As a kind of rare metals,rubidium is often used to prepare special glass,photomultiplier tubes,thermoelectric converter,organic catalysts and antidepressants.Rubidium forms no minerals of its own,hence,it often coexis...As a kind of rare metals,rubidium is often used to prepare special glass,photomultiplier tubes,thermoelectric converter,organic catalysts and antidepressants.Rubidium forms no minerals of its own,hence,it often coexists with展开更多
A sandwich-type tungstophosphate, (1,3-H2dap)8-14[Co4(H2O)2(α-B-PWgO34)2]2·5H20 (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffr...A sandwich-type tungstophosphate, (1,3-H2dap)8-14[Co4(H2O)2(α-B-PWgO34)2]2·5H20 (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and UV spectroscopy. The title compound crystallizes in triclinic, space group P1 with a = 13.691(3), b = 17.744(4), c = 20.620(5) A, a =113.466(5), β = 91.184(5), Y = 104.223(5)°, V = 4414.3(17)A^3, C24H96Co8N16O145P4W36, Mr = 10143.09, Dc = 3.816 g/cm^3,μ(MoKa) = 24.210 mm^-1, F(000) = 4452, Z = 1, the final R = 0.0694 and wR = 0.1519 for 9910 observed reflections (I 〉 2σ(I)). The compound consists of two sets of tetra-transition metal-substituted sandwich frameworks, [Co4(H2O)2(α-B-PW9O34)2]^10- having an inversion centre. Two lacunary α-B-[PW9O34]^9- Keggin units are linked by a rhomb-like Co4O14(H2O)2 cluster, in which the Co^2+ ions are coordinated by one water molecule. Isolatedly protonated 1,3-H2dap^2+ units act as counter-ions to interact with the [Co4(H2O)2(α-B-PWgO34)2]^10- heteropolyanions via hydrogen bonds, resulting in a three-dimensional framework.展开更多
A mixed valence lacunary tungstophosphate with Keggin structure was photochemically synthesized. It was proved to be an one electron reduced heteropoly 'blue' by W(V) analysis. The subsequent changes were ob...A mixed valence lacunary tungstophosphate with Keggin structure was photochemically synthesized. It was proved to be an one electron reduced heteropoly 'blue' by W(V) analysis. The subsequent changes were observed in the UV Vis, IR and 31 P NMR spectra of the mixed valence species due to the introduced 'blue' electron. The magnetic property investigated by means of the Evans method suggested that the 'blue' electron was fully delocalized over the framework of the mixed valence lacunary tungstophosphate, and the vacancy in the lacunary species did not transmit the circulating electron, which thus blocked 'ring current' in some intersecting loops.展开更多
In this paper, a new complex inorganic ion exchanger Titanium Phosphate - Ammonium Tungstophosphate (abbreviated as TiP - AWP) was synthesized, whose exchange character and chemical structure were studied, Thiscompoun...In this paper, a new complex inorganic ion exchanger Titanium Phosphate - Ammonium Tungstophosphate (abbreviated as TiP - AWP) was synthesized, whose exchange character and chemical structure were studied, Thiscompound exhibits high exchange capacity and selectivity for Cs+, its exchangecapacity attains 0. 95 mmol/g in the medium of 0. 1 mol/L HNO3, andwhich almost doesn’ t change in the 1 AW imitated waste solution. There areno change in exchange capacity and structure after several times of exchanging,eluting, regenerating, which is of great importance to the separation and uptaking of radio - nuclides. Further more, this exchanger has good thermal andradioactive stability.展开更多
A functional microcapsule was prepared by encapsulating the fine crystalline ammonium tungstophosphate (AWP) in calcium alginate polymer (CaALG). The characterization of AWP-CaALG microcapsule was examined by SEM ...A functional microcapsule was prepared by encapsulating the fine crystalline ammonium tungstophosphate (AWP) in calcium alginate polymer (CaALG). The characterization of AWP-CaALG microcapsule was examined by SEM and EPMA. The ad- sorption behavior of Cs(Ⅰ), Rb(Ⅰ), Sr(Ⅱ), Pd(II), Ru(Ⅲ), Rh(Ⅲ), La(Ⅲ), Ce(Ⅲ), Dy(Ⅲ) and Zr(IV) was investigated by the batch method. The batch experiments were carried out by varying the shaking times, HNO3 concentration, and initial concen- tration of metal ions. Relatively large K+ values above 105 cm3/g for Cs(I) were obtained in the range of 0.1-5 M HNO3, re- sulting in a separation factor of Cs/Rb exceeding 102. In contrast, the K+ values of Sr(II), Pd(II), Ru(Ⅲ), La(Ⅲ), Dy(Ⅲ), Ce(Ⅲ) and Zr(IV) were considerably lower than 50 cm3/g. The K+ value of Cs(1) decreased in the order of the coexisting ions, H+ 〉 Na+ 〉〉 NH4+, and a linear relationship with a slop of about -1 was obtained between log Kd and log [NH4+] ([NH4+] 〉 0.01 M) The adsorption of Cs(I) was found to be controlled by chemisorption mechanism, and followed a Langmuir-type adsorption equation. A high uptake percentage of 99.4% for Cs(I) was obtained by using the dissolved solutions of spent fuel from FBR-JOYO (JAEA).展开更多
The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstoph...The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstophosphates, such as α and β isomers. The β isomer is not stable and is difficult to prepare. So it is rarely reported. This note describes the synthesis and characterization of some new lanthanoid complexes with a formula M<sub>12</sub>H<sub>5</sub> [Ln(β-P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>)<sub>2</sub>·xH<sub>2</sub>O (Ln<sup>3+</sup>=La, Nd, Sm, Eu, Gd, Dy, M=Bu<sub>4</sub>N<sup>+</sup>, x=2;展开更多
A novel photochromic complex comprising of Keggin type tungstophosphate acid (PW12) and polyacrylamide (PAM) was prepared. FT-IR results showed that the Keggin geometry of PW12 was still preserved inside the composit...A novel photochromic complex comprising of Keggin type tungstophosphate acid (PW12) and polyacrylamide (PAM) was prepared. FT-IR results showed that the Keggin geometry of PW12 was still preserved inside the composite, and a charge-transfer bridge was built between PW12 and PAM via hydrogen bond. AFM images indicated that surface topography of polymer matrix changed after adding PW12. Under UV irradiation, the film was reduced photochemically to yield a blue species, which was reversible in the present of oxygen in polymeric network.展开更多
A new organic-inorganic hybrid based on tungstophosphate anions and benzotria- zole cations, [Na(BTA)E(H2O)2]2[{Cd(BTA)4(H2O)}2(P2W18O62)]·6H2O (1) (BTA = benzotriazole) has been synthesized in aque...A new organic-inorganic hybrid based on tungstophosphate anions and benzotria- zole cations, [Na(BTA)E(H2O)2]2[{Cd(BTA)4(H2O)}2(P2W18O62)]·6H2O (1) (BTA = benzotriazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray analysis showed that both {Na(BTA)2} and {Cd(BTA)4} units are supported on the a-Dawson polyoxoanion [P2W18062]6- via the surface bridging oxygen atoms. The electrochemical properties of 1 in aqueous solution are studied at room temperature. It was found that 1 presents good electrocatalytic activities for the reduction of NO2^-.展开更多
Two novel zeotype crystals, K4[Cr30(H2O) 3(OOCH) 6] 2[ P2W18O62]· 9.5H2 O and K4[ Cr3O( H2O)3( OOCH)6 ]2[ H3 P2 W17Co(H2O) O61]· 20H2O(2) , were synthesized and their structures were determined ...Two novel zeotype crystals, K4[Cr30(H2O) 3(OOCH) 6] 2[ P2W18O62]· 9.5H2 O and K4[ Cr3O( H2O)3( OOCH)6 ]2[ H3 P2 W17Co(H2O) O61]· 20H2O(2) , were synthesized and their structures were determined using X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, α= 1. 5895(2) nm, b=1.5895(2) nm, c =2.1620(4) nm, α=90°, β=90°, γ= 120°, V=4.7305(13) nm^3, Z=2, R1 =0,0726, ωR2 =0. 1542; C6H57O98K4Cr3CoP2W17 (2), hexagonal P6(3)/mmc, α = 1.61328(3) nm, b = 1.61328(3) nm, c=2.06613(9) nm, α=90°, β=90°, γ=120°, V=4.6570(2) nm^3, Z=2, R1 =0.0377, ωR2 =0. 1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal I and laeunary Wens-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.展开更多
TiO_(2)nanosheets with dominant{001}facets,coupled with Cs_(2.5)H_(0.5)PW_(12)O_(40),were successfully synthesized by a one-step hydrothermal reaction.The photocatalytic activity of nanocatalysts was evaluated by the ...TiO_(2)nanosheets with dominant{001}facets,coupled with Cs_(2.5)H_(0.5)PW_(12)O_(40),were successfully synthesized by a one-step hydrothermal reaction.The photocatalytic activity of nanocatalysts was evaluated by the degradation of Rhodamine B under UV light irradiation.The results showed that both the addition of Cs_(2.5)H_(0.5)PW_(12)O_(40)and the exposed{001}facets of TiO_(2)have a positive effect on the photocatalytic activity.The improved photoactivity of nanocomposites in comparison with that of TiO_(2)nanosheets could be attributed to the synergistic effect between Cs_(2.5)H_(0.5)PW_(12)O_(40)and TiO_(2)which facilitates the separation of photo-induced hole-electron pairs.展开更多
基金financially supported by the National High Technology Research and Development Program of China (2012AA061704)
文摘As a kind of rare metals,rubidium is often used to prepare special glass,photomultiplier tubes,thermoelectric converter,organic catalysts and antidepressants.Rubidium forms no minerals of its own,hence,it often coexists with
基金Supported by the Natural Science Foundation of Henan Province (No. 102300410021)
文摘A sandwich-type tungstophosphate, (1,3-H2dap)8-14[Co4(H2O)2(α-B-PWgO34)2]2·5H20 (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and UV spectroscopy. The title compound crystallizes in triclinic, space group P1 with a = 13.691(3), b = 17.744(4), c = 20.620(5) A, a =113.466(5), β = 91.184(5), Y = 104.223(5)°, V = 4414.3(17)A^3, C24H96Co8N16O145P4W36, Mr = 10143.09, Dc = 3.816 g/cm^3,μ(MoKa) = 24.210 mm^-1, F(000) = 4452, Z = 1, the final R = 0.0694 and wR = 0.1519 for 9910 observed reflections (I 〉 2σ(I)). The compound consists of two sets of tetra-transition metal-substituted sandwich frameworks, [Co4(H2O)2(α-B-PW9O34)2]^10- having an inversion centre. Two lacunary α-B-[PW9O34]^9- Keggin units are linked by a rhomb-like Co4O14(H2O)2 cluster, in which the Co^2+ ions are coordinated by one water molecule. Isolatedly protonated 1,3-H2dap^2+ units act as counter-ions to interact with the [Co4(H2O)2(α-B-PWgO34)2]^10- heteropolyanions via hydrogen bonds, resulting in a three-dimensional framework.
文摘A mixed valence lacunary tungstophosphate with Keggin structure was photochemically synthesized. It was proved to be an one electron reduced heteropoly 'blue' by W(V) analysis. The subsequent changes were observed in the UV Vis, IR and 31 P NMR spectra of the mixed valence species due to the introduced 'blue' electron. The magnetic property investigated by means of the Evans method suggested that the 'blue' electron was fully delocalized over the framework of the mixed valence lacunary tungstophosphate, and the vacancy in the lacunary species did not transmit the circulating electron, which thus blocked 'ring current' in some intersecting loops.
文摘In this paper, a new complex inorganic ion exchanger Titanium Phosphate - Ammonium Tungstophosphate (abbreviated as TiP - AWP) was synthesized, whose exchange character and chemical structure were studied, Thiscompound exhibits high exchange capacity and selectivity for Cs+, its exchangecapacity attains 0. 95 mmol/g in the medium of 0. 1 mol/L HNO3, andwhich almost doesn’ t change in the 1 AW imitated waste solution. There areno change in exchange capacity and structure after several times of exchanging,eluting, regenerating, which is of great importance to the separation and uptaking of radio - nuclides. Further more, this exchanger has good thermal andradioactive stability.
文摘A functional microcapsule was prepared by encapsulating the fine crystalline ammonium tungstophosphate (AWP) in calcium alginate polymer (CaALG). The characterization of AWP-CaALG microcapsule was examined by SEM and EPMA. The ad- sorption behavior of Cs(Ⅰ), Rb(Ⅰ), Sr(Ⅱ), Pd(II), Ru(Ⅲ), Rh(Ⅲ), La(Ⅲ), Ce(Ⅲ), Dy(Ⅲ) and Zr(IV) was investigated by the batch method. The batch experiments were carried out by varying the shaking times, HNO3 concentration, and initial concen- tration of metal ions. Relatively large K+ values above 105 cm3/g for Cs(I) were obtained in the range of 0.1-5 M HNO3, re- sulting in a separation factor of Cs/Rb exceeding 102. In contrast, the K+ values of Sr(II), Pd(II), Ru(Ⅲ), La(Ⅲ), Dy(Ⅲ), Ce(Ⅲ) and Zr(IV) were considerably lower than 50 cm3/g. The K+ value of Cs(1) decreased in the order of the coexisting ions, H+ 〉 Na+ 〉〉 NH4+, and a linear relationship with a slop of about -1 was obtained between log Kd and log [NH4+] ([NH4+] 〉 0.01 M) The adsorption of Cs(I) was found to be controlled by chemisorption mechanism, and followed a Langmuir-type adsorption equation. A high uptake percentage of 99.4% for Cs(I) was obtained by using the dissolved solutions of spent fuel from FBR-JOYO (JAEA).
文摘The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstophosphates, such as α and β isomers. The β isomer is not stable and is difficult to prepare. So it is rarely reported. This note describes the synthesis and characterization of some new lanthanoid complexes with a formula M<sub>12</sub>H<sub>5</sub> [Ln(β-P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>)<sub>2</sub>·xH<sub>2</sub>O (Ln<sup>3+</sup>=La, Nd, Sm, Eu, Gd, Dy, M=Bu<sub>4</sub>N<sup>+</sup>, x=2;
基金This work was supported by the National Natural Science Foundation of China (59932040).
文摘A novel photochromic complex comprising of Keggin type tungstophosphate acid (PW12) and polyacrylamide (PAM) was prepared. FT-IR results showed that the Keggin geometry of PW12 was still preserved inside the composite, and a charge-transfer bridge was built between PW12 and PAM via hydrogen bond. AFM images indicated that surface topography of polymer matrix changed after adding PW12. Under UV irradiation, the film was reduced photochemically to yield a blue species, which was reversible in the present of oxygen in polymeric network.
基金the Department of Education of Jilin Province(No.2014349 and 2015431)Science and Technology Bureau of Jilin City(No.20156418)Jilin Institute of Chemical Technology(No.201343 and 2015031)
文摘A new organic-inorganic hybrid based on tungstophosphate anions and benzotria- zole cations, [Na(BTA)E(H2O)2]2[{Cd(BTA)4(H2O)}2(P2W18O62)]·6H2O (1) (BTA = benzotriazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray analysis showed that both {Na(BTA)2} and {Cd(BTA)4} units are supported on the a-Dawson polyoxoanion [P2W18062]6- via the surface bridging oxygen atoms. The electrochemical properties of 1 in aqueous solution are studied at room temperature. It was found that 1 presents good electrocatalytic activities for the reduction of NO2^-.
基金Supported by the Dalian Municipal Science and Technology Commission and Liaoning Provincial Science and Technology Com-mission(No. 20031059)
文摘Two novel zeotype crystals, K4[Cr30(H2O) 3(OOCH) 6] 2[ P2W18O62]· 9.5H2 O and K4[ Cr3O( H2O)3( OOCH)6 ]2[ H3 P2 W17Co(H2O) O61]· 20H2O(2) , were synthesized and their structures were determined using X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, α= 1. 5895(2) nm, b=1.5895(2) nm, c =2.1620(4) nm, α=90°, β=90°, γ= 120°, V=4.7305(13) nm^3, Z=2, R1 =0,0726, ωR2 =0. 1542; C6H57O98K4Cr3CoP2W17 (2), hexagonal P6(3)/mmc, α = 1.61328(3) nm, b = 1.61328(3) nm, c=2.06613(9) nm, α=90°, β=90°, γ=120°, V=4.6570(2) nm^3, Z=2, R1 =0.0377, ωR2 =0. 1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal I and laeunary Wens-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.
基金This work was supported by the National Natural Science Foundation of China(Nos.21371035,21173050).
文摘TiO_(2)nanosheets with dominant{001}facets,coupled with Cs_(2.5)H_(0.5)PW_(12)O_(40),were successfully synthesized by a one-step hydrothermal reaction.The photocatalytic activity of nanocatalysts was evaluated by the degradation of Rhodamine B under UV light irradiation.The results showed that both the addition of Cs_(2.5)H_(0.5)PW_(12)O_(40)and the exposed{001}facets of TiO_(2)have a positive effect on the photocatalytic activity.The improved photoactivity of nanocomposites in comparison with that of TiO_(2)nanosheets could be attributed to the synergistic effect between Cs_(2.5)H_(0.5)PW_(12)O_(40)and TiO_(2)which facilitates the separation of photo-induced hole-electron pairs.