A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the ...A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.展开更多
Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydroc...Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydrochloride(CPFX·HCl) reacting with H_nXM_~12 O_~40 ·nH_2O(X=P,Si; M=W,Mo) in an aqueous solution, and characterized by elemental analysis, IR spectrometry and TG-DTA. The IR spectrum confirms the presence of Keggin-type anions of heteropoly acids and the characteristic functional groups of ciprofloxacin. The TG/DTA curves show that their thermal decomposition is a multi-step process including simultaneous collapse of the Keggin-type structure. At first, these compounds had a mass loss of water molecules, then several other mass losses occured due to the decomposition of ciprofloxacin hydrochloride and its fragments with the degradation of Keggin anions. The end product of decomposition is the mixture of WO_3(or MoO_3) and SiO_2(or P_2O_5), identified by X-ray diffraction and IR spectroscopy. The possible thermal decomposition mechanisms of these complexes are proposed. This study exemplified that the thermal stability of the complexes containing tungsten is much better than that of the complexes containing molybdenum.展开更多
Two unusual complexes [Cda(Do)4(H2O)2CI](PW12O4O)'2H2O (1) and [Aga(Do)6(PW12O40)][Ag(Do)2]2(PW12O4O)'2H2O (2) were hydrothermally synthesized by the combination of two different metallic salts, Ke...Two unusual complexes [Cda(Do)4(H2O)2CI](PW12O4O)'2H2O (1) and [Aga(Do)6(PW12O40)][Ag(Do)2]2(PW12O4O)'2H2O (2) were hydrothermally synthesized by the combination of two different metallic salts, Keggin-type polyoxometalate and 1,10-phen-5,6-dione (Do), and characterized by elemental analyses, inductively coupled plasma analyses, infrared spectra, X-ray photoelectron spectroscopy, thermal gravimetry, photoluminescent spectra and single-crystal X-ray diffraction analyses. Crystal 1 is of monoclinic, space group P21/n with a = 12.383(3), b = 18.326(4), c = 16.437(3) A, β = 90.29(3)°, V = 3730.1(13) A3, Z = 2, CdzCasH32NsC1052PW12, Mr. = 4050.24, Dc = 3.604 g'cm-3,μ(MoKa) = 19.145 mm1, F(000) = 3608, GOOF = 1.168, the final R = 0.0569 and wR = 0.0745 for 5715 observed reflections (1 〉 2σ(I)). Crystal 2 is of triclinic, space group Pi with a = 13.959(5), b = 16.972(5), c = 17.647(5)A, α = 85.970(5), β = 81.353(5), γ = 86.316(5)°, V = 4117(2) A3 Z = 1, Ag6C120H64N200102P2W24, Mr. = 8539.47, Dc = 3.444 g-cm-3,μ(MoKa) = 17.511 mm-1, F(000) = 3828, GOOF = 1.033, the final R = 0.0981 and wR = 0.1658 for 9906 observed reflections (I 〉 2σ(I)). Structural analyses show that complex 1 has a zero dimensional structure, which is further assembled into a one-dimensional ladder-like structure through hydrogen bonds. Complex 2 possesses a one-dimensional chain structure. Furthermore, solid-state luminescent spectra of complexes 1 and 2 indicate red and green fluorescent emission, respectively.展开更多
Four rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW_(12)}with general formula [{RE(DMF)_(4)(H_(2)O)_4RE(DMF)_(6)}_(2){SiW_(12)O_(40)}_(3)](RE = La(1),Pr(2),Sm(3),Eu(4),DMF=N,N-...Four rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW_(12)}with general formula [{RE(DMF)_(4)(H_(2)O)_4RE(DMF)_(6)}_(2){SiW_(12)O_(40)}_(3)](RE = La(1),Pr(2),Sm(3),Eu(4),DMF=N,N-dimethylformamide) were synthesized by the conventional solution method.Structure analyses indicate that four compounds are isostructural and are all built from three [SiW_(12)O_(40)]^(4-) polyoxoanions and DMF ligands linked by RE^(3+).Compounds 1-4 are extremely sensitive to UV light and present excellent photochromic properties,in which the coloring and fading time of samples are both no more than 2 min,and the reversible coloring-fading process can be repeated for at least 10 cycles with little fatigue,suggesting that compounds 1-4 can be a series of fast-responsive and durable photochromic materials.Moreover,the solid-state photoluminescence spectra of compounds 3(Sm) and 4(Eu)display strong characteristic emissions of rare earth ions based on f-f transitions.Meanwhile,compound4(Eu) has a longer fluorescence lifetime up to 566.74 μs.Notably,co mpounds 3(Sm) and 4(Eu) exhibit the switchable luminescence behavior induced by photochromism,which allows them to be used as potential molecular switches.展开更多
Cesium heteropolysalts Cs3PMo12O40 and HCs3PVMo11O40 were synthesized by modifying the preparation conditions in order to get materials with a much higher surface area than the original Keggin-type heteropolyacids(H3P...Cesium heteropolysalts Cs3PMo12O40 and HCs3PVMo11O40 were synthesized by modifying the preparation conditions in order to get materials with a much higher surface area than the original Keggin-type heteropolyacids(H3PMo12O40 and H4PVMo11O40).These solids were used as carriers for the dispersion of H4PVMo11O40 heteropolyacid by the incipient wetness impregnation technique.The textural and structural properties of supports and catalysts were examined by scanning electron microscopy,N2 adsorption-desorption isotherms and Raman spectroscopy.The supported catalysts were studied before and after red/ox pretreatments by X-ray photoelectron spectroscopy,which showed that both the surface composition and oxidized to reduced species ratio depend on the used carrier.The catalytic performances of these novel supported catalysts in the selective oxidation of isobutane to methacrylic acid and methacrolein were studied.The best catalytic properties were obtained when H4PVMo11O40 was supported on HCs3PVMo11O40.The isobutane conversion and yield of the desired oxygenates increased along the unsupported H4PVMo11O40<H4PVMo11O40/Cs3PMo12O40<H4PVMo11O40/HCs3PVMo11O40 series.展开更多
The redox properties of α-Keggin-type heteropolyanion clusters [XM12O40]n-(X = Si,P; M = Mo,W) mainly depend on their constituent outer metal-oxygen cages {M12O36}. They act as "reservoirs",through which th...The redox properties of α-Keggin-type heteropolyanion clusters [XM12O40]n-(X = Si,P; M = Mo,W) mainly depend on their constituent outer metal-oxygen cages {M12O36}. They act as "reservoirs",through which the transfer and transition of electrons and protons may occur. At the atomic and molecular level,the redox properties of these clusters can be controlled and also tuned by modifying the metal M in the cages and the central heteroatom X of the clusters. Combined with relevant experimental results,this review summarizes our recent theoretical investigations of the effect of vanadium substitution on the redox properties of Keggin anion clusters. Theoretical modeling and calculation results showed that the oxidative ability of the modified species was increased by partial substitution of the cage M atoms of the Keggin clusters by vanadium atoms which have lower electronegativity. A linear correlation between the catalytic efficiency per vanadium atom and the microstructures of the vanadium(V)-substituted heteropolyanions [PVnMo12-nO40](3+n)-(n = 1-3) was established for the first time. This relationship may be suitable to interpret the catalytic behavior of the title compounds in the hydroxylation of benzene to phenol,and may also be used in understanding other reactions such as the oxidative dehydrogenation of isobutyric acid and the nitration of adamantine. The establishment of this nearly linear structure-property relationship may lay the foundations of understanding the behavior of the title compounds in homogeneous catalytic oxidation reactions,and may direct the design of future catalysts and the choice of other catalytic reactions.展开更多
Keggin-type molybdovanadophosphoric acids (HPA), H4PMo11VO40 (1), H5PMo10V2O40 (2) and H6PMo9V3O40 (3) were anchored onto γ-aminopropyltriethoxysilane (APTS) aminosilylated silica mesoporous SBA-15 through ...Keggin-type molybdovanadophosphoric acids (HPA), H4PMo11VO40 (1), H5PMo10V2O40 (2) and H6PMo9V3O40 (3) were anchored onto γ-aminopropyltriethoxysilane (APTS) aminosilylated silica mesoporous SBA-15 through acid-base neutralization and the resulting HPA/APTS/SBA-15 were characterized by BET, TEM, XRD, ICP, FFIR and ^31p MAS NMR. The characterization results indicate that the Keggin-structure of these HPAs is preserved within the mesoporous silica host. The samples were tested for catalytic aerobic oxidation of acetaldehyde heterogeneously in liquid phase under ambient condition. The electrostatic force between heteropoly acid and amino groups grafted on the silica channel surface leads to strong immobilization of HPA inside SBA-15 which is against the leaching during the reaction. The good catalytic performance and easy recycle of these catalysts make them as potential environmental friendly catalysts for elimination of indoor air pollutants.展开更多
Molybdenum trioxide(MoO_(3))can be employed as an excellent host for intercalation due to its 2D lay-ered structure that connected by van der Waals interactions.Herein,a series of polyoxometalate-based MoO_(3) composi...Molybdenum trioxide(MoO_(3))can be employed as an excellent host for intercalation due to its 2D lay-ered structure that connected by van der Waals interactions.Herein,a series of polyoxometalate-based MoO_(3) composites(Al_(13)@MoO_(3))were successfully prepared by interpolating the Keggin-type polycationic AlO_(4)Al_(12)(OH)_(24)H_(2)O_(12)^(7+)(Al_(13))into MoO_(3)gallery.These composites can be applied to rapidly adsorb the anionic dye methyl orange(MO)through strong electrostatic interactions lead to compact and sta-ble gathering in the surrounding of the numerous charged Al_(13).Adsorption behaviors of composites with the different amount of Al_(13) were determined,these results revealed that Al_(13)-3.34%@MoO_(3)exhibited the most remarkable adsorption capacity.More importantly,the composite maintains superior adsorption capacity for five consecutive adsorption/desorption cycles,suggesting that Al_(13)@MoO_(3)can be an efficient and durable adsorbent.展开更多
The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\...The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\}Cl\533H\-2O and \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\-2\[NaP\-5W\-\{30\}O\-\{110\}\]\524H\-2O, consisting of Keggin cations and heteropolyoxometalates, has been synthesized and characterized by ICP, IR and NMR. It is proved that the intrinsic identities of Keggin cation and heteropolyanions of the clusters are preserved within the gels.展开更多
基金National Natural Science Foundation of China(Grant No.52006225).
文摘A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.
文摘Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydrochloride(CPFX·HCl) reacting with H_nXM_~12 O_~40 ·nH_2O(X=P,Si; M=W,Mo) in an aqueous solution, and characterized by elemental analysis, IR spectrometry and TG-DTA. The IR spectrum confirms the presence of Keggin-type anions of heteropoly acids and the characteristic functional groups of ciprofloxacin. The TG/DTA curves show that their thermal decomposition is a multi-step process including simultaneous collapse of the Keggin-type structure. At first, these compounds had a mass loss of water molecules, then several other mass losses occured due to the decomposition of ciprofloxacin hydrochloride and its fragments with the degradation of Keggin anions. The end product of decomposition is the mixture of WO_3(or MoO_3) and SiO_2(or P_2O_5), identified by X-ray diffraction and IR spectroscopy. The possible thermal decomposition mechanisms of these complexes are proposed. This study exemplified that the thermal stability of the complexes containing tungsten is much better than that of the complexes containing molybdenum.
基金Program for New Century Excellent Talents in University(NCET-10-0176)of ChinaNatural Science Foundation Project of Jiangsu University(No.09JDG001,No.11jdg104 and BK2011528)
文摘Two unusual complexes [Cda(Do)4(H2O)2CI](PW12O4O)'2H2O (1) and [Aga(Do)6(PW12O40)][Ag(Do)2]2(PW12O4O)'2H2O (2) were hydrothermally synthesized by the combination of two different metallic salts, Keggin-type polyoxometalate and 1,10-phen-5,6-dione (Do), and characterized by elemental analyses, inductively coupled plasma analyses, infrared spectra, X-ray photoelectron spectroscopy, thermal gravimetry, photoluminescent spectra and single-crystal X-ray diffraction analyses. Crystal 1 is of monoclinic, space group P21/n with a = 12.383(3), b = 18.326(4), c = 16.437(3) A, β = 90.29(3)°, V = 3730.1(13) A3, Z = 2, CdzCasH32NsC1052PW12, Mr. = 4050.24, Dc = 3.604 g'cm-3,μ(MoKa) = 19.145 mm1, F(000) = 3608, GOOF = 1.168, the final R = 0.0569 and wR = 0.0745 for 5715 observed reflections (1 〉 2σ(I)). Crystal 2 is of triclinic, space group Pi with a = 13.959(5), b = 16.972(5), c = 17.647(5)A, α = 85.970(5), β = 81.353(5), γ = 86.316(5)°, V = 4117(2) A3 Z = 1, Ag6C120H64N200102P2W24, Mr. = 8539.47, Dc = 3.444 g-cm-3,μ(MoKa) = 17.511 mm-1, F(000) = 3828, GOOF = 1.033, the final R = 0.0981 and wR = 0.1658 for 9906 observed reflections (I 〉 2σ(I)). Structural analyses show that complex 1 has a zero dimensional structure, which is further assembled into a one-dimensional ladder-like structure through hydrogen bonds. Complex 2 possesses a one-dimensional chain structure. Furthermore, solid-state luminescent spectra of complexes 1 and 2 indicate red and green fluorescent emission, respectively.
基金Project supported by the National Natural Science Foundation of China(22172022,21872021,21671033,21901135)。
文摘Four rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW_(12)}with general formula [{RE(DMF)_(4)(H_(2)O)_4RE(DMF)_(6)}_(2){SiW_(12)O_(40)}_(3)](RE = La(1),Pr(2),Sm(3),Eu(4),DMF=N,N-dimethylformamide) were synthesized by the conventional solution method.Structure analyses indicate that four compounds are isostructural and are all built from three [SiW_(12)O_(40)]^(4-) polyoxoanions and DMF ligands linked by RE^(3+).Compounds 1-4 are extremely sensitive to UV light and present excellent photochromic properties,in which the coloring and fading time of samples are both no more than 2 min,and the reversible coloring-fading process can be repeated for at least 10 cycles with little fatigue,suggesting that compounds 1-4 can be a series of fast-responsive and durable photochromic materials.Moreover,the solid-state photoluminescence spectra of compounds 3(Sm) and 4(Eu)display strong characteristic emissions of rare earth ions based on f-f transitions.Meanwhile,compound4(Eu) has a longer fluorescence lifetime up to 566.74 μs.Notably,co mpounds 3(Sm) and 4(Eu) exhibit the switchable luminescence behavior induced by photochromism,which allows them to be used as potential molecular switches.
文摘Cesium heteropolysalts Cs3PMo12O40 and HCs3PVMo11O40 were synthesized by modifying the preparation conditions in order to get materials with a much higher surface area than the original Keggin-type heteropolyacids(H3PMo12O40 and H4PVMo11O40).These solids were used as carriers for the dispersion of H4PVMo11O40 heteropolyacid by the incipient wetness impregnation technique.The textural and structural properties of supports and catalysts were examined by scanning electron microscopy,N2 adsorption-desorption isotherms and Raman spectroscopy.The supported catalysts were studied before and after red/ox pretreatments by X-ray photoelectron spectroscopy,which showed that both the surface composition and oxidized to reduced species ratio depend on the used carrier.The catalytic performances of these novel supported catalysts in the selective oxidation of isobutane to methacrylic acid and methacrolein were studied.The best catalytic properties were obtained when H4PVMo11O40 was supported on HCs3PVMo11O40.The isobutane conversion and yield of the desired oxygenates increased along the unsupported H4PVMo11O40<H4PVMo11O40/Cs3PMo12O40<H4PVMo11O40/HCs3PVMo11O40 series.
基金Supported by the Special Project of Key Laboratory of the Sichuan Provincial Department of Education (Grant No. 2006ZD051)the National Natural Science Foundation of China (Grant No. 20072024)the Doctoral Fund Project of Yibin University (Grant No. 2006B03)
文摘The redox properties of α-Keggin-type heteropolyanion clusters [XM12O40]n-(X = Si,P; M = Mo,W) mainly depend on their constituent outer metal-oxygen cages {M12O36}. They act as "reservoirs",through which the transfer and transition of electrons and protons may occur. At the atomic and molecular level,the redox properties of these clusters can be controlled and also tuned by modifying the metal M in the cages and the central heteroatom X of the clusters. Combined with relevant experimental results,this review summarizes our recent theoretical investigations of the effect of vanadium substitution on the redox properties of Keggin anion clusters. Theoretical modeling and calculation results showed that the oxidative ability of the modified species was increased by partial substitution of the cage M atoms of the Keggin clusters by vanadium atoms which have lower electronegativity. A linear correlation between the catalytic efficiency per vanadium atom and the microstructures of the vanadium(V)-substituted heteropolyanions [PVnMo12-nO40](3+n)-(n = 1-3) was established for the first time. This relationship may be suitable to interpret the catalytic behavior of the title compounds in the hydroxylation of benzene to phenol,and may also be used in understanding other reactions such as the oxidative dehydrogenation of isobutyric acid and the nitration of adamantine. The establishment of this nearly linear structure-property relationship may lay the foundations of understanding the behavior of the title compounds in homogeneous catalytic oxidation reactions,and may direct the design of future catalysts and the choice of other catalytic reactions.
基金Project supported by the National Natural Science Foundation Committee of China (Nos. 20371013, 20273017, 20421303) and the Major State Basic Research Development Program of China (No. 2003CB615807).
文摘Keggin-type molybdovanadophosphoric acids (HPA), H4PMo11VO40 (1), H5PMo10V2O40 (2) and H6PMo9V3O40 (3) were anchored onto γ-aminopropyltriethoxysilane (APTS) aminosilylated silica mesoporous SBA-15 through acid-base neutralization and the resulting HPA/APTS/SBA-15 were characterized by BET, TEM, XRD, ICP, FFIR and ^31p MAS NMR. The characterization results indicate that the Keggin-structure of these HPAs is preserved within the mesoporous silica host. The samples were tested for catalytic aerobic oxidation of acetaldehyde heterogeneously in liquid phase under ambient condition. The electrostatic force between heteropoly acid and amino groups grafted on the silica channel surface leads to strong immobilization of HPA inside SBA-15 which is against the leaching during the reaction. The good catalytic performance and easy recycle of these catalysts make them as potential environmental friendly catalysts for elimination of indoor air pollutants.
基金the National Natural Science Foundation of China(Nos.21872021,21671033,22172022 and 22071019).
文摘Molybdenum trioxide(MoO_(3))can be employed as an excellent host for intercalation due to its 2D lay-ered structure that connected by van der Waals interactions.Herein,a series of polyoxometalate-based MoO_(3) composites(Al_(13)@MoO_(3))were successfully prepared by interpolating the Keggin-type polycationic AlO_(4)Al_(12)(OH)_(24)H_(2)O_(12)^(7+)(Al_(13))into MoO_(3)gallery.These composites can be applied to rapidly adsorb the anionic dye methyl orange(MO)through strong electrostatic interactions lead to compact and sta-ble gathering in the surrounding of the numerous charged Al_(13).Adsorption behaviors of composites with the different amount of Al_(13) were determined,these results revealed that Al_(13)-3.34%@MoO_(3)exhibited the most remarkable adsorption capacity.More importantly,the composite maintains superior adsorption capacity for five consecutive adsorption/desorption cycles,suggesting that Al_(13)@MoO_(3)can be an efficient and durable adsorbent.
文摘The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\}Cl\533H\-2O and \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\-2\[NaP\-5W\-\{30\}O\-\{110\}\]\524H\-2O, consisting of Keggin cations and heteropolyoxometalates, has been synthesized and characterized by ICP, IR and NMR. It is proved that the intrinsic identities of Keggin cation and heteropolyanions of the clusters are preserved within the gels.