The present paper reports eight heteropoty blues of double 2:17 motybdophosphates tanthanide comptexes with tacunary Dawson structure, i.e., K_(17)H_2[Ln(P_2Mo_2~ⅤMo_(15)~ⅥO_(16))_2], nH_2O and K_(17)H_4 [Ln(P_2Mo~...The present paper reports eight heteropoty blues of double 2:17 motybdophosphates tanthanide comptexes with tacunary Dawson structure, i.e., K_(17)H_2[Ln(P_2Mo_2~ⅤMo_(15)~ⅥO_(16))_2], nH_2O and K_(17)H_4 [Ln(P_2Mo~Ⅴ_4Mo_(13)~ⅥO_(61))_2], nH_2O(Ln=La, Pr, Sm, Yb). They were characterized by etementat anatyses, potentiometric titration, IR, UV, potarography, cyclic vottammetry, X-ray photoelectron spectra, X-ray powder diffraction, thermat analyses and ESR. The results show that the properties of these heteropoty btues are different from those of heteropoty blues with saturated Dawson structure and other tacunary series. They are more stabte than their parent heteropoty acids in aqueous sotution and have the abitity of anti-base decomposition.展开更多
Lithium heteropoly blue(Li 5PW Ⅵ 10 W Ⅴ 2O 40 ) was used as a non aqueous electrolyte in the polyacenic semiconductor (PAS) Li secondary battery instead of LiClO 4. The properties of the PAS Li secon...Lithium heteropoly blue(Li 5PW Ⅵ 10 W Ⅴ 2O 40 ) was used as a non aqueous electrolyte in the polyacenic semiconductor (PAS) Li secondary battery instead of LiClO 4. The properties of the PAS Li secondary battery, especially the effect of Li 5PW Ⅵ 10 W Ⅴ 2O 40 on the capacity, the cycle property and the self discharging of the battery have been investigated. The results indicate that not only Li 5PW Ⅵ 10 W Ⅴ 2O 40 can overcome the disadvantages of LiClO 4, which is apt to explode when heated or rammed, but also the PAS Li secondary battery assembled with the novel electrolyte has a larger capacity and smaller self discharging than that assembled with LiClO 4. Therefore, it is believed that lithium heteropoly blue is a better and novel electrolyte for the PAS secondary battery and exhibits significant and practical application.展开更多
For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated...For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated by means of polarograms,cyclic voltammetry,31P NMR and X-ray diffraction methods.The heteropolynier of PMo12 and AsMo12 converte to their β-isomers during isomerization reaction which were found to have antiacidolysis property.展开更多
The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic...The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic system with space group P , Mr=2117.73, a= 13.702(4), b=14.107(3), c=14.184(2) ; α=119.27(1), β=93.14(2), ;γ=110. 3(2)°, V=2154.29~3, Z=2, F(000)=1999, μ=36.39cm^(-1), Dc=3.26 g/cm^3. Final R factor is 0.0515. Mo(Ⅴ) is situated in two different edge-shared Mo_3O_(13) groups. The heteropoly blue was characterized by IR, UV, polarography, X-ray photoelectron spectra and ESR. All the results show that the structure of the heteropoly anion with Keggin structure remains unchanged basically in the process of reduction.展开更多
The title heteropoly blue, (Bu_4N)_6H_(10)[PMo_(11)~ⅥMo~ⅤO_(40)]_4·H_2Ohas been photochemically synthesized and characterized with elemental analysis, solid diffusionreflectance electronic spectra, CV, ESR, XPS...The title heteropoly blue, (Bu_4N)_6H_(10)[PMo_(11)~ⅥMo~ⅤO_(40)]_4·H_2Ohas been photochemically synthesized and characterized with elemental analysis, solid diffusionreflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and X-ray singlecrystal analysis. The crystallographic data for C_(96)H_(218)Mo_(48)N_6O_(169)P_4 are as follows:M_r = 8889.76, triclinic, P_1, a = 1.4142(3) nm, b = 2.6027(5) nm, c = 2.6403(5) nm, α=113.96(3)°, β = 90.05(3)°, γ= 105.71(3)°, V = 8.481(3) nm^3, Z = 1, D_c = 1.741 g/cm^3, F(000)= 4264, μ= 1.798 mm^(-1). The X-ray crystal structure analysis reveals that there is oneindependent molecule in the unit cell of the title heteropoly blue which contains four mixed-valenceheteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structurepossesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is in thecrystallographic inversion center of the heteropoly anion and the eight oxygen atoms surroundingcentral phosphorus atom comprise of a distorted hexahedron. Heteropoly anion has two equal sets ofPO_4 tetrahedron. The PO_4 tetrahedron and the MoO_6 octahedron in the polyanion are greatlydistorted.展开更多
文摘The present paper reports eight heteropoty blues of double 2:17 motybdophosphates tanthanide comptexes with tacunary Dawson structure, i.e., K_(17)H_2[Ln(P_2Mo_2~ⅤMo_(15)~ⅥO_(16))_2], nH_2O and K_(17)H_4 [Ln(P_2Mo~Ⅴ_4Mo_(13)~ⅥO_(61))_2], nH_2O(Ln=La, Pr, Sm, Yb). They were characterized by etementat anatyses, potentiometric titration, IR, UV, potarography, cyclic vottammetry, X-ray photoelectron spectra, X-ray powder diffraction, thermat analyses and ESR. The results show that the properties of these heteropoty btues are different from those of heteropoty blues with saturated Dawson structure and other tacunary series. They are more stabte than their parent heteropoty acids in aqueous sotution and have the abitity of anti-base decomposition.
基金Supported by Education Com mittee Foundation of L iaoning Province(No.970 912 12 11) .
文摘Lithium heteropoly blue(Li 5PW Ⅵ 10 W Ⅴ 2O 40 ) was used as a non aqueous electrolyte in the polyacenic semiconductor (PAS) Li secondary battery instead of LiClO 4. The properties of the PAS Li secondary battery, especially the effect of Li 5PW Ⅵ 10 W Ⅴ 2O 40 on the capacity, the cycle property and the self discharging of the battery have been investigated. The results indicate that not only Li 5PW Ⅵ 10 W Ⅴ 2O 40 can overcome the disadvantages of LiClO 4, which is apt to explode when heated or rammed, but also the PAS Li secondary battery assembled with the novel electrolyte has a larger capacity and smaller self discharging than that assembled with LiClO 4. Therefore, it is believed that lithium heteropoly blue is a better and novel electrolyte for the PAS secondary battery and exhibits significant and practical application.
文摘For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated by means of polarograms,cyclic voltammetry,31P NMR and X-ray diffraction methods.The heteropolynier of PMo12 and AsMo12 converte to their β-isomers during isomerization reaction which were found to have antiacidolysis property.
文摘The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic system with space group P , Mr=2117.73, a= 13.702(4), b=14.107(3), c=14.184(2) ; α=119.27(1), β=93.14(2), ;γ=110. 3(2)°, V=2154.29~3, Z=2, F(000)=1999, μ=36.39cm^(-1), Dc=3.26 g/cm^3. Final R factor is 0.0515. Mo(Ⅴ) is situated in two different edge-shared Mo_3O_(13) groups. The heteropoly blue was characterized by IR, UV, polarography, X-ray photoelectron spectra and ESR. All the results show that the structure of the heteropoly anion with Keggin structure remains unchanged basically in the process of reduction.
文摘The title heteropoly blue, (Bu_4N)_6H_(10)[PMo_(11)~ⅥMo~ⅤO_(40)]_4·H_2Ohas been photochemically synthesized and characterized with elemental analysis, solid diffusionreflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and X-ray singlecrystal analysis. The crystallographic data for C_(96)H_(218)Mo_(48)N_6O_(169)P_4 are as follows:M_r = 8889.76, triclinic, P_1, a = 1.4142(3) nm, b = 2.6027(5) nm, c = 2.6403(5) nm, α=113.96(3)°, β = 90.05(3)°, γ= 105.71(3)°, V = 8.481(3) nm^3, Z = 1, D_c = 1.741 g/cm^3, F(000)= 4264, μ= 1.798 mm^(-1). The X-ray crystal structure analysis reveals that there is oneindependent molecule in the unit cell of the title heteropoly blue which contains four mixed-valenceheteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structurepossesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is in thecrystallographic inversion center of the heteropoly anion and the eight oxygen atoms surroundingcentral phosphorus atom comprise of a distorted hexahedron. Heteropoly anion has two equal sets ofPO_4 tetrahedron. The PO_4 tetrahedron and the MoO_6 octahedron in the polyanion are greatlydistorted.
