. 036 mm-1 and final R= 0. 0763 and Rw= 0. 2176 for 15951 reflections [Ⅰ>2δ(I)]. The Nd(Ⅲ) coordinated with 9 oxygen atoms forms a mono-capped square-antiprism configuration, while the Mo (Ⅵ) ions have several different coordinationnumbers such as 4, 5 and 6 with different configurations such as tetrahedron, distortedsquare pyramid and octahedron respectively.展开更多
A novel compound [(NH_4)_6][Gd_2Mo_(36)O_(112)(H_2O)_(20)]·52H_2O (1) was obtained from the reaction of (NH_4)_6Mo7O24·4H_2O with GdCl3 at pH = 1.32. The X-ray structural analysis reveals that 1 crystallizes...A novel compound [(NH_4)_6][Gd_2Mo_(36)O_(112)(H_2O)_(20)]·52H_2O (1) was obtained from the reaction of (NH_4)_6Mo7O24·4H_2O with GdCl3 at pH = 1.32. The X-ray structural analysis reveals that 1 crystallizes in monoclinic system, space group C2/c, Mr = 6937.77, a = 42.313(1), b=12.924(1), c=26.404(1) ?, β= 127.07(1)o, V=15086.2(6) ? 3, Z = 4, Dc = 2.976g·cm－3, ( = 3.316 mm－1, F(000) = 12963, the final R = 0.0585 and wR = 0.1490 for 5431 observed reflections. It contains a usual structural unit {Mo36}, which is linked to two eight-coordinated Gd3+ cations with the Gd-O distances from 2.31(5) to 2.46(5)展开更多
基金This project was financially supported by the National Science Foundation of China (No. 20371012)
文摘Two new organic-inorganic compounds [（CH2）5NH2]3[PMo12O40]·3[（CH2）NH] 1 and [（CH2）5NH2]6[P2Mo18O62]·5H2O 2 have been synthesized using conventional and hydrothermal methods, respectively, and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. X-ray analyses show that in these compounds heteropolymolybdates [PMo12O40]^3- and [P2Mo18O62]^6- are reserved their Keggin or Dawson structures and linked to piperidine through electrostatic and hydrogen-bonding interactions.
文摘Nanoscale hybrid organic/inorganic Langmuir-Blodgett films of cerium-substituted heteropolymolybdates(Ce-HPMo) and π-conjugated macromolecule poly(1,2-dihydro-2,2,4-trimethyl)quinoline(PQ) were obtained with auxiliary film-forming material stearic acid(SA) or octadecylamine(ODA). The surface pressure-area isotherms illuminate the formation of the hybrid LB films of PQ/ODA/Ce-HPMo and PQ/SA/Ce-HPMo. The different film-forming mechanism was discussed when the different auxiliary film-forming materials were used in the system. The absorption spectra indicate that the molecules of PQ and Ce-HPMo are incorporated into the LB films. Tapping-mode AFM image reveals a granular surface texture of nanosized Ce-substituted heteropolymolybdate. STM image shows that the conductivity is greatly improved after Ce-substituted heteropolymolybdates are incorporated in the films.
文摘A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H202 with high selectivity, was studied. In this system, heteropolymolybdate [C7H7N（CH3）3]3 {PO4[MoO（O2）2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.
文摘Single crystals of the title complex Na4 (NH4)10[Nd4Mo29O100(H2O)16]·34H2O obtained from the reaction of (NH4)6Mo7O24 and Nd (NO3)3, crystallize in themonoclinic, space group C2/c, with a= 19. 556(8), b= 43. 22 (2), c= 20. 389 (7) A,β= 117. 43(3)°, V= 15297(10) A3, Z=4, Dc= 1. 331g· cm-3, F(000) =5824, μ=1. 875 mm-1, final R(wR) = 0. 0816 (0. 2039) for 6128 unique intensity data [I≥2σ(I)]. In the molecule, each Nd heteroatom is coordinated by nine oxygen atoms with amono-capped square-antiprism configuration[1], while the Mo (VI) ions have severaldifferent coordination numbers (4, 5 and 6) with different configurations such as tetra-hedron, distorted square pyramid and octahedron respectively.
基金Supported by the Science Foundation of Fujian Science Committee.
文摘The title complex crystallizes in the triclinic system, space group P1 with a=16.9568(5), b=18.8631(6), c=24.1640(8), α=100.110(1), β=92\^330(1), γ=113.368(1)°, V=7602.54(4)~3, D_c=3.002 g/cm^3, F(000)=5893, M_r=6245.25, μ(Mo Kα)=5.010mm^-1, Z=2 and final R=0.0722 and wR=0\^1960 for 16015 observed reflections with I≥2σ(I). The Gd(Ⅲ) ion is coordinated by nine oxygen atoms, forming a distorted mono-capped square antiprism, while the Mo(Ⅵ) ions have their different coordination numbers such as 4,5 and 6 with different configurations such as tetrahedron, square pyramid and octahedron, respectively.
基金Czech Science Foundation(Project P106/11/0902) for financial support
文摘Al2O3-CeO2 supports containing 1-10 wt%Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH4HCO3.Heteropolymolybdate,（NH4）4NiMo6O（24）,was used as the precursor of the Ni and Mo to prepare NiMo6/Al2O3-CeO2 components in catalysts by impregnation method.The physicochemical properties of the catalysts were determined using chemical analysis,X-ray diffraction,temperature-programmed H2 reduction,temperature-programmed NH3 desorption,X-ray photoelectron spectroscopy（XPS）,and the Brunauer-Emmett-Teller method.The catalyst acidity decreased with increasing Ce concentration in the support.XPS showed that the NiS/MoS ratio decreased two-fold for the Ce-modified alumina support.NiMo6/Al2O3,which had the highest acidity,showed the highest activity in hydrodesulfurization of 1-benzothiophene（normalized per weight of catalyst）.The concentration of surface MoOxSy species（which is equal to the concentration of Mo^（5＋）） gradually decreased to zero for catalysts with Ce concentrations 10 wt%.However,the activities of all the catalysts prepared mechanochemically from Al2O3 and Al2O3-CeO2supports significantly exceeded that of a reference NiMo6/Al2O3 catalyst prepared by impregnation method using the same precursor and with the same composition.
基金This work was supported by the National Natural Science Foundation of China (20073048) NSF of Fujian and the Chinese Academy of Sciences
文摘A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4-bpy (4,4-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4-bpy)]2 [Mo8O26]4H2O 1. Single-crystal X-ray analysis has revealed that 1 (C68H56N12O30Cu4Mo8) crystallizes in the triclinic system, space group P with a = 11.270(3), b = 13.113(6), c = 13.906(3) ? = 103.33(4), b = 98.54(2), g = 101.29(2)? V = 1920.1(1) ?3, Mr = 2542.93, Z = 1, Dc = 2.199 g/cm3, m = 2.435 mm-1, F(000) = 1240, the final R = 0.0445, wR = 0.1082 and S = 1.021 for 5052 observed reflections with I >2s(I). It consists of copper (Ⅰ) tetramer units and -[Mo8O26]4- anions, which are further attached into a three-dimensional framework through hydrogen bonding and - stacking interactions.
文摘The title complex crystallized in triclinic system with space group P1;Mr=5862. 35 a= 17.04(1), b= 18. 989(5), c= 24. 240(6) A ;a= 100. 18(2), β=92. 24(3), γ= 113. 04(3)°; V=7054(6) A3, Z=2, Dc= 2. 664 g. cm-3, F(000) =5306, μ= 4. 036 mm-1 and final R= 0. 0763 and Rw= 0. 2176 for 15951 reflections [Ⅰ>2δ(I)]. The Nd(Ⅲ) coordinated with 9 oxygen atoms forms a mono-capped square-antiprism configuration, while the Mo (Ⅵ) ions have several different coordinationnumbers such as 4, 5 and 6 with different configurations such as tetrahedron, distortedsquare pyramid and octahedron respectively.
基金the State Education Ministry, the State Personal Ministry, National Natural Science Foundation of China (20073048) and the Chine
文摘A novel compound [(NH_4)_6][Gd_2Mo_(36)O_(112)(H_2O)_(20)]·52H_2O (1) was obtained from the reaction of (NH_4)_6Mo7O24·4H_2O with GdCl3 at pH = 1.32. The X-ray structural analysis reveals that 1 crystallizes in monoclinic system, space group C2/c, Mr = 6937.77, a = 42.313(1), b=12.924(1), c=26.404(1) ?, β= 127.07(1)o, V=15086.2(6) ? 3, Z = 4, Dc = 2.976g·cm－3, ( = 3.316 mm－1, F(000) = 12963, the final R = 0.0585 and wR = 0.1490 for 5431 observed reflections. It contains a usual structural unit {Mo36}, which is linked to two eight-coordinated Gd3+ cations with the Gd-O distances from 2.31(5) to 2.46(5)
