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Sample records for polyoxometalate keggin clusters

  1. Catalytic Consequences of Composition in Polyoxometalate Clusters with Keggin Structure

    SciTech Connect

    Macht, Josef; Janik, Michael J.; Neurock, Matthew; Iglesia, Enrique

    2007-10-15

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Reliable correlations among structure, composition, and function in heterogeneous catalysis require well-defined atomic connectivity within active structures and the assessment of the specific elementary steps and reaction intermediates responsible for the relevant catalytic function. The non-uniform nature of typical active structures creates significant challenges because probes of structure and function average such heterogeneity in complex ways. Polyoxometalate (POM) clusters with stable Keggin structures and well-defined atomic connectivity provide the compositional diversity required for a rigorous assessment of the consequences of composition on catalytic reactivity.

  2. Trapping the δ Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand.

    PubMed

    Sartzi, Harikleia; Miras, Haralampos N; Vilà-Nadal, Laia; Long, De-Liang; Cronin, Leroy

    2015-12-14

    We report the synthesis, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate polyanion. A family of δ-Keggin polyoxoanions of the general formula, (TEA)Hp Naq [H2 M12 (XO4 )O33 (TEA)]⋅r H2 O where p, q, r=[2,3,8] for 1 and [4,1,4] for 2 were isolated by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster thereby stabilizing the polyanionic δ-Keggin archetype. The δ-Keggin species were characterized by single-crystal X-ray diffraction, FT-IR, UV/Vis, NMR, and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited multi-electron transfer and reversible photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations accompanied with color changes under light. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A novel dumbbell-like polyoxometalate assembled of copper(II)-disubstituted monovacant keggin polyoxoanions with a tetranuclear copper cluster.

    PubMed

    Miao, Hao; Xu, Xiao; Ju, Wei-Wei; Wan, Hong-Xiang; Zhang, Yu; Zhu, Dun-Ru; Xu, Yan

    2014-03-17

    A dimeric Keggin polyoxometalate, [Cu(bpy)(μ2-OH)]4[(H2O)(bpy)2HPW11Cu2O39]2·2CH3CH2OH·10H2O (1), constructed from two dicopper(II)-substituted monovacant Keggin polyoxoanions bridged by a Cu4 cluster, has been hydrothermally synthesized. Magnetic analysis indicates predominantly an antiferromagnetic interaction between copper(II) centers. Compound 1 also shows very high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester.

  4. Effects of support on bifunctional methanol oxidation pathways catalyzed by polyoxometallate keggin clusters

    SciTech Connect

    Liu, Haichao; Iglesia, Enrique

    2003-12-26

    H5PV2Mo10O40 polyoxometallate Keggin clusters supported on ZrO2, TiO2, SiO2, and Al2O3 are effective catalysts for CH3OH oxidation reactions to form HCHO, methyl formate (MF), and dimethoxymethane (DMM). Rates and selectivities and the structure of supported clusters depend on the surface properties of the oxide supports. Raman spectroscopy showed that Keggin structures remained essentially intact on ZrO2, TiO2, and SiO2 after treatment in air at 553 K, but decomposed to MoOx and VOx oligomers on Al2O3. Accessible protons per Keggin unit (KU) were measured during CH3OH oxidation by titration with 2,6-di-tert-butyl pyridine. For similar KU surface densities (0.28 0.37 KU/nm2), the number of accessible protons was larger on SiO2 than on ZrO2 and TiO2 and much smaller on Al2O3 supports, even though residual dimethyl ether (DME) synthesis rates after titrant saturation indicated that the fractional dispersion of KU was similar on the first three supports. These effects of support on structure and on H+ accessibility reflect varying extents of interaction between polyoxometallate clusters and supports. Rates of CH3OH oxidative dehydrogenation per KU were higher on ZrO2 and TiO2 than on SiO2 at similar KU surface densities (0.28 0.37 KU/nm2) and dispersion, indicating that redox properties of Keggin clusters depend on the identity of the support used to disperse them. ZrO2 and TiO2 supports appear to enhance the reducibility of anchored polyoxometallate clusters. Rates were much lower on Al2O3, because structural degradation led to less reactive MoOx and VOx domains. CH3OH reactions involve primary oxidation to form HCHO and subsequent secondary reactions to form DMM and MF. These reactions involve HCHO CH3OH acetalization steps leading to methoxymethanol (CH3OCH2OH) or hemiacetal intermediates, which condense with CH3OH on acid sites to form DMM or dehydrogenate to form MF. COx formation rates are much lower than those of other reactions, and DME forms in parallel

  5. Two new polyoxometalate-based hybrids consisting of Keggin-type cluster modified by (Ag{sub 4}) group

    SciTech Connect

    Zhao, Xiaofang; Sun, Xiaowei; Han, Zhangang; Zhao, Chuan; Yu, Haitao; Zhai, Xueliang

    2013-11-15

    Two new supramolecular polyoxometalate compounds [Ag{sub 2}(mbpy){sub 3}][Ag(mbpy){sub 2}][PW{sub 12}O{sub 40}] (1) and [Ag{sub 2}(mbpy){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. The structural feature of 1–2 is in the cationic moiety of a tetra-core (Ag{sub 4}) cluster through weak Ag…Ag interactions. The silver(I) centers show three-, four- and five-coordinated geometries. In 1 the tetrameric silver atoms in ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} covalently bind to [PW{sub 12}O{sub 40}]{sup 3−} anion via Ag3O bonds, while there is only intermolecular hydrogen bonding between ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} and [SiW{sub 12}O{sub 40}]{sup 4−} in 2. The coordination environments of the tetrameric silver cations have a great influence on the structure richness of the Keggin-based hybrids. The fluorescence properties of compounds 1 and 2 also have been discussed. - Graphical abstract: New polyoxometalate-based hybrids consisting of Keggin-type clusters modified by (Ag{sub 4}) groups had been synthesized and characterized, and their photoluminescence properties were also discussed. Display Omitted - Highlights: • Two Keggin-type polyoxometalates consisting of (Ag{sub 4}) clusters through weak Ag…Ag interactions have been synthesized. • There exist face-to-face and dot-to-face π…π interactions in (Ag-ligand){sub 4} fragment. • The fluorescence properties of (Ag{sub 4}) modified POMs are also discussed.

  6. A Supramolecular Tetra-Keggin Polyoxometalate

    PubMed

    Kim; Zeng; VanDerveer; Hill

    1999-11-02

    Giant polyoxometalates with catalytic, magnetic, and antiviral properties, which are in part attributable to their structures, are currently of great interest. Herein is described the synthesis and characterization of 1, a structurally novel tetrameric complex from Keggin ions (see picture). This complex is stable under the physiological conditions of the stomach (pH 1-2), which is interesting since related keggin anions are among the least toxic and yet most potent antiviral agents of the more than 300 polyoxometalates investigated biologically and pharmacologically.

  7. Two new polyoxometalate tri-supported transition metal complexes constructed from bi-capped Keggin molybdenum vanadium clusters and copper complex fragments

    NASA Astrophysics Data System (ADS)

    Cui, Ji-Wen; Cui, Xiao-Bing; Xu, Jia-Ning; Yu, Hai-Hui; Xu, Ji-Qing; Duan, Wei-Jie; Wang, Tie-Gang

    2008-11-01

    Two new molybdenum-vanadium polyoxometalate tri-supported transition metal complexes [Cu(2,2 '-bipy)] [Cu(2,2 '-bipy) 2] 2[PMo 8V 6O 42]· nH 2O ( n = 1.5 ( 1) and n = 2 ( 2); 2,2 '-bipy = 2,2 '-bipyridine) have been hydrothermally synthesized and characterized by elemental analyses, IR, XPS and single-crystal X-ray diffraction analyses. Both compound 1 and compound 2 contain molybdenum-vanadium polyoxometalates, each of which support one [Cu(2,2 '-bipy)] 2+ cation and two [Cu(2,2 '-bipy) 2] 2+ cations, respectively. The difference between compound 1 and compound 2 is that the polyoxoanion of 1 is a bi-capped α-Keggin cluster and that of 2 is a bi-capped pseudo-Keggin one. Studies of magnetic properties indicated the presence of ferromagnetic behaviors for compounds 1 and 2.

  8. Mixed-valence polyoxometalate clusters. I. Delocalization of electronic pairs in dodecanuclear heteropoly blues with keggin structure

    NASA Astrophysics Data System (ADS)

    Borrás-Almenar, J. J.; Clemente, J. M.; Coronado, E.; Tsukerblat, B. S.

    1995-06-01

    The problem of delocalization of a pair of electrons over dodecanuclear polyoxometalate clusters with the Keggin structure is considered with the aim of explaining the spin pairing in these multi-nuclear mixed-valence systems. A general approach that considers the Coulomb interactions between the two delocalized electrons, as well as the single and double electron transfer processes which can be operative in delocalization of the electronic pairs is developed. The new approach is based on the site-symmetry concept which makes possible a group theoretical classification for the delocalized states of electronic pairs. This procedure proves to be very efficient in the calculation of the transfer matrices which are expressed in terms of the Coulomb energy, and the single- and double-transfer parameters. The influence of these electronic parameters on the spectrum of the low-lying energy levels of the cluster is discussed, and the conditions giving rise to the stabilization of a singlet ground spin state for the electronic pair are elucidated.

  9. Two new polyoxometalate-based hybrids consisting of Keggin-type cluster modified by {Ag4} group

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaofang; Sun, Xiaowei; Han, Zhangang; Zhao, Chuan; Yu, Haitao; Zhai, Xueliang

    2013-11-01

    Two new supramolecular polyoxometalate compounds [Ag2(mbpy)3][Ag(mbpy)2][PW12O40] (1) and [Ag2(mbpy)3]2[SiW12O40] (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. The structural feature of 1-2 is in the cationic moiety of a tetra-core {Ag4} cluster through weak Ag…Ag interactions. The silver(I) centers show three-, four- and five-coordinated geometries. In 1 the tetrameric silver atoms in {[Ag2(mbpy)3]2}4+ covalently bind to [PW12O40]3- anion via Ag3O bonds, while there is only intermolecular hydrogen bonding between {[Ag2(mbpy)3]2}4+ and [SiW12O40]4- in 2. The coordination environments of the tetrameric silver cations have a great influence on the structure richness of the Keggin-based hybrids. The fluorescence properties of compounds 1 and 2 also have been discussed.

  10. Mechanistic Consequences of Composition in Acid Catalysis by Polyoxometalate Keggin Clusters

    SciTech Connect

    Macht, Josef; Janik, Michael J.; Neurock, Matthew; Iglesia, Enrique

    2008-08-06

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The kinetics and mechanism of ether and alkanol cleavage reactions on Brønsted acid catalysts based on polyoxometalate (POM) clusters are described in terms of the identity and dynamics of elementary steps and the stability of the transition states involved. Measured rates and theoretical calculations show that the energies of cationic transition states and intermediates depend on the properties of reactants (proton affinity), POM clusters (deprotonation enthalpy), and ion-pairs in transition states or intermediates (stabilization energy). Rate equations and elementary steps were similar for dehydration of alkanols (2- propanol, 1- and 2-butanol, tert-butanol) and cleavage of sec-butyl-methyl ether on POM clusters with different central atoms (P, Si, Co, Al). Dehydration rates depend on the rate constant for elimination from adsorbed alkanols or ethers and on the equilibrium constant for the formation of unreactive reactant dimers. Elimination involves E1 pathways and late carbenium-ion transition states. This is consistent with small kinetic isotope effects for all deuterated alkanols, with strong effects of substituents on elimination rates, and with the similar alkene stereoselectivities measured for alkanol dehydration, ether cleavage, and alkene double-bond isomerization. n-Donor reactants (alkanols, ethers) and products (water) inhibit dehydration rates by forming stable dimers that do not undergo elimination; their stability is consistent with theoretical estimates, with the dynamics of homogeneous analogues, and with the structure and proton affinity of the n-donors. Elimination rate constants increased with increasing valence of the central POM atom, because of a

  11. Mixed-valence polyoxometalate clusters. III. Vibronic problem for the 2-electron reduced heteropoly blue with the Keggin structure

    NASA Astrophysics Data System (ADS)

    Borrás-Almenar, J. J.; Clemente, J. M.; Coronado, E.; Tsukerblat, B. S.

    1995-06-01

    A general approach to the vibronic problem of delocalized electronic pairs in mixed-valence compounds is developed and applied to understand the ways of electron delocalization in dodecanuclear polyoxometalate clusters containing two moving electrons. The interplay between electronic and vibronic interactions is examined. The electronic spectrum is shown to consist of two spin triplets 3T 1 and 3T 2 and three spin singlets 1A 1, 1E and 1T 2 levels determined by the double-transfer processes (parameter P). Jahn-Teller and pseudo-Jahn-Teller problems ( 3T1 + 3T2) ⊗ ( e + t2) and ( 1A1 + 1E + 1T2) ⊗ ( e + t2) have been considered in the framework of the Piepho-Krausz-Schatz model dealing with the only vibronic parameter. Several kinds of spatial electronic distribution have been found corresponding to the stable points of the energy surfaces. For spin-triplet states, potential surfaces contain six minima in e space corresponding to partially delocalized electronic pairs over four sides of the T d structure (limiting case of weak coupling), or delocalized over two opposite sides (limiting case of strong coupling). The former situation restricts electron delocalization to two of the three metal octahedra of each M 3O 12 triad in such a way that each electron moves over a tetrameric unit in which the metal sites are alternatively sharing edges and corners. In the t 2 space the electronic pair can be either delocalized over three sides, giving rise to a trigonal-type distortion of the cluster and a partial electron delocalization over two opposite M 3O 12 triads (four trigonal minima in the case of strong transfer or relatively weak vibronic interaction), or be completely localized (case of strong vibronic coupling). For spin-singlet states the system possesses a stable point in the high-symmetrical nuclear configuration, corresponding to a full delocalization of the electronic pairs in the Keggin cluster. The influence of vibronic interaction on the nature of the

  12. Bi-antimony capped Keggin polyoxometalate modified with Cu-ligand fragment

    SciTech Connect

    Huang, Jiao; Han, Zhangang; Zhang, Heng; Yu, Haitao; Zhai, Xueliang

    2012-10-15

    Three polyoxometalates consisting of bi-antimony capped Keggin-type clusters: [Cu(mbpy){sub 2}]{sub 2}[PMo{sub 12}O{sub 40}Sb{sub 2}]{center_dot}4H{sub 2}O (1), [Cu(mbpy){sub 2}][PMo{sub 12}O{sub 40}Sb{sub 2}] (2) and {l_brace}Cu(mbpy)[Cu(mbpy){sub 2}]{sub 2}{r_brace}[VMo{sub 8}V{sub 4}O{sub 40}Sb{sub 2}]{center_dot}2H{sub 2}O (3) (mbpy=4,4 Prime -dimethyl-2,2 Prime - dipyridyl in 1 and 2; 5,5 Prime -dimethyl-2,2 Prime -dipyridyl in 3) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. Single-crystal analysis revealed that all of three compounds are built upon bi-antimony capped Keggin-type polyoxoanions and Cu-mbpy cations. In 1-3, two Sb{sup III} centers located at the two opposite of anionic surface adopt fundamentally tetragonal pyramidal coordination geometry. Both compounds 1 and 2 consist of P-centered Keggin structure, while compound 3 presents a V-centered Keggin anion. The Keggin-type anions present different structural features: isolated cluster in 1 and Cu-ligand-supported cluster in 2 and 3. - Graphical abstract: Three hybrid compounds consisting of bi-antimony capped Keggin-type clusters modified with Cu-ligand cations have been synthesized and characterized. Highlights: Black-Right-Pointing-Pointer Three hybrid compounds consisting of bi-antimony capped Keggin-type clusters have been synthesized. Black-Right-Pointing-Pointer Two Sb{sup III} centers located at the two opposite of anionic surface adopt tetragonal pyramidal coordination geometry. Black-Right-Pointing-Pointer The anions present different structural features: isolated and Cu-ligand-supported cluster.

  13. Bi-antimony capped Keggin polyoxometalate modified with Cu-ligand fragment

    NASA Astrophysics Data System (ADS)

    Huang, Jiao; Han, Zhangang; Zhang, Heng; Yu, Haitao; Zhai, Xueliang

    2012-10-01

    Three polyoxometalates consisting of bi-antimony capped Keggin-type clusters: [Cu(mbpy)2]2[PMo12O40Sb2]·4H2O (1), [Cu(mbpy)2][PMo12O40Sb2] (2) and {Cu(mbpy)[Cu(mbpy)2]2}[VMo8V4O40Sb2]·2H2O (3) (mbpy=4,4'-dimethyl-2,2'- dipyridyl in 1 and 2; 5,5'-dimethyl-2,2'-dipyridyl in 3) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. Single-crystal analysis revealed that all of three compounds are built upon bi-antimony capped Keggin-type polyoxoanions and Cu-mbpy cations. In 1-3, two SbIII centers located at the two opposite of anionic surface adopt fundamentally tetragonal pyramidal coordination geometry. Both compounds 1 and 2 consist of P-centered Keggin structure, while compound 3 presents a V-centered Keggin anion. The Keggin-type anions present different structural features: isolated cluster in 1 and Cu-ligand-supported cluster in 2 and 3.

  14. Two polyoxometalate-based coordination polymers constructed from Mn(II)-4,4‧-bipyridine-N,N‧-dioxide building blocks and Keggin-type clusters: Syntheses, crystal structures and spectral properties

    NASA Astrophysics Data System (ADS)

    Bai, Yan; Li, Meng-Meng; Huang-Fu, You-Jing; Dang, Dong-Bin

    2013-11-01

    Two polyoxometalate-based coordination polymers {[Mn2(dpdo)4(H2O)6](GeMo12O40)(H2O)4}n (1) and {[Mn2(dpdo)4(H2O)6](GeW12O40)(H2O)3}n (2) (dpdo = 4,4‧-bipyridine-N,N‧-dioxide) have been synthesized and characterized by IR, elemental analysis, XRPD, TG technique and X-ray crystallography. The polymers 1 and 2 are basically isostructural and feature a 3D supramolecular framework decorated with Keggin-type polyanion clusters based on one-dimension polymeric chains, which formed through the coordination interaction of Mn(II) and dpdo. The luminescent properties of the polymers were investigated in the solid state at room temperature.

  15. Two polyoxometalate-based coordination polymers constructed from Mn(II)-4,4'-bipyridine-N,N'-dioxide building blocks and Keggin-type clusters: Syntheses, crystal structures and spectral properties.

    PubMed

    Bai, Yan; Li, Meng-Meng; Huang-Fu, You-Jing; Dang, Dong-Bin

    2013-11-01

    Two polyoxometalate-based coordination polymers {[Mn2(dpdo)4(H2O)6](GeMo12O40)(H2O)4}n (1) and {[Mn2(dpdo)4(H2O)6](GeW12O40)(H2O)3}n (2) (dpdo=4,4'-bipyridine-N,N'-dioxide) have been synthesized and characterized by IR, elemental analysis, XRPD, TG technique and X-ray crystallography. The polymers 1 and 2 are basically isostructural and feature a 3D supramolecular framework decorated with Keggin-type polyanion clusters based on one-dimension polymeric chains, which formed through the coordination interaction of Mn(II) and dpdo. The luminescent properties of the polymers were investigated in the solid state at room temperature. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms.

    PubMed

    Pang, Haijun; Gómez-García, Carlos J; Peng, Jun; Ma, Huiyuan; Zhang, Chunjing; Wu, Qingyin

    2013-12-21

    The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d-4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39](8-) cluster (SiW11) is connected to ten metals (five Ag(+) and five Ln(3+) cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol(-1) per Ce(3+) and Pr(3+) ion, respectively) and confirm the presence of isolated Ce(3+) and Pr(3+) ions.

  17. One-dimensional coordination polymers constructed from bicapped Keggin polyoxometalate and cyclic tetranuclear Cu I cluster bridged by asymmetrical bipyridine derivative

    NASA Astrophysics Data System (ADS)

    Tian, Aixiang; Han, Zhangang; Peng, Jun; Sha, Jingquan; Zhao, Yulong; Pang, Haijun; Zhang, Pengpeng; Zhu, Min

    2008-10-01

    This article reports two new bicapped Keggin-based hybrid compounds, {[Cu 4I(cppy) 4][PMo 7VIMo 5VO 40(V IVO) 2]}·2H 2O ( 1) and {[Cu 4I(cppy) 4][SiMo 8VIMo 4VO 40(V IVO) 2]}·2H 2O ( 2) (cppy = 4-(5-(4-chlorophenyl)pyridin-2-yl)pyridine), synthesized under hydrothermal conditions and characterized by X-ray single-crystal diffraction, elemental analyses, IR, XPS, TG and CV analyses. Structural characterization shows that the two compounds are isostructural, consisting of square tetranuclear [Cu 4I(cppy) 4] 4+ circuits and reduced bivanadyl Keggin clusters. The tetranuclear [Cu 4I(cppy) 4] 4+ circuit is 'windstick'-style. The polyoxoanions acting as junctures connect the tetranuclear circuits to construct a chain. These chains are further connected through π⋯π interactions, halogen bonding and hydrogen bonding interactions to construct a 3D superamolecular structure. The electrochemical behaviors of the 1-CPE have been studied in detail.

  18. Novel intercluster compound between a heptakis{triphenylphosphinegold(I)}dioxonium cation and an α-Keggin polyoxometalate anion.

    PubMed

    Yoshida, Takuya; Nomiya, Kenji; Matsunaga, Satoshi

    2012-09-07

    A novel intercluster compound, [{{Au(PPh(3))}(4)(μ(4)-O)}{{Au(PPh(3))}(3)(μ(3)-O)}][α-PW(12)O(40)]·EtOH (1) constructed between a heptakis{triphenylphosphinegold(i)}dioxonium cation and an α-Keggin polyoxometalate (POM) is synthesized and unequivocally characterized by elemental analysis, TG/DTA, FTIR, X-ray crystallography, solid-state CPMAS (31)P NMR and solution ((1)H, (31)P{(1)H}) NMR. The heptagold(i) cluster was formed during the course of carboxylate elimination of a monomeric phosphinegold(i) carboxylate precursor, i.e., [Au((RS)-pyrrld)(PPh(3))] ((RS)-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid), in the presence of the sodium salt of an α-Keggin POM, Na(3)[α-PW(12)O(40)]·9H(2)O. Compound 1 was formed by ionic interaction between the heptagold(i) cluster cation and the α-Keggin POM anion. The heptagold(i) cluster unit was formed by four inter-cationic aurophilic interactions between the tetragold(i) cluster unit and trigold(i) cluster unit. The tetragold(i) cluster unit and trigold(i) cluster unit contained μ(4)-O and μ(3)-O atoms, respectively.

  19. Synergistic combination of multi-Zr(IV) cations and lacunary Keggin germanotungstates leading to a gigantic Zr24-cluster-substituted polyoxometalate.

    PubMed

    Huang, Ling; Wang, Sa-Sa; Zhao, Jun-Wei; Cheng, Lin; Yang, Guo-Yu

    2014-05-28

    Synergistic directing roles of six lacunary fragments resulted in an unprecedented Zr24-cluster substituted poly(polyoxotungstate) Na10K22[Zr24O22(OH)10(H2O)2(W2O10H)2(GeW9O34)4(GeW8O31)2]·85H2O (Na10K22·1·85H2O), which contains the largest [Zr24O22(OH)10(H2O)2] (Zr24) cluster in all the Zr-based poly(polyoxometalate)s to date. The most remarkable feature is that the centrosymmetric Zr24-cluster-based hexamer contains two symmetry-related [Zr12O11(OH)5(H2O)(W2O10H)(GeW9O34)2(GeW8O31)](16-) trimers via six μ3-oxo bridges and was simultaneously trapped by three types of different segments of B-α-GeW9O34, B-α-GeW8O31, and W2O10. The other interesting characteristic is that there are two pairs of intriguing triangular atom alignments: one is composed of the Zr(2,4,6,8,11) and W21 atoms and the other contains the Ge(1-3), Zr(3,5,7,9,10,12) and W26 atoms, and the Zr5 atom is inside the triangle; a linking mode is unobserved. The oxygenation reactions of thioethers by H2O2 were evaluated when Na10K22·1·85H2O served as a catalyst. Results show that it is an effective catalyst for oxygenation of thioethers by H2O2. The unique redox property of oxygen-enriched polyoxotungstate fragments and Lewis acidity of the Zr cluster imbedded in Na10K22·1·85H2O provide a sufficient driving force for the catalytic conversion from thioethers to sulfoxides/sulfones.

  20. Two new hybrid compounds assembled from Keggin-type polyoxometalates and transition metal coordination complexes

    SciTech Connect

    Wang Yan; Zou, Bo; Xiao Lina; Jin Ning; Peng Yu; Wu Fengqing; Ding Hong; Wang Tiegang; Gao Zhongmin; Zheng Dafang; Cui Xiaobing; Xu Jiqing

    2011-03-15

    Two new hybrid compounds based on Keggin-type polyoxometalates: {l_brace}[PMo{sub 12}O{sub 40}][Ni(Phen){sub 2}(H{sub 2}O)]{sub 2{r_brace}}.K.2OH{sup -} (1) and [Cd{sub 2}(Phen){sub 4}Cl{sub 2}][HPW{sub 12}O{sub 40}].H{sub 2}O (2) (Phen=1,10-phenanthroline), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Compound 1 exhibits a 1-D chain structure constructed from Pseudo-Keggin polyoxometalate bi-supported transition metal coordination complexes linked by K{sup +} ions. Compound 2 contains Pseudo-Keggin polyoxoanions [HPW{sub 12}O{sub 40}]{sup 2-} and novel metal-chloride-ligand coordination complexes [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+}. -- Graphical abstract: Two new hybrid compounds based on different Keggin-type polyoxometalates have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS, XRD, elemental analysis and single crystal X-ray diffraction analysis. Display Omitted Research highlights: {yields} Two hybrids based on Pseudo-Keggin polyanions and metal coordination complexes. {yields} 1-D structure formed by polyanion bisupported metal coordination units linked by K{sup +}. {yields} A metal-chloride-ligand coordination complex [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+}. {yields} A hybrid based on polyanions and metal-chloride-ligand coordination complexes.

  1. A polyoxometalate-based inorganic-organic hybrid polymer constructed from silver-Schiff base building block and Keggin-type cluster: Synthesis, crystal structure and photocatalytic performance for the degradation of rhodamine B.

    PubMed

    Li, Lei; Cheng, Meng; Bai, Yan; An, Bing; Dang, Dongbin

    2015-11-05

    One polyoxometalate-based inorganic-organic hybrid polymer [Ag3L4(PMo12O40)(CH3OH)]·CH3OH (1), where L is N,N'-bis(furan-2-ylmethylene)hydrazine, has been synthesized at room temperature and structurally characterized by infrared spectroscopy, ultraviolet-visible spectroscopy, elemental analysis, X-ray powder diffraction and X-ray single-crystal crystallography. The structure of 1 exhibits a crystalline one-dimensional polymer constructed by the connections of Keggin-type [PMo12O40](3-) anions and [Ag3L4](3+) units, in which each Ag(I) center adopted a distorted square pyramidal environment. The spectroscopic experiments show that polymer 1 not only is potential semiconductor materials but also displays the obvious photocatalytic performance for the degradation of rhodamine B. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Energetics of Al13 Keggin cluster compounds

    PubMed Central

    Armstrong, Christopher R.; Casey, William H.; Navrotsky, Alexandra

    2011-01-01

    The ϵ-Al13 Keggin aluminum hydroxide clusters are essential models in establishing molecular pathways for geochemical reactions. Enthalpies of formation are reported for two salts of aluminum centered ϵ-Keggin clusters, Al13 selenate, (Na(AlO4)Al12(OH)24(SeO4)4•12H2O) and Al13 sulfate, (NaAlO4Al12(OH)24(SO4)4•12H2O). The measured enthalpies of solution, ΔHsol, at 28 °C in 5 N HCl for the ε-Al13 selenate and sulfate are −924.57 (± 3.83) and −944.30 ( ± 5.66) kJ·mol-1, respectively. The enthalpies of formation from the elements, ΔHf,el, for Al13 selenate and sulfate are −19,656.35 ( ± 67.30) kJ·mol-1, and −20,892.39 ( ± 70.01) kJ·mol-1, respectively. In addition, ΔHf,el for sodium selenate decahydrate was calculated using data from high temperature oxide melt solution calorimetry measurements: −4,006.39 ( ± 11.91) kJ·mol-1. The formation of both ε-Al13 Keggin cluster compounds is exothermic from oxide-based components but energetically unfavorable with respect to a gibbsite-based assemblage. To understand the relative affinity of the ϵ-Keggin clusters for selenate and sulfate, the enthalpy associated with two S-Se exchange reactions was calculated. In the solid state, selenium is favored in the Al13 compound relative to the binary chalcogenate, while in 5 N HCl, sulfur is energetically favored in the cluster compound compared to the aqueous solution. This contribution represents the first thermodynamic study of ε-Al13 cluster compounds and establishes a method for other such molecules, including the substituted versions that have been created for kinetic studies. Underscoring the importance of ε-Al13 clusters in natural and anthropogenic systems, these data provide conclusive thermodynamic evidence that the Al13 Keggin cluster is a crucial intermediate species in the formation pathway from aqueous aluminum monomers to aluminum hydroxide precipitates. PMID:21852572

  3. Magneto-Structural Analysis of Iron(III) Keggin Polyoxometalates.

    PubMed

    Bandeira, Nuno A G; Sadeghi, Omid; Woods, Toby J; Zhang, Yuan-Zhu; Schnack, Jürgen; Dunbar, Kim; Nyman, May; Bo, Carles

    2017-02-16

    A computational study and magnetic susceptibility measurements of three homonuclear Fe(III) Keggin structures are herein presented: the [FeO4@Fe12F24(μ-OCH3)12](5-) anion (1), the [Bi6{FeO4@Fe12O12(OH)12}(μ-O2CCCl3)12](+) cation (2) and its polymorph [Bi6{FeO4@Fe12O12(OH)10(H2O)2}(μ-O2CCF3)10](3+) (3). These results are contrasted with the exchange interactions present in the previously characterized [Fe6(OH)3Ge2W18O68(OH)6](11-) and [H12As4Fe8W30O120(H2O)2](4-) anions. The computational analysis shows that the most significant antiferromagnetic spin coupling takes place at the junction between each of the {Fe3O6(OH)3}/{Fe3F6(OCH3)3} framework motifs, a possibility that had been previously discarded in the literature on the basis of the Fe-Fe distances. For all the examined iron(III) Keggin structures, it is found that the magnitude of the magnetic couplings within each structural subunit follows the same trend.

  4. Intriguing Role of a Quaternary Ammonium Cation in the Dissociation Chemistry of Keggin Polyoxometalate Anions

    NASA Astrophysics Data System (ADS)

    Cao, Jie; Li, Chenchen; Zhang, Zhengxiang; Xu, Chong; Yan, Jie; Cui, Fengyun; Hu, Changwen

    2012-02-01

    The gas-phase fragmentations of a series of Keggin polyoxometalate anions with molecular formula of TBAn[XM12O40] (X = P, Si; M = Mo, W) were studied by electrospray ionization tandem mass spectrometry. The bare polyoxoanions [XM12O40]n- as well as the non-covalent complexes {TBA[XM12O40]}(n-1)- and {TBAm[XM12O40]2}3- displayed characteristic dissociation pathways. Fragmentation of [XM12O40]n- led to pairs of complementary product anions whose total stoichiometry and charge matched those of the precursor anion, consistent with the previous study by Ma et al. The nature of the non-covalent interaction between [XM12O40]n- and TBA+ was addressed in detail via the example of {TBA[XM12O40]}(n-1)-. The non-covalent interaction [1] primarily dominated by the Coulombic attraction of the opposite charges completely changed the dissociation chemistry of [XM12O40]n-. The non-covalent complexes {TBA[XM12O40]}(n-1)- and {TBAm[XM12O40]2}3-, formed by the charge reduction during the electrospray process, underwent distinct dissociation routes: {TBA[XM12O40]}(n-1)- fragmented to give rise to its product ion {(C4H9)[XM12O40]}(n-1)- by cleaving the N-C covalent bond inside the TBA+ cation whereas {TBAm[XM12O40]2}3- dissociated into a pair of product ions, {TBAi[XM12O40]}2- and {TBAm-i[XM12O40]}-, by breaking the non-covalent bond between [XM12O40]n- and TBA+. In addition, energy-variable CID was used to map the relative stabilities of the ion clusters in the gas phase, which was in excellent agreement with the relative orders of thermal stability in the condensed phase.

  5. Transformation of Tri-Titanium(IV)-Substituted α-Keggin Polyoxometalate (POM) into Tetra-Titanium(IV)-Substituted POMs : Reaction Products of Titanium(IV) Sulfate with the Dimeric Keggin POM Precursor under Acidic Conditions

    PubMed Central

    Mouri, Yuki; Sakai, Yoshitaka; Kobayashi, Yoshitaka; Yoshida, Shoko; Nomiya, Kenji

    2010-01-01

    Reaction products of titanium(IV) sulfate in HCl-acidic aqueous solution with the dimeric species linked through three intermolecular Ti-O-Ti bonds of the two tri-titanium(IV)-substituted α-Keggin polyoxometalate (POM) subunits are described. Two novel titanium(IV)-containing α-Keggin POMs were obtained under different conditions. One product was a dimeric species through two intermolecular Ti-O-Ti bonds of the two tetra-titanium(IV)-substituted α-Keggin POM subunits, i.e., [[{Ti(H2O)3}2(μ-O)](α-PW9Ti2O38)]26- (1). The other product was a monomeric α-Keggin species containing the tetra-titanium(IV) oxide cluster and two coordinated sulfate ions, i.e., [{Ti4(μ-O)3(SO4)2(H2O)8}(α-PW9O34)]3- (2). Molecular structures of 1 and 2 were also discussed based on host (lacunary site)-guest (titanium atom) chemistry.

  6. A remarkable member of the polyoxometalates: the eight-nickel-capped alpha-keggin polyoxoazonickelate.

    PubMed

    Dong, Lanjun; Huang, Rudan; Wei, Yongge; Chu, Wei

    2009-08-17

    The eight-nickel-capped polyoxoazonickelate, [Ni(20)(OH)(24)(MMT)(12)(SO(4))](NO(3))(2).6H(2)O (1; MMT = 2-mercapto-5-methyl-1,3,4-thiadiazole), has been synthesized, which has an alpha-Keggin structure with eight nickel caps. In this structure, the polyatom is the late transition metal Ni(II); the central heteroatom is S, and the organic terminal ligand becomes the primary part of the Keggin structure. This is a Keplerate-type cluster, which shows a central Ni(II)(12) cuboctahedron formed by the 12 Ni(II) centers of the classical alpha-Keggin core and a Ni(II)(8) hexahedron formed by the eight nickel caps.

  7. A new Keggin-type polyoxometalate catalyst for degradation of aqueous organic contaminants

    NASA Astrophysics Data System (ADS)

    Olgun, Asim; Çolak, Alper Tolga; Gübbük, İ. Hilal; Şahin, Onur; Kanar, Ebru

    2017-04-01

    In this study, a new polyoxometalate, K16[Ni(H2O)6]2[BW12O40]4·48H2O (1) was synthesized at room temperature and characterized by X-ray single crystal diffractions, elemental analyses, IR spectra, and thermo gravimetric analyses (TGA). Crystal structure analysis reveals that compound 1 exhibits a supramolecular structure containing one Keggin-type [BW12O40]4 heteropoly anion. The catalytic properties of this molecule for the degradation of Methyl red (MR), Rhodamine B (RhB), Methyl orange (MO) and Congo red (CR) were investigated. The results show that the compound 1 is a promising catalyst candidate for dye degradation.

  8. Preparation and application of L-cysteine-doped Keggin polyoxometalate microtubes

    SciTech Connect

    Shen Yan; Peng Jun; Zhang Huanqiu; Meng Cuili; Zhang Fang

    2012-01-15

    L-cysteine-doped tungstosilicate (Lcys-SiW{sub 12}) microtubes are prepared, and the amount of L-cysteine doped in the microtubes can be tuned to some extent. The as-prepared Lcys-SiW{sub 12} microtubes are sensitive to ammonia gas exhibited through the distinct color change of the microtubes from light purple to dark blue after exposing to ammonia gas. A possible mechanism of the coloration is that the adsorbed ammonia molecules increase the basicity of the Lcys-SiW{sub 12} microtubes and promote the redox reaction between L-cysteine and polyoxometalate. This is a pH-dependent solid-solid redox reaction, which is triggered by proton capture agent. The Lcys-SiW{sub 12} microtubes show application in chemical sensors for alkaline gases. - Graphical abstract: The Lcys-SiW{sub 12} microtubes were formed during transformation of the monolacunary Keggin-type [{alpha}-SiW{sub 11}O{sub 39}]{sup 8-} to the saturated Keggin-type [{alpha}-SiW{sub 12}O{sub 40}]{sup 4-}, meanwhile L-cysteine molecules were doped during the growth of the microtubes. Highlights: Black-Right-Pointing-Pointer L-cysteine-doped polyoxometalate microtubes are prepared. Black-Right-Pointing-Pointer Amount of L-cysteine doped in the microtubes can be tuned to some extent. Black-Right-Pointing-Pointer Lcys-SiW{sub 12} microtubes can be applied as a sensor for detecting alkaline gases. Black-Right-Pointing-Pointer This is a proton capture agent-triggered solid-solid redox reaction.

  9. Desulfurization of 4-methyl dibenzothiophene using titanium supported Keggin type polyoxometalate

    NASA Astrophysics Data System (ADS)

    Lesbani, Aldes; Anggraini, Ana; Mohadi, Risfidian; Rohendi, Dedi; Said, Muhammad

    2017-03-01

    Titanium supported Keggin type polyoxometalate H5PV2Mo10O40.nH2O has been prepared using tetra isopropyl orthotitanate by sol-gel method and microemulsion to form H5PV2Mo10O40/TiO2. Compound H5PV2Mo10O40.nH2O/TiO2 was characterized using FTTR spectroscopy, X-Ray analysis, and acidity measurement. FTTR spectrum showed that all vibration of titanium and polyoxometalate were appeared in H5PV2Mo10O40.nH2O/TiO2 with decreasing crystallinity. The acidity of H5PV2Mo10O40.nH2O/TiO2 was higher than H5PV2Mo10O40.nH2O. Desulfurization of 4-methyl dibenzothiophene (4-MDBT) using H5PV2Mo10O40.nH2O/TiO2 as catalyst resulted conversion of 4-MDBT was 99% and higher than desulfurization using H5PV2Mo10O40.nH2O under mild conditions.

  10. Tetrahedral connection of ε-Keggin-type polyoxometalates to form an all-inorganic octahedral molecular sieve with an intrinsic 3D pore system.

    PubMed

    Zhang, Zhenxin; Sadakane, Masahiro; Murayama, Toru; Izumi, Shoko; Yasuda, Nobuhiro; Sakaguchi, Norihito; Ueda, Wataru

    2014-01-21

    A new type of polyoxometalate-based porous material was successfully synthesized. The new material is the first fully inorganic Keggin-type polyoxometalate-based microporous material with intrinsically ordered open micropores and is the third member of the small family of octahedral molecular sieves (OMSs). Twelve MoO6 or VO6 octahedra surround a central VO4 tetrahedron to form ε-Keggin polyoxometalate building blocks (ε-VMo9.4V2.6O40) that are linked by Bi(III) ions to form crystalline Mo-V-Bi oxide with a diamondoid topology. The presence of a tetrahedral shape of the ε-Keggin polyoxometalate building block results in arrangement of microporosity in a tetrahedral fashion which is new in OMSs. Owing to its microporosity, this Mo-V-Bi oxide shows zeolitic-like properties such as ion-exchange and molecule adsorption.

  11. Effects of heteroatoms on electronic states of divanadium-substituted γ-Keggin-type polyoxometalates.

    PubMed

    Uehara, Kazuhiro; Miyachi, Takuya; Nakajima, Takahito; Mizuno, Noritaka

    2014-04-07

    Effects of heteroatoms on electronic states of divanadium-substituted γ-Keggin-type polyoxometalates (TBA)4[γ-XV2W10O38(μ-OH)(μ-OR)] (X = Ge, Si; R = Me, Et, n-Pr, H; TBA = tetra(n-butyl)ammonium) and (TBA)4[γ-XV2W10O38(μ-O)] (X = Ge, Si) were investigated, using a combination of nuclear magnetic resonance spectroscopy and density functional theory (DFT) calculations. Both the substitution of SiO4 heteroatom units with larger GeO4 ones and the introduction of more electronegative alkoxo groups in place of hydroxo groups resulted in deshielding of the vanadium nuclei. DFT calculations using the Def2-SVP basis set at TPSSh level of theory could well-reproduce the anionic moieties of a series of divanadium-substituted γ-Keggin-type polyoxometalates, and the estimated chemical shifts approximately reproduced the experimental ones with the individual gauge localized orbital method (SO-IGLO) taking the spin-orbit interaction into account. The magnetic shielding (σ) consists of σd + σp + σSD + σFC, where σd, σp, σSD, and σFC are diamagnetic, paramagnetic, spin-dipolar, and Fermi contact terms, respectively. The σp changed much among (TBA)4[γ-XV2W10O38(μ-OH)2], (TBA)4[γ-XV2W10O38(μ-OH)(μ-OR)], and (TBA)4[γ-XV2W10O38(μ-O)], while σd, σSD, and σFC did not change much. Therefore, the σp largely contributed to the magnetic shielding. Moreover, σp consisted of the occupied-occupied transitions (s-terms) and the occupied-virtual ones (u-terms), and the u-terms were predominant for σp. The most contributing occupied localized orbital consisted of the dz(2) orbital of vanadium, the pz orbital of terminal oxygen related to the V═O bond, and the pz orbital of oxygen of the XO4 unit, whereas the two virtual localized orbitals consisted of the dyz orbital of vanadium and the py orbital of terminal oxygen. Analysis of the structural and electronic characteristics of a series of divanadium-substituted γ-Keggin-type POMs revealed a linear correlation

  12. Biological evaluation of two Keggin-type polyoxometalates containing glycine as mushroom tyrosinase inhibitors.

    PubMed

    Xing, Rui; Wang, Fang; Zheng, Aping; Wang, Li; Fei, Dan; Yu, Yaping

    2016-09-01

    Two Keggin-type polyoxometalates (POMs) containing glycine, (HGly)3 PW12 O40 and (HGly)4 SiW12 O40 , were synthesized and evaluated as mushroom tyrosinase inhibitors. The spectrophotometric method results showed that both (HGly)3 PW12 O40 and (HGly)4 SiW12 O40 could strongly inhibit the diphenolase activity of the tyrosinase and that their inhibition mechanisms were reversible. Their half-inhibition concentration values were estimated to be 1.55 and 1.39 mmol/L, respectively. The inhibition kinetics analysis by Lineweaver-Burk plots indicated that (HGly)3 PW12 O40 was an uncompetitive inhibitor with KIS  = 0.046 mmol/L, whereas (HGly)4 SiW12 O40 was a noncompetitive inhibitor with KI  = KIS  = 2.17 mmol/L. This study may help to extend the application of POMs in the fields of medicine and food preservation.

  13. Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

    SciTech Connect

    Shi Zhenyu; Peng Jun . E-mail: jpeng@nenu.edu.cn; Gomez-Garcia, Carlos J.

    2006-01-15

    Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen){sub 2}]{sub 2}{l_brace}[Cu(phen)]{sub 2} [SiMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace} (1), {l_brace}[Zn(phen){sub 2}]{sub 2}[GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Zn(phen){sub 2}(H{sub 2}O)]{sub 2} [GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.3H{sub 2}O (2) and {l_brace}[Co(phen){sub 2}]{sub 2}[PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Co(phen){sub 2}(OH)]{sub 2} [PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.2.5H{sub 2}O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo{sub 12}O{sub 4}(VO){sub 2}]{sup 2-} linked to two [Cu(phen)]{sup +} complexes with two [Cu(phen){sub 2}]{sup +} countercations. Compound 2 contains two bicapped Keggin anions [GeMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-}, one linked to two [Zn(phen){sub 2}(H{sub 2}O)]{sup 2+} cations and the other one linked to two [Zn(phen){sub 2}]{sup 2+} cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions. -- Graphical

  14. Hydrothermal syntheses, crystal structures of three new organic-inorganic hybrids constructed from Keggin-type [BW 12O 40] 5- clusters and transition metal complexes

    NASA Astrophysics Data System (ADS)

    Wang, Jing-Ping; Guo, Gui-Ling; Niu, Jing-Yang

    2008-08-01

    Three new organic-inorganic hybrid compounds constructed from Keggin-type polyanions and transition metal complexes, [Mn(2,2'-bipy) 3] 1.5[BW 12O 40Mn(2,2'-bipy) 2(H 2O)]·0.25H 2O ( 1), [Fe(2,2'-bipy) 3] 1.5[BW 12O 40Fe(2,2'-bipy) 2(H 2O)]·0.5H 2O ( 2) and [Cu 2(phen) 2(OH) 2] 2H[Cu(H 2O) 2{BW 12O 40Cu 0.75(phen)(H 2O)} 2]·1.5H 2O ( 3), have been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. Compounds 1 and 2 are isostructural and both exhibit monosupporting polyoxometalate cluster structure, each of which contains a [BW 12O 40] 5- cluster decorated by one transition metal complex. Compound 3 contains a bisupporting polyoxometalate cluster anion where two {Cu 0.75(phen)(H 2O)} 0.75+ fragments are supported on the polyoxometalate dimer {Cu(H 2O) 2(BW 12O 40) 2} 8-, this represents the first bisupporting polyoxometalate cluster based on a Keggin-type polyoxometalate dimer, which are further packed together via π-π stacking contacts into an extended 1-D chain.

  15. Chiral heteropoly blues and controllable switching of achiral polyoxometalate clusters.

    PubMed

    Wang, Yizhan; Li, Haolong; Wu, Che; Yang, Yang; Shi, Lei; Wu, Lixin

    2013-04-22

    Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

  16. Inorganic-organic hybrid materials based on keggin type polyoxometalates and organic polyammonium cations

    NASA Astrophysics Data System (ADS)

    Vasylyev, Maxym; Popovitz-Biro, Ronit; Shimon, Linda J. W.; Neumann, Ronny

    2003-08-01

    Co-crystallization of a tri-ammonium cation with short and somewhat flexible ‘arms', [N,N,N-tris[2-(dimethylamino)ethyl]-1,3,5-benzenetricarboxamide]3+, with a polyoxometalate trianion, PW12O403-, yielded an insoluble channeled or microporous structure. The polyoxometalate clusters are arranged in a layered and zig-zag fashion along the xy plane. Looking along the x-axis, channels of a dimension of ∼3.5×∼6.5 Å are observed. It was found that C-H⋯O bonds aided in determining the crystal packing by providing directionality to the anion-cation interaction. On the other hand the co-crystallization of a tetraammonium cation with an extended and rigid tetrahedral configuration, 1,3,5,7-tetrakis{4-[(E)-2(N-methylpyridinium-4-yl)vinyl]phenyl adamantane tetraiodide, with a polyoxometalate tetracation, SiW12O404-, yielded a lamellar structure with alternating layers with spacing of 16.6 Å of the inorganic-organic hybrid material.

  17. Eu(III) luminescence and tryptophan fluorescence spectroscopy as a tool for understanding interactions between hen egg white lysozyme and metal-substituted Keggin type polyoxometalates.

    PubMed

    Goovaerts, Vincent; Stroobants, Karen; Absillis, Gregory; Parac-Vogt, Tatjana N

    2015-09-01

    The interaction between the lacunary Keggin K7PW11O39, the Eu(III)-substituted Keggin K4EuPW11O39 (Eu-Keggin) and the Ce(IV)-substituted Keggin [Me2NH2]10[Ce(PW11O39)2] (Ce-Keggin) polyoxometalates (POMs), and the proteins hen egg white lysozyme (HEWL) and the structurally homologous α-lactalbumin (α-LA) was studied by steady state and time-resolved Eu(III) luminescence and tryptophan (Trp) fluorescence spectroscopy. The excitation spectrum of Eu-Keggin at lower concentrations ([Eu-Keggin]<100 μM) is dominated by a ligand-to-metal charge transfer band (291 nm). For higher concentrations ([Eu-Keggin]>250 μM) the (5)L6←(7)F0 transition becomes the most intense peak. In the absence of protein, the number of coordinated water molecules to the Eu(III) centre of Eu-Keggin is 4, indicating a 1:1 Eu(III):POM species. In the presence of phosphate buffer this number linearly decreases from 4 to 2 upon increasing phosphate buffer concentration. Upon addition of HEWL, there are no coordinated water molecules, suggesting interaction between Eu-Keggin and the protein surface. In addition, this interaction results in a more than threefold increase of the hypersensitive (5)D0→(7)F2 transition for the Eu-Keggin/HEWL mixture. The calculated association constant amounted to 2.2×10(2) M(-1) for the Eu-Keggin/HEWL complex. Tryptophan fluorescence quenching studies were performed and the quenching constants were calculated to be 9.1×10(4) M(-1), 4×10(4) M(-1) and 4.1×10(5) M(-1) for the lacunary Keggin/HEWL, the Eu-Keggin/HEWL and the Ce-Keggin/HEWL complexes, respectively. The number of bound POM molecules to HEWL was 1.04 for the lacunary Keggin POM, and 1.0 for Eu-Keggin, indicating the formation of a 1:1 POM/HEWL complex. The value of 1.38 for Ce-Keggin might indicate a transition from 1:1 to 1:2 interaction.

  18. Keggin-Type Polyoxometalate-Based Metal-Organic Networks for Photocatalytic Dye Degradation.

    PubMed

    Hao, Hong-Fang; Zhou, Wen-Zhe; Zang, Hong-Ying; Tan, Hua-Qiao; Qi, Yan-Fei; Wang, Yong-Hui; Li, Yang-Guang

    2015-08-01

    The reaction of Keggin-type polyoxometalate (POM) units, transition-metal (TM) ions, and a rigid bis(imidazole) ligand (1,4-bis(1-imidazolyl)benzene (bimb)) in a hydrothermal environment led to the isolation of four new POM-based metal-organic networks, [H2 L][CuL][SiW12 O40 ]⋅2 H2 O (1), [H2 L]2 [Co(H2 O)3 L][SiW11 CoO39 ]⋅6 H2 O (2), KH[CuL]2 [SiW11 CoO39 (H2 O)]⋅2 H2 O (3), and [CuL]4 [GeW12 O40 ]⋅H2 O (4; L=bimb). All four compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1 and 3 are new 3D networks with 1D channels. Compounds 2 and 4 contain 2D networks, which further stack into 3D supramolecular networks. The contributions of pH value, the negative charge of the POM, and the TM coordination modes to the construction of 3D networks were elucidated by comparing the synthetic conditions and structures of compounds 1-4. The photocatalytic properties of compounds 1-4 were investigated using methylene blue (MB) degradation under UV light. All compounds showed good catalytic activity and structural stability. The possible catalytic mechanism was discussed on the basis of active-species trapping experiments. The different photocatalytic activities of compounds 1-4 were explained by comparison of the band gaps of different POM species and different packing modes of POM units in these hybrid compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Design, synthesis and excellent third-order NLO properties of two new polyoxometalates constructed from Keggin polyanions bonded by a solvent molecule.

    PubMed

    Miao, Hao; Dong, Yayu; Chen, Ziwang; He, Xingxiang; Hu, Gonghao; Xu, Yan

    2016-08-09

    Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)](5-), while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively.

  20. Energetics of Al₁₃ Keggin cluster compounds.

    PubMed

    Armstrong, Christopher R; Casey, William H; Navrotsky, Alexandra

    2011-09-06

    The ε-Al(13) Keggin aluminum hydroxide clusters are essential models in establishing molecular pathways for geochemical reactions. Enthalpies of formation are reported for two salts of aluminum centered ε-Keggin clusters, Al(13) selenate, (Na(AlO(4))Al(12)(OH)(24)(SeO(4))(4)•12H(2)O) and Al(13) sulfate, (NaAlO(4)Al(12)(OH)(24)(SO(4))(4)•12H(2)O). The measured enthalpies of solution, ΔH(sol), at 28 °C in 5 N HCl for the ε-Al(13) selenate and sulfate are -924.57 (± 3.83) and -944.30 ( ± 5.66) kJ·mol(-1), respectively. The enthalpies of formation from the elements, ΔH(f,el), for Al(13) selenate and sulfate are -19,656.35 ( ± 67.30) kJ·mol(-1), and -20,892.39 ( ± 70.01) kJ·mol(-1), respectively. In addition, ΔH(f,el) for sodium selenate decahydrate was calculated using data from high temperature oxide melt solution calorimetry measurements: -4,006.39 ( ± 11.91) kJ·mol(-1). The formation of both ε-Al(13) Keggin cluster compounds is exothermic from oxide-based components but energetically unfavorable with respect to a gibbsite-based assemblage. To understand the relative affinity of the ε-Keggin clusters for selenate and sulfate, the enthalpy associated with two S-Se exchange reactions was calculated. In the solid state, selenium is favored in the Al(13) compound relative to the binary chalcogenate, while in 5 N HCl, sulfur is energetically favored in the cluster compound compared to the aqueous solution. This contribution represents the first thermodynamic study of ε-Al(13) cluster compounds and establishes a method for other such molecules, including the substituted versions that have been created for kinetic studies. Underscoring the importance of ε-Al(13) clusters in natural and anthropogenic systems, these data provide conclusive thermodynamic evidence that the Al(13) Keggin cluster is a crucial intermediate species in the formation pathway from aqueous aluminum monomers to aluminum hydroxide precipitates.

  1. Hydrolysis of the RNA model substrate catalyzed by a binuclear Zr(IV)-substituted Keggin polyoxometalate.

    PubMed

    Luong, Thi Kim Nga; Absillis, Gregory; Shestakova, Pavletta; Parac-Vogt, Tatjana N

    2015-09-21

    The reactivity and solution behaviour of the binuclear Zr(IV)-substituted Keggin polyoxometalate (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]·7H2O (ZrK 2 : 2) towards phosphoester bond hydrolysis of the RNA model substrate 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP) was investigated at different reaction conditions (pD, temperature, concentration, and ionic strength). The hydrolysis of the phosphoester bond of HPNP, followed by means of (1)H NMR spectroscopy, proceeded with an observed rate constant, kobs = 11.5(±0.42) × 10(-5) s(-1) at pD 6.4 and 50 °C, representing a 530-fold rate enhancement in comparison with the spontaneous hydrolysis of HPNP. (1)H and (31)P NMR spectra indicate that at these reaction conditions the only products of hydrolysis are p-nitrophenol and the corresponding cyclic phosphate ester. The pD dependence of kobs exhibits a bell-shaped profile, with the fastest rate observed at pD 6.4. The formation constant (Kf = 455 M(-1)) and catalytic rate constant (kc = 42 × 10(-5) s(-1)) for the HPNP-ZrK 2 : 2 complex, activation energy (Ea) of 63.35 ± 1.82 kJ mol(-1), enthalpy of activation (ΔH(‡)) of 60.60 ± 2.09 kJ mol(-1), entropy of activation (ΔS(‡)) of -133.70 ± 6.13 J mol(-1) K(-1), and Gibbs activation energy (ΔG(‡)) of 102.05 ± 0.13 kJ mol(-1) at 37 °C were calculated from kinetic experiments. Binding between ZrK 2 : 2 and the P-O bond of HPNP was evidenced by the change in the (31)P chemical shift and signal line-broadening of the (31)P atom in HPNP upon addition of ZrK 2 : 2. Based on (31)P NMR experiments and isotope effect studies, a mechanism for HPNP hydrolysis in the presence of ZrK 2 : 2 was proposed.

  2. Synthesis, characterization, and reactivity of Ti(IV)-monosubstituted Keggin polyoxometalates.

    PubMed

    Kholdeeva, Oxana A; Trubitsina, Tatiana A; Maksimov, Gennadii M; Golovin, Anatolii V; Maksimovskaya, Raisa I

    2005-03-07

    Ti(IV)-monosubstituted Keggin-type polyoxometalates (Ti-POMs), mu-oxo dimer [Bu4N]8[(PTiW11O39)2O] (1), and three monomers [Bu4N]4[PTi(L)W11O39], where L = OH (2), OMe (3), and OAr (4, ArOH = 2,3,6-trimethylphenol (TMP)), have been prepared starting from mu-hydroxo dimer [Bu4N]7[(PTiW11O39)2OH] (5) or heteropolyacid H5PW11TiO40 or both. The compounds have been characterized by elemental analysis, IR, UV-vis, and multinuclear (31P, 1H, 183W) NMR. The interaction of 1 and 3-5 with H2O in MeCN produces 2. The hydrolysis constants, estimated from 31P and 1H NMR data, are 0.006 and 0.04 for 1 and 3, respectively. Studies by 31P NMR, IR, potentiometric titration, and cyclic voltammetry revealed that 1-3 and 5 afford the same protonated titanium peroxo complex [Bu4N]4[HPTi(O2)W11O39] (I) upon interaction with aqueous H2O2 in MeCN. The rates of formation of I correlate with the rates of hydrolysis of the Ti-POMs and follow the order of 5 > 1 > 3. A two-step mechanism of the reaction of Ti-POMs with H2O2, which involves hydrolysis of the Ti-L bonds to yield 2 followed by fast interaction of 2 with hydrogen peroxide producing I, is suggested. The equilibrium constant for the reaction of 2 with H2O2 to yield I and H2O, estimated using 31P NMR, is 10. The interaction of the Ti-POMs with TMP follows the trends similar to their interaction with H2O) and requires preliminary hydrolysis of the Ti-L bonds. All of the Ti-POMs catalyze the oxidation of TMP with H2O2 in MeCN to give 2,3,5-trimethyl-p-benzoquinone and 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol. The product distribution is similar for all of the Ti-POMs. The catalytic activities of the Ti-POMs correlate with the rates of formation of I and follow the order of 2 > 5 > 1 > 3. The findings lay a basis for a better understanding of the nature of the reactivity of titanium in Ti-catalyzed oxidations.

  3. One-dimensional polyoxometalate polymer constructed from V-W cluster by using asymmetrical bipyridine ligand

    NASA Astrophysics Data System (ADS)

    Han, Zhangang; Chai, Tao; Zhai, Xueliang; Wang, Jiye; Hu, Changwen

    2009-11-01

    The asymmetrical organic molecule 2,4'-bipyridine (bpy) is explored to assemble polyoxometalate into a one-dimensional hybrid and compound [Cu I(bpy) 2] 3[Cu I3(bpy) 4][V VW VI9W V3O 40] ( 1) is achieved. Compound 1 represents a V-centered Keggin [V VW VI9W V3O 40] 6- cluster bonded together by incorporating secondary metal coordination group of Cu-bpy. The thermogravimetric analysis of 1 has also been researched.

  4. Syntheses, structures, properties and DFT study of hybrid inorganic-organic architectures constructed from trinuclear lanthanide frameworks and Keggin-type polyoxometalates.

    PubMed

    Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein; Lotfian, Nahid; Salimi, Alireza; Bauzá, Antonio; Van Deun, Rik; Decadt, Roel; Barceló-Oliver, Miquel; Frontera, Antonio

    2014-01-28

    In this paper we report the synthesis and X-ray characterization of four novel hybrid inorganic-organic assemblies generated from H4SiW12O40 as Keggin-type polyoxometalates (POM) and, in three of them, a trinuclear lanthanide cluster of type {Na(H2O)3[Ln(HCAM)(H2O)3]3}(4+) is formed, where Ln metal is La in compound 1, Ce in compound 2, and Eu in compound 3 (H3CAM = chelidamic acid or 2,6-dicarboxy-4-hydroxypyridine). These compounds represent the first POM-based inorganic-organic assemblies using chelidamic acid as an organic ligand. The thermal stability of the organic ligand is crucial, since pyridine-2,6-bis(monothiocarboxylate) instead of chelidamic acid is used (compound 4) under the same synthesis conditions, the decomposition of the ligand to pyridine was observed leading to the formation of colorless crystals of a pseudo hybrid inorganic-organic assembly. In compound 4 the hybrid inorganic-organic assembly is not formed and the organic part simply consists of four molecules of protonated pyridine acting as counterions of the [SiW12O40](4-) counterpart. The luminescent properties of compounds and have been investigated and their solid state architectures have been analyzed. Whereas compound only shows ligand emission, the Eu(3+) emission in compound 3 is discussed in detail. We have found that unprecedented anion-π interactions between the POM, which is a tetra-anion, and the aromatic rings play a crucial role in the crystal packing formation. To the best of our knowledge, this is the first report that describes and analyzes this interaction in Keggin-type POM based inorganic-organic frameworks. The energetic features of these interactions in the solid state have been analyzed using DFT calculations in some model systems predicted by us.

  5. Structural Characterization of the Complex between Hen Egg-White Lysozyme and Zr(IV) -Substituted Keggin Polyoxometalate as Artificial Protease.

    PubMed

    Sap, Annelies; De Zitter, Elke; Van Meervelt, Luc; Parac-Vogt, Tatjana N

    2015-08-10

    Successful co-crystallization of a noncovalent complex between hen egg-white lysozyme (HEWL) and the monomeric Zr(IV) -substituted Keggin polyoxometalate (POM) (Zr1 K1), (Et2 NH2)3 [Zr(PW11 O39)] (1), has been achieved, and its single-crystal X-ray structure has been determined. The dimeric Zr(IV) -substituted Keggin-type polyoxometalate (Zr1 K2), (Et2 NH2)10 [Zr(PW11 O39 )2] (2), has been previously shown to exhibit remarkable selectivity towards HEWL hydrolysis. The reported X-ray structure shows that the hydrolytically active Zr(IV) -substituted Keggin POM exists as a monomeric species. Prior to hydrolysis, this monomer interacts with HEWL in the vicinity of the previously identified cleavage sites found at Trp28-Val29 and Asn44-Arg45, through water-mediated H-bonding and electrostatic interactions. Three binding sites are observed at the interface of the negatively charged Keggin POM and the positively charged regions of HEWL at: 1) Gly16, Tyr20, and Arg21; 2) Asn44, Arg45, and Asn46; and 3) Arg128. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electron transfer from alpha-keggin anions to dioxygen

    Treesearch

    Yurii V. Geletii; Rajai H. Atalla; Craig L. Hill; Ira A. Weinstock

    2004-01-01

    Polyoxometalates (POMs), of which alpha-Keggin anions are representative, are a diverse and rapidly growing class of water-soluble cluster-anion structures with applications ranging from molecular catalysis to materials. [1] POMs are inexpensive, minimally or non-toxic, negatively charged clusters comprised of early transition-metals, usually in their do electronic...

  7. Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: Transition metal substituted effects

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Guang; Zheng, Ting; Liu, Shuang; Zhang, Han-Yu

    2016-04-01

    In the present paper, Keggin-type polyoxometalates (POMs) (NH4)3[PW12O40] and its mono-transition-metal-substituted species (NH4)5[{PW11O39}MII(H2O)] (M = Mn, Fe, Co, Ni, Cu, Zn) have been synthesized and used as photocatalyst to activate O2 for the degradation of dye molecule under visible-light irradiation. Because of the strong adsorption on the surface of POM catalyst, malachite green (MG) molecule was employed as a molecular probe to test their photocatalytic activity. The photodegradation study shows that introduction of transition metal ion leads to an increase in the degradation of MG in the following order: Mn < Fe < Co < [PW12O40]3- < Ni < Cu < Zn, which indicates that the photocatalytic activity of these POMs is sensitive to the transition metal substituted effects. Electronic structure analysis based on the density functional theory calculations shows that a moderate decrease of oxidizing ability of POM catalyst may improve the photocatalytic activity in the degradation of dye molecule under visible-light irradiation. Meanwhile, intermediate products about the photocatalytic oxidation of MG molecule were proposed on the basis of gas chromatograph mass spectrometer analysis.

  8. Photocatalytic property of a keggin-type polyoxometalates-containing bilayer system for degradation organic dye model.

    PubMed

    Li, Taohai; Gao, Shuiying; Li, Feng; Cao, Rong

    2009-10-15

    The photocatalytic activity composite films incorporating the Keggin-type polyoxometalates (POM) K6CoW12O40.-16H2O and K3PW12O40.-nH2O (MW12 (M=P, Co)) and [Cu(II)(1,8-dimethyl-1, 3, 6, 8, 10, 13-hexaazacycloteradecane)](2+)(L) have been prepared by the layer-by-layer (LbL) self-assembly method. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. Atomic force microscopy (AFM) images of the L/MW12 composite films indicate that the film surface is relatively uniform and smooth. In addition, the films show high photocatalytic activity to the degradation of organic dye model (methyl orange (MO)), attributed to the formation of an O-->W charge-transfer excited state at W-O-W bridge bond, resulting in generating highly reactive holes and electrons; The photocatalytic efficiency of the films have little change after several times of photocatalytic cycle, indicating that the composite films are stable, reused and recovered.

  9. Intercluster compound between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a keggin polyoxometalate (POM): formation during the course of carboxylate elimination of a monomeric triphenylphosphinegold(I) carboxylate in the presence of POMs.

    PubMed

    Nomiya, Kenji; Yoshida, Takuya; Sakai, Yoshitaka; Nanba, Arisa; Tsuruta, Shinichiro

    2010-09-20

    The preparation and structural characterization of a novel intercluster compound, [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PW(12)O(40)](2)·4EtOH (1), constructed between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a saturated α-Keggin polyoxometalate (POM) are described. The tetragold(I) cluster oxonium cation was formed during the course of carboxylate elimination of a monomeric phosphinegold(I) carboxylate complex, i.e., [Au((R,S)-pyrrld)(PPh(3))] [(R,S)-Hpyrrld = (R,S)-2-pyrrolidone-5-carboxylic acid], in the presence of the free acid form of a Keggin POM, H(3)[α-PW(12)O(40)]·7H(2)O. The liquid-liquid diffusion between the upper water/EtOH phase containing the Keggin POM and the lower CH(2)Cl(2) phase containing the monomeric gold(I) complex gave a pure crystalline sample of 1 in good yield (42.1%, 0.242 g scale). Complex 1 was formed by ionic interaction between the tetragold(I) cluster cation and the Keggin POM anion. As a matter of fact, the POM anion in 1 can be exchanged with the BF(4)(-) anion using an anion-exchange resin (Amberlyst A-27) in BF(4)(-) form. By using other Keggin POMs, such as H(4)[α-SiW(12)O(40)]·10H(2)O and H(3)[α-PMo(12)O(40)]·14H(2)O, the same tetragold(I) cluster cation was also formed, i.e., in the forms of [{Au(PPh(3))}(4)(μ(4)-O)](2)[α-SiW(12)O(40)]·2H(2)O (2) and [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PMo(12)O(40)](2)·3EtOH (3). Compounds 1-3, as dimethyl sulfoxide-soluble, EtOH- and Et(2)O-insoluble dark-yellowish white solids, were characterized by complete elemental analysis, thermogravimetric and differential thermal analyses, Fourier transform IR, X-ray crystallography, and solid-state (CPMAS (31)P and (29)Si) and solution ((31)P{(1)H} and (1)H) NMR spectroscopy. The molecular structures of 1 and 2 were successfully determined. The tetragold(I) cluster cation was composed of four PPh(3)Au(I) units bridged by a central μ(4)-oxygen atom in the geometry of a trigonal pyramid or distorted tetrahedron.

  10. Copper benzene tricarboxylate metal-organic framework with wide permanent mesopores stabilized by Keggin polyoxometallate ions.

    PubMed

    Wee, Lik H; Wiktor, Christian; Turner, Stuart; Vanderlinden, Willem; Janssens, Nikki; Bajpe, Sneha R; Houthoofd, Kristof; Van Tendeloo, Gustaaf; De Feyter, Steven; Kirschhock, Christine E A; Martens, Johan A

    2012-07-04

    Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal-organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu(3)(BTC)(2) (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores.

  11. Effect of the Keggin anions on assembly of CuI-bis(tetrazole) thioether complexes containing multinuclear CuI-cluster

    NASA Astrophysics Data System (ADS)

    Wang, Xiu-Li; Gao, Qiang; Tian, Ai-Xiang; Hu, Hai-Liang; Liu, Guo-Cheng

    2012-03-01

    In order to investigate the effect of polyoxometalate (POM) on the assembly of transition metal-bis(tetrazole) thioether complexes, three new complexes based on different Keggin anions and multinuclear CuI-cluster [CuI12(bmtr)9(HSiMo12O40)4] (1), [CuI3(bmtr)3(PM12O40)] (M=W for 2; Mo for 3) (bmtr=1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, two kinds of nanometer-scale tetranuclear subunits linked by [SiMo12O40]4- polyanions assemble a (3, 4)-connected three-dimensional (3D) self-penetrating framework. Compounds 2 and 3 are isostructural, exhibiting a 1D chain with [PW12O40]3-/[PMo12O40]3- polyanions and trinuclear clusters arranging alternately. The distinct structural differences between these POM-based CuI-bmtr complexes of 1 and 2/3 maybe rest on the contrast of Keggin-type polyoxometalate with different central heteroatoms, which have been discussed in detail. In addition, the electrochemical properties of the title complexes have been investigated.

  12. Amide bond hydrolysis in peptides and cyclic peptides catalyzed by a dimeric Zr(IV)-substituted Keggin type polyoxometalate.

    PubMed

    Ly, Hong Giang T; Absillis, Gregory; Parac-Vogt, Tatjana N

    2013-08-14

    Detailed kinetic studies on the hydrolysis of glycylserine (Gly-Ser) and glycylglycine (Gly-Gly) in the presence of the dimeric zirconium(IV)-substituted Keggin type polyoxometalate (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]·7H2O (1) were performed by a combination of (1)H, (13)C and (31)P NMR spectroscopy. The observed rate constants for the hydrolysis of Gly-Ser and Gly-Gly at pD 5.4 and 60 °C were 63.3 × 10(-7) s(-1) and 4.44 × 10(-7) s(-1) respectively, representing a significant acceleration as compared to the uncatalyzed reactions. The pD dependence of the rate constant for both reactions exhibited a bell-shaped profile with the fastest hydrolysis observed in the pD range of 5.5-6.0. Interaction of 1 with Gly-Ser and Gly-Gly via their amine nitrogen and amide oxygen was proven by (13)C NMR spectroscopy. The effective hydrolysis of Gly-Ser in the presence of 1 is most likely a combination of the polarization of the amide oxygen due to its binding to the Zr(IV) ion in 1 and the intramolecular attack of the Ser hydroxyl group on the amide carbonyl carbon. The effect of temperature, inhibitors, and ionic strength on the hydrolysis rate constant was also examined. The solution structure of 1 was investigated by means of (31)P NMR spectroscopy, revealing that its stability is highly dependent on pH, concentration and temperature. A 2.0 mM solution of 1 was found to be fully stable under hydrolytic conditions (pD 5.4 and 60 °C) both in the presence and in the absence of the dipeptides.

  13. In operando X-ray absorption fine structure studies of polyoxometalate molecular cluster batteries: polyoxometalates as electron sponges.

    PubMed

    Wang, Heng; Hamanaka, Shun; Nishimoto, Yoshio; Irle, Stephan; Yokoyama, Toshihiko; Yoshikawa, Hirofumi; Awaga, Kunio

    2012-03-14

    We carried out in operando Mo K-edge X-ray absorption fine structure measurements on the rechargeable molecular cluster batteries (MCBs) of polyoxometalates (POMs), in which a Keggin-type POM, [PMo(12)O(40)](3-), is utilized as a cathode active material with a lithium metal anode. The POM-MCBs exhibit a large capacity of ca. 270 (A h)/kg in a voltage range between V = 4.0 V and V = 1.5 V. X-ray absorption near-edge structure analyses demonstrate that all 12 Mo(6+) ions in [PMo(12)O(40)](3-) are reduced to Mo(4+) in the discharging process. This means the formation of a super-reduced state of the POM, namely, [PMo(12)O(40)](27-), which stores 24 electrons, and this electron number can explain the large capacity of the POM-MCBs. Furthermore, extended X-ray absorption fine structure analyses reveal the molecular structure of [PMo(12)O(40)](27-), which is slightly reduced in size compared to the original [PMo(12)O(40)](3-) and involves Mo(4+) metal-metal-bonded triangles. Density functional theory calculations suggest that these triangles are formed because of the large number of additional electrons in the super-reduced state.

  14. Effect of the Keggin anions on assembly of Cu{sup I}-bis(tetrazole) thioether complexes containing multinuclear Cu{sup I}-cluster

    SciTech Connect

    Wang Xiuli; Gao Qiang; Tian Aixiang; Hu Hailiang; Liu Guocheng

    2012-03-15

    In order to investigate the effect of polyoxometalate (POM) on the assembly of transition metal-bis(tetrazole) thioether complexes, three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster [Cu{sup I}{sub 12}(bmtr){sub 9}(HSiMo{sub 12}O{sub 40}){sub 4}] (1), [Cu{sup I}{sub 3}(bmtr){sub 3}(PM{sub 12}O{sub 40})] (M=W for 2; Mo for 3) (bmtr=1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, two kinds of nanometer-scale tetranuclear subunits linked by [SiMo{sub 12}O{sub 40}]{sup 4-} polyanions assemble a (3, 4)-connected three-dimensional (3D) self-penetrating framework. Compounds 2 and 3 are isostructural, exhibiting a 1D chain with [PW{sub 12}O{sub 40}]{sup 3-}/[PMo{sub 12}O{sub 40}]{sup 3-} polyanions and trinuclear clusters arranging alternately. The distinct structural differences between these POM-based Cu{sup I}-bmtr complexes of 1 and 2/3 maybe rest on the contrast of Keggin-type polyoxometalate with different central heteroatoms, which have been discussed in detail. In addition, the electrochemical properties of the title complexes have been investigated. - Graphical abstract: Three new complexes based on different Keggin anions and multinuclear Cu{sup I}-cluster have been synthesized under hydrothermal conditions. The Keggin polyanions with different central heteroatoms play a key role. Highlights: Black-Right-Pointing-Pointer The flexible bis(tetrazole)-based thioether ligand with some advantages have been used. Black-Right-Pointing-Pointer The effect of Keggin anions with different central heteroatoms has been discussed in detail. Black-Right-Pointing-Pointer The electrochemical behaviors and electrocatalysis property have been investigated.

  15. Copper based metal-organic molecular ring with inserted Keggin-type polyoxometalate: a stable photofunctional host-guest molecular system.

    PubMed

    Fu, Zhiyong; Zeng, Yu; Liu, Xiaoling; Song, Desheng; Liao, Shijun; Dai, Jingcao

    2012-06-21

    Keggin polyphosphotungstate cluster was captured by a porous molecular ring with light sensitizing TPT molecules as connectors and copper ions as nodes. The self-assembly reaction gives a stable host-guest supramolecular system, demonstrating efficient heterogeneous photocatalytic behavior for the degradation of methyl orange in near-neutral conditions.

  16. Sizing and Discovery of Nanosized Polyoxometalate Clusters by Mass Spectrometry

    PubMed Central

    2016-01-01

    Ion mobility-mass spectrometry (IM-MS) is a powerful technique for structural characterization, e.g., sizing and conformation, particularly when combined with quantitative modeling and comparison to theoretical values. Traveling wave IM-MS (TW-IM-MS) has recently become commercially available to nonspecialist groups and has been exploited in the structural study of large biomolecules, however reliable calibrants for large anions have not been available. Polyoxometalate (POM) species—nanoscale inorganic anions—share many of the facets of large biomolecules, however, the full potential of IM-MS in their study has yet to be realized due to a lack of suitable calibration data or validated theoretical models. Herein we address these limitations by reporting DT-IM (drift tube) data for a set of POM clusters {M12} Keggin 1, {M18} Dawson 2, and two {M7} Anderson derivatives 3 and 4 which demonstrate their use as a TW-IM-MS calibrant set to facilitate characterization of very large (ca. 1–4 nm) anionic species. The data was also used to assess the validity of standard techniques to model the collision cross sections of large inorganic anions using the nanoscale family of compounds based upon the {Se2W29} unit including the trimer, {Se8W86O299} A, tetramer, {Se8W116O408} B, and hexamer {Se12W174O612} C, including their relative sizing in solution. Furthermore, using this data set, we demonstrated how IM-MS can be used to conveniently characterize and identify the synthesis of two new, i.e., previously unreported POM species, {P8W116}, unknown D, and {Te8W116}, unknown E, which are not amenable to analysis by other means with the approximate formulation of [H34W118X8M2O416]44–, where X = P and M = Co for D and X = Te and M = Mn for E. This work establishes a new type of inorganic calibrant for IM-MS allowing sizing, structural analysis, and discovery of molecular nanostructures directly from solution. PMID:26906879

  17. Two new organic-inorganic hybrid compounds based on metal-pyrazine coordination polymers and Keggin polyoxometalates: effect of metal ions on thestructure

    NASA Astrophysics Data System (ADS)

    Cui, Feng-Yun; Ma, Xiao-Yu; Li, Cong; Dong, Tao; Gao, Yuan-Zhe; Han, Zhan-Gang; Chi, Ying-Nan; Hu, Chang-Wen

    2010-12-01

    Through changing the metal ions, two Keggin polyoxometalates-based hybrid compounds, [Cu 5(pz) 6(Cl)(SiW 12O 40)] ( 1) and [Ag 4(pz) 3(H 2O) 2(SiW 12O 40)] ( 2) (pz=pyrazine), were hydrothermally synthesized and characterized by an elemental analysis, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. In compound 1, the metal-organic motif exhibits a 6 3 topological 2-D sheet, which is further fused by the [SiW 12O 40] 4- anions to construct a (6·7·8)(6 3·7·8 2)(6 3)(6 5·7)(6 5·8) topological 3D structure. In compound 2, the bridging groups Ag 2(pz) connect the [SiW 12O 40] 4- anions to form a (5 3) 2(5 4·8 2) topological 2-D layer, which is further linked by an [Ag(pz)] nn+ chains to construct a 3D structure with the (3 4·4 16·5 24·6 12·7 8·8 2)(3 4·4 6·5 4·6) 2(4·5 2) 2 topology. It represents the highest connected network topology presently known for the polyoxometalates system. The structure differences of compounds 1 and 2 reveal that the coordination numbers and geometries of the metal ions have a great influence on the final structure and topology of the Keggin POMs-based hybrid compounds. In addition, the electrochemistry properties of the two compounds have been studied.

  18. Zeolitic polyoxometalates metal organic frameworks (Z-POMOF) with imidazole ligands and epsilon-Keggin ions as building blocks; computational evaluation of hypothetical polymorphs and a synthesis approach.

    PubMed

    Rodriguez Albelo, L Marleny; Ruiz-Salvador, A Rabdel; Lewis, Dewi W; Gómez, Ariel; Mialane, Pierre; Marrot, Jérome; Dolbecq, Anne; Sampieri, Alvaro; Mellot-Draznieks, Caroline

    2010-08-14

    We investigate here a new family of zeolitic Metal Organic Frameworks (MOFs) based on imidazole (im) as the ligand and epsilon-type Keggin PolyOxoMetalates (POMs) as building units. The POM used in this study is the epsilon-{PMo(12)O(40)} Keggin isomer capped by four Zn(ii) ions (noted epsilon-Zn) in tetrahedral coordination. We describe here our methods to first construct and then evaluate the stability of hypothetical 3-D POMOFs possessing a tetrahedral network, typified by dense silica polymorphs and zeotypes and referred here to as Z-POMOFs. We use the analogy between the connectivity of silicon ion in dense minerals or zeolites and the epsilon-Zn, using imidazolate ligands to mimic the role of oxygen atoms in zeolites. Handling the epsilon-Keggin and imidazole as the constitutive building-blocks, a selection of 40 polymorphs were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like and zni-structure were identified as the most stable candidates. In parallel, we have attempted to synthesize Z-POMOF structures with epsilon-Zn POMs, synthesized in situ under hydrothermal conditions, and imidazole ligands. We present our first experimental result, the extended material [NBu(4)][PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)(im)(Him)], named epsilon(im)(2). The structure of the hybrid framework is built by the connection of dimerized epsilon-Zn POMs to imidazole ligands in two directions. The obtaining of the first POMOF based on imidazole ligand is an encouraging step towards the synthesis of a new family of POMOFs.

  19. Two new organic-inorganic hybrid compounds based on metal-pyrazine coordination polymers and Keggin polyoxometalates: effect of metal ions on the structure

    SciTech Connect

    Cui Fengyun; Ma Xiaoyu; Li Cong; Dong Tao; Gao Yuanzhe; Han Zhangang; Chi Yingnan; Hu Changwen

    2010-12-15

    Through changing the metal ions, two Keggin polyoxometalates-based hybrid compounds, [Cu{sub 5}(pz){sub 6}(Cl)(SiW{sub 12}O{sub 40})] (1) and [Ag{sub 4}(pz){sub 3}(H{sub 2}O){sub 2}(SiW{sub 12}O{sub 40})] (2) (pz=pyrazine), were hydrothermally synthesized and characterized by an elemental analysis, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. In compound 1, the metal-organic motif exhibits a 6{sup 3} topological 2-D sheet, which is further fused by the [SiW{sub 12}O{sub 40}]{sup 4-} anions to construct a (6.7.8)(6{sup 3}.7.8{sup 2})(6{sup 3})(6{sup 5}.7)(6{sup 5}.8) topological 3D structure. In compound 2, the bridging groups Ag{sub 2}(pz) connect the [SiW{sub 12}O{sub 40}]{sup 4-} anions to form a (5{sup 3}){sub 2}(5{sup 4}.8{sup 2}) topological 2-D layer, which is further linked by an [Ag(pz)]{sub n}{sup n+} chains to construct a 3D structure with the (3{sup 4}.4{sup 16}.5{sup 24}.6{sup 12}.7{sup 8}.8{sup 2})(3{sup 4}.4{sup 6}.5{sup 4}.6){sub 2}(4.5{sup 2}){sub 2} topology. It represents the highest connected network topology presently known for the polyoxometalates system. The structure differences of compounds 1 and 2 reveal that the coordination numbers and geometries of the metal ions have a great influence on the final structure and topology of the Keggin POMs-based hybrid compounds. In addition, the electrochemistry properties of the two compounds have been studied. -- Graphical Abstract: Two new highly connected Keggin POMs-based hybrids have been synthesized by changing metal ions under hydrothermal conditions and the effect of metal ions on the final structure and topology of the POMs-based hybrid compounds was discussed. Display Omitted

  20. A new Keggin-like niobium-phosphate cluster that reacts reversibly with hydrogen peroxide.

    PubMed

    Son, Jung-Ho; Casey, William H

    2015-08-18

    Polyoxoniobate clusters that are stable in acidic solutions are rare and particularly useful in industrial processes. Here we report a new pentaphosphate niobate polyoxometalate cluster (TMA)9H3Nb9P5O41·28H2O (Nb9P5) that is stable over a wide pH range and that can be converted reversibly into the peroxo form.

  1. Self-assembly of two novel bisupporting Keggin-polyoxometalate derivatives: Hydrothermal synthesis and structure characterization of [Cu(2,2-bpy)][HXMo10VIMo2VO]·2HO (X = P, m = 1; X = Si, m = 2)

    NASA Astrophysics Data System (ADS)

    Chen, Jing; Sha, Jing-quan; Peng, Jun; Shi, Zhen-yu; Dong, Bao-xia; Tian, Ai-xiang

    2007-11-01

    Two novel organic-inorganic hybrid polyoxometalates, [Cu(2,2'-bpy)2]2[XMo]·2HO (X = P, m = 1 1; X = Si, m = 2 2; 2,2'-bpy = 2,2'-bpyridine), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. They are isostructural, possessing orthorhombic, and the parameters of unit cells for compound 1 are space group Pbca, a = 17.317(4) Å, b = 17.092(3) Å, c = 20.587(4) Å, V = 6445(2) Å 3, Z = 4; for compound 2 are space group Pcab, a = 17.181(3) Å, b = 18.198(4) Å, c = 20.672(4) Å, V = 6463(2) Å 3, Z = 4. The two compounds show a layer framework constructed from Keggin-polyoxoanion clusters and [Cu (2, 2'-bpy) 2] 2+ coordination polymer fragments via weak covalent interactions, resulting in a 3D network via supramolecular interactions. Their electrochemical properties are studied in detail.

  2. Preparation and application of multiple-component-doped keggin polyoxometalate microtubes--towards a component-tunable hollow structure.

    PubMed

    Shen, Yan; Peng, Jun; Pang, Haijun; Zhang, Pengpeng; Chen, Dan; Chen, Changyun; Zhang, Huanqiu; Meng, Cuili; Su, Zhongmin

    2011-03-21

    In this paper, the preparation of ascorbic acid (AA)-doped polyoxometalate (SiW(12)-AA) microtubes is described. The SiW(12)-AA microtubes convert to heteropoly blue microtubes upon exposure to ammonia gas, which is an ammonia-triggered solid-solid redox reaction between AA molecules and polyoxometalates, and can possibly be applied to a chemical sensor for detecting ammonia and volatile organic amines. Furthermore, the SiW(12)-AA microtubes have been applied to the in situ synthesis of Ag nanoparticles (NPs) through the redox reaction between the AA component and Ag(+) ions occurring on the surfaces of the SiW(12)-AA microtubes to give silver NPs immobilized on polyoxometalate microtubes (Ag@SiW(12)). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Phosphate Ester Bond Hydrolysis Promoted by Lanthanide-Substituted Keggin-type Polyoxometalates Studied by a Combined Experimental and Density Functional Theory Approach.

    PubMed

    Luong, Thi Kim Nga; Mihaylov, Tzvetan T; Absillis, Gregory; Shestakova, Pavletta; Pierloot, Kristine; Parac-Vogt, Tatjana N

    2016-10-03

    Hydrolytic cleavage of 4-nitrophenyl phosphate (NPP), a commonly used DNA model substrate, was examined in the presence of series of lanthanide-substituted Keggin-type polyoxometalates (POMs) [Me2NH2]11[Ce(III)(PW11O39)2], [Me2NH2]10[Ce(IV)(PW11O39)2] (abbreviated as (Ce(IV)(PW11)2), and K4[EuPW11O39] by means of NMR and luminescence spectroscopies and density functional theory (DFT) calculations. Among the examined complexes, the Ce(IV)-substituted Keggin POM (Ce(IV)(PW11)2) showed the highest reactivity, and its aqueous speciation was fully determined under different conditions of pD, temperature, concentration, and ionic strength by means of (31)P and (31)P diffusion-ordered NMR spectroscopy. The cleavage of the phosphoester bond of NPP in the presence of (Ce(IV)(PW11)2) proceeded with an observed rate constant kobs = (5.31 ± 0.06) × 10(-6) s(-1) at pD 6.4 and 50 °C. The pD dependence of NPP hydrolysis exhibits a bell-shaped profile, with the fastest rate observed at pD 6.4. The formation constant (Kf = 127 M(-1)) and catalytic rate constant (kc = 19.41 × 10(-5) s(-1)) for the NPP-Ce(IV)-Keggin POM complex were calculated, and binding between Ce(IV)(PW11)2 and the phosphate group of NPP was also evidenced by the change of the chemical shift of the (31)P nucleus in NPP upon addition of the POM complex. DFT calculations revealed that binding of NPP to the parent catalyst Ce(IV)(PW11)2 is thermodynamically unlikely. On the contrary, formation of complexes with the monomeric 1:1 species, Ce(IV)PW11, is considered to be more favorable, and the most stable complex, [Ce(IV)PW11(H2O)2(NPP-κO)2](7-), was found to involve two NPP ligands coordinated to the Ce(IV)center of Ce(IV)PW11 in the monodentate fashion. The formation of such species is considered to be responsible for the hydrolytic activity of Ce(IV)(PW11)2 toward phosphomonoesters. On the basis of these findings a principle mechanism for the hydrolysis of NPP by the POM is proposed.

  4. Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

    PubMed

    Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

    2014-06-25

    Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated

  5. Two hybrid compounds constructed from Ni-tris(imidazolyl) complexes and Keggin clusters: Syntheses, structures and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuanfang; Sun, Xiaojun; Ma, Huiyuan; Pang, Haijun; Li, Shaobin; Zhao, Chunyan

    2016-07-01

    By introducing different polyoxotungstates into the Ni-tib (tib = 1, 3, 5-tris (1-imidazolyl)benzene) system, two new polyoxometalate-based inorganic-organic hybrids with distinct architectures, [Ni(Htib)4][PW12O40]2 (1) and [Nitib]2(H2O)4](GeW12O40)·2H2O (2) have been synthesized under the same hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD) patterns and thermogravimetic (TG) analyses. Structural analyses show that compound 1 is a dimer, in which two neighboring mono-connected [PW12O40]3- (PW12) clusters are linked together by a [Ni(Htib)4] complex cation. In contrast to compound 1, compound 2 presents a 2D grid layer formed by bi-connected [GeW12O40]4- (GeW12) clusters and [Ni2(H2O)4(tib)2] complex cations, and the adjacent layers are further linked together by the hydrogen bondings to form a highly opened 3D framework. The distinct structural features of two hybrids suggest that the charge of the Keggin anions should play a key role in the process of assembly. Additionally, the electrochemical properties of compounds 1 and 2 have been investigated, and the results indicated that 1 and 2 have good electrocatalytic activities towards reduction of nitrite and oxidation of ascorbic acid.

  6. Asymmetrically fused polyoxometalate-silver alkynide composite cluster.

    PubMed

    Kurasawa, Mariko; Arisaka, Fumio; Ozeki, Tomoji

    2015-02-16

    We demonstrate that an asymmetric composite cluster, [Ag25{C≡CC(CH3)3}16(CH3CN)4(P2W15Nb3O62)] (1), consisting of directly fused polyoxometalate and silver alkynide moieties can be facilely synthesized by a one-pot reaction between a Nb-substituted Dawson-type polyoxometalate, H4[α-P2W15Nb3O62](5-), and the mixture of (CH3)3CC≡CAg and CF3SO3Ag. Single-crystal X-ray diffraction revealed the structure of 1, where Ag atoms are selectively attached to the Nb-substituted hemisphere of the pedestal Dawson anion. Its structural integrity in the solution was demonstrated by (31)P NMR spectroscopy and analytical ultracentrifugation. The latter method also unveiled the stepwise formation mechanism of 1.

  7. Towards polyoxometalate-cluster-based nano-electronics.

    PubMed

    Vilà-Nadal, Laia; Mitchell, Scott G; Markov, Stanislav; Busche, Christoph; Georgiev, Vihar; Asenov, Asen; Cronin, Leroy

    2013-12-02

    We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom-built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non-volatile molecular memories (NVMM) or flash-RAM. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Design of polystyrene latex particles covered with polyoxometalate clusters via multiple covalent bonding.

    PubMed

    Chen, Xinyue; Li, Hui; Yin, Panchao; Liu, Tianbo

    2015-04-11

    Polyoxometalates (POMs) covalently functionalized with methyl methacrylate groups were applied as surfactants in the emulsion polymerization reaction of styrene. Due to the copolymerization of the methyl methacrylate groups and the styrene monomers, the polyoxometalate clusters are covalently grafted onto the surface of polystyrene latex nanoparticles. Such latex particles are fully covered with catalytic POM clusters and might serve as quasi-homogeneous catalysts.

  9. Binary superlattices from colloidal nanocrystals and giant polyoxometalate clusters.

    PubMed

    Bodnarchuk, Maryna I; Erni, Rolf; Krumeich, Frank; Kovalenko, Maksym V

    2013-04-10

    We report a new kind of long-range ordered binary superlattices comprising atomically defined inorganic clusters and colloidally synthesized nanocrystals. In a model system, we combined surfactant-encapsulated, nearly spherical giant polyoxometalate clusters containing 2.9 nm polyoxomolybdate or 2.5 nm polyoxovanadomolybdate cores with monodisperse colloidal semiconductor nanocrystals (PbS, CdSe, PbS/CdS; 4-11 nm). The results are rationalized on the basis of dense packing principles of sterically stabilized particles with predominantly hard-spherelike interparticle interactions. By varying the size-ratios and relative concentrations of constituents, we obtained known thermodynamically stable binary packings of hard-spheres such as NaCl, AlB2, and NaZn13 lattices and also CaCu5-type lattice and aperiodic quasicrystals with 12-fold symmetry. These results suggest that other kinds of cluster materials such as fullerenes and magic-sized metallic and semiconductor clusters can also be integrated into supramolecular assemblies with nanocrystals. Furthermore, synergistic effects are expected from the combination of redox and catalytic properties of polyoxometalates with excitonic and plasmonic properties of inorganic nanocrystals.

  10. Polyoxometalate-directed assembly of water-soluble AgCl nanocubes.

    PubMed

    Neyman, Alevtina; Wang, Yifeng; Sharet, Shelly; Varsano, Neta; Botar, Bogdan; Kögerler, Paul; Meshi, Louisa; Weinstock, Ira A

    2012-02-21

    "Out-of-pocket" association of Ag(+) to the tetradentate defect site of mono-vacant Keggin and Wells-Dawson polyoxometalate (POM) cluster-anions is used to direct the formation of water-soluble AgCl nanocubes. This journal is © The Royal Society of Chemistry 2012

  11. A new Ni12 cluster based on polyoxometalate ligands.

    PubMed

    Zhang, Hong-Mei; Li, Yang-Guang; Lu, Ying; Clérac, Rodolphe; Zhang, Zhi-Ming; Wu, Qiong; Feng, Xiao-Jia; Wang, En-Bo

    2009-12-07

    A new Ni(12) cluster based on polyoxometalate ligands [Ni(12)(OH)(9)WO(4)(W(7)O(26)(OH))(PW(9)O(34))(3)](25-) (1) has been assembled in aqueous solution containing [PW(9)O(34)](9-), WO(4)(2-), and NiCl(2) x 6 H(2)O. The Ni(12) core in 1 shows a unique three-petal flower-shaped structure composed of three Ni(4) cubane units. Magnetic investigation indicates the presence of dominantly ferromagnetic interactions within the Ni(12) core.

  12. A polyoxometalate-based manganese carboxylate cluster.

    PubMed

    Fang, Xikui; Kögerler, Paul

    2008-08-07

    The functionalization of a pre-formed, high oxidation state {CeIV MnIV 6} cluster with a lacunary phosphotungstate, [alpha-P2 W15 O 56]12-, exemplifies a straightforward route for grafting redox-active building blocks to existing Mn-carboxylate clusters and modeling their deposition onto metal oxide surfaces.

  13. Magnetic excitations in polyoxometalate tetrameric clusters

    NASA Astrophysics Data System (ADS)

    Aebersold, M.; Andres, H. P.; Büttner, H.; Borrás-Almenar, J. J.; Clemente, J. M.; Coronado, E.; Güdel, H. U.; Kearley, D.

    1997-02-01

    The metal-oxide clusters with formula [M 4(D 2O) 2(PW 9O 34) 2] 10- which contain a tetrameric magnetic cluster M 4O 16 provide an ideal series for the study of magnetic exchange interactions in polymetallic molecular clusters. To get a more direct information on the splitting of the spin states caused by the exchange interactions we have performed inelastic neutron scattering measurements on the Co, Mn and Ni clusters. Magnetic excitations have been observed in the range 0.5-6 meV. A tentative interpretation of these data from a Heisenberg exchange Hamiltonian and a single ion zero-field splitting is presented for Ni cluster.

  14. Uranium pyrophosphate / methylenediphosphonate polyoxometalate cage clusters

    SciTech Connect

    Ling, Jie; Qiu, Jie; Sigmon, Ginger E.; Ward, Matt; Szymanowski, Jennifer E.S.; Burns, Peter C

    2010-09-29

    Despite potential applications in advanced nuclear energy systems, nanoscale control of uranium materials is in its infancy. In its hexavalent state, U occurs as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by various ligands to give square, pentagonal, or hexagonal bipyramids. Creation and design of nanostructured uranyl materials requires interruption of the tendency of uranyl bipyramids to share equatorial edges to form infinite sheets that occur in extended structures. Where a bidentate peroxide group bridges uranyl bipyramids, the configuration is inherently bent, fostering formation of cage clusters. Here the bent configurations of four- and five-membered rings of uranyl peroxide hexagonal bipyramids are bridged by pyrophosphate or methylenediphosphonate, creating eight chemically complex cage clusters with specific topologies. Chemical complexity in such clusters provides opportunities for the tuning of cage sizes, pore sizes, and properties such as aqueous solubility. Several of these are topological derivatives of simpler clusters that contain only uranyl bipyramids, whereas others exhibit new topologies.

  15. A polyoxometalate-based manganese carboxylate cluster

    SciTech Connect

    Fang, X.; Kogerler, P.

    2008-01-01

    The functionalization of a pre-formed, high oxidation state {l_brace}Ce{sup IV}Mn{sup IV}{sub 6}{r_brace} cluster with a lacunary phosphotungstate, [{alpha}-P{sub 2}W{sub 15}O{sub 56}]{sup 12-}, exemplifies a straightforward route for grafting redox-active building blocks to existing Mn-carboxylate clusters and modeling their deposition onto metal oxide surfaces.

  16. Two new helical compounds based on Keggin clusters and N-donor multidentate ligand: Syntheses, structures and properties

    SciTech Connect

    Zhou, Shi; Liu, Bo; Li, Xiao-Min; Shi, Tian; Chen, Ya-Guang

    2014-11-15

    Two isostructural polyoxometalate-based inorganic–organic hybrids with 1D helical chain, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2), where L=2,4,5-tri(4-pyridyl)-imidazole have been synthesized under hydrothermal conditions. It is the first time to use the L ligand to synthesis the Keggin-type polyoxometalate-based inorganic–organic hybrids. The two compounds possess the left- and right-handed helical chains and the POMs as pendants attach in the helical chains through Cu–O bonds. The two compounds have been characterized by elemental analyses, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA) and photoluminescent spectroscopy. Moreover, nitrogen adsorption−desorption measurement, electrochemical and photocatalysis properties for degradation of methylene blue (MB) upon a UV irradiation of compound 1 have been examined. - Graphical abstract: Two new compounds, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2) have been synthesized under hydrothermal conditions. The two compounds possess the left- and right-handed helical chains. - Highlights: • The tridentate L ligand is first used to synthesis Keggin-type polyoxometalates. • The two compounds possess the left- and right-handed Cu–L helical chains. • Relationship between surface properties and photocatalytic activity was studied. • Two compounds exhibit photoluminescence of ligand-to-metal charge transfer.

  17. Micropatterned surfaces with covalently grafted unsymmetrical polyoxometalate-hybrid clusters lead to selective cell adhesion.

    PubMed

    Song, Yu-Fei; McMillan, Nicola; Long, De-Liang; Kane, Struan; Malm, Jakob; Riehle, Mathis O; Pradeep, Chullikkattil P; Gadegaard, Nikolaj; Cronin, Leroy

    2009-02-04

    Mn-Anderson based polyoxometalate clusters with different terminal groups have been patterned successfully onto self-assembled monolayer (SAM) using microcontact printing. Studies of the interactions between the designed SAMs and human fibroblast (hTERT-BJ1) cells have been reported, and it was observed that cells attach and spread efficiently for monolayer presenting a terminal aromatic pyrene platform with a polyoxometalate Mn-Anderson cluster as linker, demonstrating the crucial role played by the polyoxometalate metal oxide cluster as an intermediary in cell adhesion to the surface.

  18. Polyoxometalates as a novel class of artificial proteases: selective hydrolysis of lysozyme under physiological pH and temperature promoted by a cerium(IV) Keggin-type polyoxometalate.

    PubMed

    Stroobants, Karen; Moelants, Eva; Ly, Hong Giang T; Proost, Paul; Bartik, Kristin; Parac-Vogt, Tatjana N

    2013-02-18

    Hen-egg-white lysozyme (HEWL) is specifically cleaved at the Trp28-Val29 and Asn44-Arg45 peptide bonds in the presence of a Keggin-type [Ce(α-PW(11)O(39))(2)](10-) polyoxometalate (POM; 1) at pH 7.4 and 37 °C. The reactivity of 1 towards a range of dipeptides was also examined and the calculated reaction rates were comparable to those observed for the hydrolysis of HEWL. Experiments with α-lactalbumin (α-LA), a protein that is structurally highly homologous to HEWL but has a different surface potential, showed no evidence of hydrolysis, which indicates the importance of electrostatic interactions between 1 and the protein surface for the hydrolytic reaction to occur. A combination of spectroscopic techniques was used to reveal the molecular interactions between HEWL and 1 that lead to hydrolysis. NMR spectroscopy titration experiments showed that on protein addition the intensity of the (31)P NMR signal of 1 gradually decreased due to the formation of a large protein/polyoxometalate complex and completely disappeared when the HEWL/1 ratio reached 1:2. Circular dichroism (CD) measurements of HEWL indicate that addition of 1 results in a clear decrease in the signal at λ=208 nm, which is attributed to changes in the α-helical content of the protein. (15)N-(1)H heteronuclear single quantum coherence (HSQC) NMR measurements of HEWL in the presence of 1 reveal that the interaction is mainly observed for residues that are located in close proximity to the first site in the α-helical part of the structure (Trp28-Val29). The less pronounced NMR spectroscopic shifts around the second cleavage site (Asn44-Arg45), which is found in the β-strand region of the protein, might be caused by weaker metal-directed binding, compared with strong POM-directed binding at the first site. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Construction of polyoxometalate-based inorganic-organic compounds using silver(I) double helicates as secondary building blocks.

    PubMed

    Dang, Dongbin; Zheng, Guangshui; Bai, Yan; Yang, Fan; Gao, Hui; Ma, Pengtao; Niu, Jingyang

    2011-09-05

    Two polyoxometalate-based silver(I) compounds including a three-dimensional porous crystalline array and a double-helicate bisupporting cluster were achieved using metal-organic helicates and Keggin [PMo(12)O(40)](3-) as secondary building blocks.

  20. Designed Assembly of Heterometallic Cluster Organic Frameworks Based on Anderson-Type Polyoxometalate Clusters.

    PubMed

    Li, Xin-Xiong; Wang, Yang-Xin; Wang, Rui-Hu; Cui, Cai-Yan; Tian, Chong-Bin; Yang, Guo-Yu

    2016-05-23

    A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Design of polystyrene latex particles covered with polyoxometalate clusters via multiple covalent bonding

    DOE PAGES

    Chen, Xinyue; Li, Hui; Yin, Panchao; ...

    2015-01-01

    In this study, polyoxometalates (POMs) covalently functionalized with methyl methacrylate groups were applied as surfactants in the emulsion polymerization reaction of styrene. Due to the copolymerization of the methyl methacrylate groups and the styrene monomers, the polyoxometalate clusters are covalently grafted onto the surface of polystyrene latex nanoparticles. Finally, such latex particles are fully covered with catalytic POM clusters and might serve as quasi-homogeneous catalysts.

  2. ε-Keggin-based coordination networks: Synthesis, structure and application toward green synthesis of polyoxometalate@graphene hybrids.

    PubMed

    Rodriguez-Albelo, L Marleny; Rousseau, Guillaume; Mialane, Pierre; Marrot, Jérôme; Mellot-Draznieks, Caroline; Ruiz-Salvador, A Rabdel; Li, Shiwen; Liu, Rongji; Zhang, Guangjin; Keita, Bineta; Dolbecq, Anne

    2012-09-07

    Four coordination networks based on the {ε-PMo(V)(8)Mo(VI)(4)O(40)(OH)(4)Zn(4)} Keggin unit (εZn) have been synthesized under hydrothermal conditions. (TBA)(3){PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)}[C(6)H(4)(COO)(2)](2) (ε(isop)(2)) is a 2D material with monomeric εZn units connected via 1,3 benzenedicarboxylate (isop) linkers and tetrabutylammonium (TBA) counter-cations lying between the planes. In (TPA)(3){PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)}[C(6)H(3)(COO)(3)] (TPA[ε(trim)](∞)), 1D inorganic chains formed by the connection of εZn POMs, via Zn-O bonds, are linked via 1,3,5 benzenetricarboxylate (trim) ligands into a 2D compound with tetrapropylammonium (TPA) cations as counter-cations. (TBA){PMo(V)(8)Mo(VI)(4)O(40)Zn(4)}(C(7)H(4)N(2))(2)(C(7)H(5)N(2))(2)·12H(2)O (ε(bim)(4)) is a molecular material with monomeric εZn POMs bound to terminal benzimidazole (bim) ligands. Finally, (TBA)(C(10)H(10)N(4))(2)(HPO(3)){PMo(V)(8)Mo(VI)(4)O(40)Zn(4)}(2)(C(10)H(9)N(4))(3)(C(10)H(8)N(4)) (ε(2)(pazo)(4)) is a 1D compound with dimeric (εZn)(2) POMs connected by HPO(3)(2-) ions and terminal para-azobipyridine (pazo) ligands. In this compound an unusual bond cleavage of the central N[double bond, length as m-dash]N bond of the pazo ligand is observed. We report also a green chemistry-type one-step synthesis method carried out in water at room temperature using ε(2)(pazo)(4) and ε(isop)(2) as reducing agent of graphite oxide (GO) to obtain graphene (G). The POM@G hybrids were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, powder X-ray diffraction, energy dispersive X-ray analysis, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and cyclic voltammetry.

  3. Microwave-assisted hydrolysis of polysaccharides over polyoxometalate clusters.

    PubMed

    Tsubaki, Shuntaro; Oono, Kiriyo; Ueda, Tadaharu; Onda, Ayumu; Yanagisawa, Kazumichi; Mitani, Tomohiko; Azuma, Jun-ichi

    2013-09-01

    Polyoxometalate (POM) clusters were utilized as recyclable acid catalysts and microwave-absorbing agents for the microwave-assisted hydrolysis of corn starch and crystalline cellulose. Phosphotungstic (PW) and silicotungstic (SiW) acids showed high hydrolyzing activity, while phosphomolybdic acid (PMo) showed lower glucose stability. The PW catalyst could be recycled by ether extraction at least 4 times without changing its catalytic activity. The addition of PW could reduce the energy demand required for running the hydrolysis by 17-23%. The dielectric property of the aqueous PW solution was important for increasing the microwave-absorption capability of the reaction system and reducing the energy consumption. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Anion-Dependent Assembly of Heterometallic 3d-4f Clusters Based on a Lacunary Polyoxometalate.

    PubMed

    Cai, Jing; Zheng, Xiu-Ying; Xie, Jing; Yan, Zhi-Hao; Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Lan-Sun

    2017-07-17

    A series of heterometallic 3d-4f clusters, formulated as Na17[Ln3(H2O)5Ni(II)(H2O)3(Sb4O4)(SbW9O33)3(Ni(II)W6O24)(WO2)3(CH3COO)]·(H2O)65 [abbreviated as Ln3Ni2, where Ln = La(3+) (1), Pr(3+) (2), and Nd(3+) (3)], K5Na11[Ln3(H2O)3Ni(II)3(H2O)6(SbW9O33)3(WO4)(CO3)]·(H2O)40 [abbreviated as Ln3Ni3, where Ln = La(3+) (4), Pr(3+) (5), and Nd(3+) (6)], and K3Na27[Ln3Ni(II)9(μ3-OH)9(SbW9O33)2(PW9O34)3(CH3COO)3]·(H2O)80 [abbreviated as Ln3Ni9, where Ln = Dy(3+) (7) and Er(3+) (8)], were obtained through the reaction of the lacunary {SbW9O33} precursor with Ln(NO3)3·6H2O and NiCl2·6H2O in a NaAc/HAc buffer in the presence of different anions. Single-crystal X-ray structure analysis revealed that compounds 1-3 possessed tetrameric architectures featuring three Keggin-type {SbW9O33} and one Anderson-type {Ni(II)W6O24} building blocks encapsulating one {Sb4O4} cluster, three WO2 units, three Ln(3+) metal ions, and two Ni(2+) metal ions. Compounds 4-6 displayed cyclic trimeric aggregates of three {SbW9O33} units enveloping one CO3(2-)-templated trinuclear [Ln3(CO3)](7+) and one WO4(2-)-templated [Ni(II)3(WO4)](+) unit. Compounds 7 and 8 exhibited unique pentameric architectures that featured three 3d-4f cubane clusters of {LnNi3(μ3-OH)3} capped by two {SbW9O33} and three {PW9O34} building blocks. Interestingly, the structural regulation of the heterometallic 3d-4f clusters in the polyoxometalate systems with trimers, tetramers, and pentamers was realized by introducing different anions.

  5. Two new helical compounds based on Keggin clusters and N-donor multidentate ligand: Syntheses, structures and properties

    NASA Astrophysics Data System (ADS)

    Zhou, Shi; Liu, Bo; Li, Xiao-Min; Shi, Tian; Chen, Ya-Guang

    2014-11-01

    Two isostructural polyoxometalate-based inorganic-organic hybrids with 1D helical chain, [CuH3L2(GeMo12O40)]·2H2O (1) and [CuH3L2(SiMo12O40)]·2H2O (2), where L=2,4,5-tri(4-pyridyl)-imidazole have been synthesized under hydrothermal conditions. It is the first time to use the L ligand to synthesis the Keggin-type polyoxometalate-based inorganic-organic hybrids. The two compounds possess the left- and right-handed helical chains and the POMs as pendants attach in the helical chains through Cu-O bonds. The two compounds have been characterized by elemental analyses, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA) and photoluminescent spectroscopy. Moreover, nitrogen adsorption-desorption measurement, electrochemical and photocatalysis properties for degradation of methylene blue (MB) upon a UV irradiation of compound 1 have been examined.

  6. Hydrothermal synthesis and crystal structural characterization of two new modified polyoxometalates constructed of positive and negative metal oxo cluster ions

    NASA Astrophysics Data System (ADS)

    Sun, Ying-Hua; Xu, Ji-Qing; Ye, Ling; Cui, Xiao-Bing; Li, Yong; Yu, Hai-Hui; Li, Guang-Hua; Yang, Guang-Di; Chen, Yan

    2005-04-01

    Two new interesting polyoxometalate derivatives {[HO]2[Mo3VMo5VIV8IVO(PO)]}{[O]2[Mo3VMo5VIV8IVO(PO)]}·5HO1 and {[HO]4[Mo4VMo4VIV8IVO(PO)]}{[HO]2[Mo3VMo5VIV8IVO(PO)]}(HO)·4HO2 constructed of modified metal-oxo cluster ions carrying positive and negative changes, respectively, was hydrothermally prepared and structurally characterized by IR, ESR, XPS, elemental analysis and X-ray crystallography. The result of structure determination shows that compound 1 and 2 are isostructural and both contain polyoxocation and polyoxoanion, and both cation and anion are built on mixed Mo-V tetra-capped pseudo-Keggin units with P centre, [Mo 8V 8O 40(PO 4)] n- , bonded to four or two [Ni(2,2'-bipy) 2H 2O] 2+ complexes, respectively, via terminal oxygen of the capping V atoms. Magnetism measurement indicates that there exists antiferromagnetic interaction in complex 1 and 2.

  7. Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow-fiber micro-solid-phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design.

    PubMed

    Naddaf, Ezzat; Ebrahimi, Mahmoud; Es'haghi, Zarrin; Bamoharram, Fatemeh Farrash

    2015-07-01

    A sensitive technique to determinate naproxen in hair samples was developed using hollow-fiber micro-solid-phase combined with fluorescence spectrophotometry. The incorporation of multi-walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol-gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow-fiber micro-solid-phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4(6) ) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2-10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103-95%. The relative standard deviation for fiber-to-fiber repeatability was 3.9%.

  8. First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands

    SciTech Connect

    Wang Lamei; Fan Yong; Wang Yan; Xiao Lina; Hu Yangyang; Peng Yu; Wang Tiegang; Gao Zhongmin; Zheng Dafang; Cui Xiaobing; Xu Jiqing

    2012-07-15

    Two new organic-inorganic compounds based on polyoxometalates, metal halide clusters and organic ligands: [BW{sub 12}O{sub 40}]{sub 2}[Cu{sub 2}(Phen){sub 4}Cl](H{sub 2}4, 4 Prime -bpy){sub 4}{center_dot}H{sub 3}O{center_dot}5H{sub 2}O (1) and [HPW{sub 12}O{sub 40}][Cd{sub 2}(Phen){sub 4}Cl{sub 2}](4, 4 Prime -bpy) (2) (Phen=1, 10-phenanthroline, bpy=bipyridine), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 is constructed from [BW{sub 12}O{sub 40}]{sup 5-}, metal halide clusters [Cu{sub 2}(Phen){sub 4}Cl]{sup +}and 4, 4 Prime -bpy ligands, while compound 2 is constructed from [PW{sub 12}O{sub 40}]{sup 3-}, metal halide cluster [Cd{sub 2}(Phen){sub 4}Cl{sub 2}]{sup 2+} and 4, 4 Prime -bpy ligands. Compound 1 and compound 2 are not common hybrids based on polyoxometalates and metal halide clusters, they also contain dissociated organic ligands, therefore, compound 1 and 2 are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. - Graphical Abstract: Two new compounds have been synthesized and characterized. Structure analyses revealed that the two compounds are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Highlights: Black-Right-Pointing-Pointer First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Two different kinds of metal halide clusters. Black-Right-Pointing-Pointer Supramolecular structures based on polyoxometalates, metal halide clusters and organic ligands. Black-Right-Pointing-Pointer Hybridization of three different of building blocks.

  9. Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices.

    PubMed

    Long, De-Liang; Burkholder, Eric; Cronin, Leroy

    2007-01-01

    Polyoxometalates represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form structures that can bridge several length scales. The new building block principles that have been discovered are beginning to allow the design of complex clusters with desired properties and structures and several structural types and novel physical properties are examined. In this critical review the synthetic and design approaches to the many polyoxometalate cluster types are presented encompassing all the sub-types of polyoxometalates including, isopolyoxometalates, heteropolyoxometalates, and reduced molybdenum blue systems. As well as the fundamental structure and bonding aspects, the final section is devoted to discussing these clusters in the context of contemporary and emerging interdisciplinary interests from areas as diverse as anti-viral agents, biological ion transport models, and materials science.

  10. Heteroanionic Materials Based on Copper Clusters, Bisphosphonates, and Polyoxometalates: Magnetic Properties and Comparative Electrocatalytic NO(x) Reduction Studies.

    PubMed

    Oms, Olivier; Yang, Shu; Salomon, William; Marrot, Jérôme; Dolbecq, Anne; Rivière, Eric; Bonnefont, Antoine; Ruhlmann, Laurent; Mialane, Pierre

    2016-02-15

    Three compounds associating for the first time polyoxotungstates, bisphosphonates, and copper ions were structurally characterized. They consist in heteropolyanionic monodimensional materials where [Cu6(Ale)4(H2O)4](4-) (Ale = alendronate = [O3PC(O)(C3H6NH3)PO3](4-)) complexes alternate with polyoxometalate (POM) units. In Na12[{SiW9O34Cu3(Ale)(H2O)}{Cu6(Ale)4(H2O)4}]·50H2O (SiW9CuAle), the polyoxometalate core consists in a {SiW9Cu3} monomer capped by a pentacoordinated Ale ligand, while sandwich-type Keggin {(SbW9O33)2Cu3(H2O)(2.5)Cl(0.5)} and Dawson {(P2W15O56)2Cu4(H2O)2} complexes are found in Na8Li29[{(SbW9O33)2Cu3(H2O)(2.5)Cl(0.5)}2{Cu6(Ale)4(H2O)4}3]·163H2O (SbW9CuAle) and Na20[{(P2W15O56)2Cu4(H2O)2}{Cu6(Ale)4(H2O)4}]·50H2O (P2W15CuAle), respectively. A comparative magnetic study of the SiW9CuAle and SbW9CuAle compounds enabled full quantification of the Cu(II) superexchange interactions both for the POM and non-POM subunits, evidencing that, while the paramagnetic centers are anti-ferromagnetically coupled in the polyoxometalate units, both anti-ferromagnetic and ferromagnetic interactions coexist in the {Cu6(Ale)4(H2O)4} cluster. All the studied compounds present a good efficiency upon the reduction of HNO2 or NO2(-), the POM acting as a catalyst. However, it has been found that SbW9CuAle is inactive toward the reduction of nitrates, highlighting that both the {(SbW9O33)2Cu3} unit and the {Cu6(Ale)4(H2O)4} cluster do not act as electrocatalysts for this reaction. In contrast, SiW9CuAle and P2W15CuAle have shown a significant activity upon the reduction of NO3(-) and thus both at pH 1 and pH 5, evidencing that the chemical nature of the polyoxometalate is a crucial parameter even if it acts as precatalyst. Moreover, comparison of the activities of P2W15CuAle and [(P2W15O56)2Cu4(H2O)2](16-) evidenced that if the [Cu6(Ale)4(H2O)4](4-) cluster does not act as electrocatalyst, it acts as a cofactor, significantly enhancing the catalytic efficiency of the

  11. Quantum chemical studies on Re-Re quadruple-bonded Keggin-type polyoxometalate ([ ? (PW11O39)2]8-): Bonding feature and electron spectrum

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Guang

    2011-07-01

    Density functional theory (DFT) was employed to calculate the bonding feature, electron spectrum, and redox properties of a dumbbell-shaped polyoxometalate (POM) cluster, [ ? (PW11O39)2]8-. Our DFT calculations confirm that the quadruple bond interaction between two ReIII centers consists of σ, 2π, and δ orbital overlaps, and the strength of the bonding interactions is in the order σ-bond > π-bond>δ-bond. Time-dependent (TD) DFT calculations suggest that this cluster possesses one strong and four weak absorption bands between 0.7 and 2.5 eV. Excited state calculations show that the Re-Re bond length increases when one electron of the Re-Re bonding δ orbital is shifted to the Re-Re δ* antibonding orbital. Molecular orbital predictions and spin unrestricted calculations indicate that the two Re atoms form the reduced center. The Re-Re bond length increases in one- and two-electron reduction processes because the Re-Re δ* antibonding orbital becomes occupied. However, these changes in the Re-Re bond length in excitation and reduction processes are not substantial because of the weak δ bond. The substitution effect of the central tetrahedron heteroatom of the POM ligand affects the Re-Re bond length, with the Re-Re distance decreasing with the substitution of X from Al to S, Al (2.345 Å) > Si (2.310 Å) > P (2.282 Å) > S (2.257 Å).

  12. Polyoxometalate Cluster-Incorporated Metal-Organic Framework Hierarchical Nanotubes.

    PubMed

    Xu, Xiaobin; Chen, Shuangming; Chen, Yifeng; Sun, Hongyu; Song, Li; He, Wei; Wang, Xun

    2016-06-01

    A simple method to prepare metal-organic framework (MOF) nanotubes is developed by employing polyoxometalates (POMs) as modulators. The local structure of the MOF nanotubes is investigated combining XANES and EXAFS studies. These nanotubes show both an excellent catalytic performance in the detoxification of sulfur compounds in O2 atmosphere and a remarkable cycling stability as the anode material for lithium-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization.

    PubMed

    Nagashima, Eri; Yoshida, Takuya; Matsunaga, Satoshi; Nomiya, Kenji

    2016-09-14

    The effect of counteranions on the molecular structures of phosphanegold(i) cluster cations formed by polyoxometalate (POM)-mediated clusterization was investigated. A novel intercluster compound, [{(AuLCl)2(μ-OH)}2]3[α-PMo12O40]2·3EtOH (1-PMo12), was obtained as orange-yellow plate crystals in 12.0% yield from a 6 : 1 molar ratio reaction of the monomeric phosphanegold(i) carboxylato complex [Au(RS-pyrrld)(LCl)] (RS-Hpyrrld = RS-2-pyrrolidone-5-carboxylic acid; LCl = tris(4-chlorophenyl)phosphane) in CH2Cl2 with the free acid-form of Keggin polyoxometalate (POM), H3[α-PMo12O40]·14H2O. An EtOH/H2O (5 : 1, v/v) solvent mixture was used. The dimeric cation [{(AuLCl)2(μ-OH)}2](2+) in 1-PMo12 was in a parallel-edge arrangement that was formed by self-assembly through the inter-cationic aurophilic interactions of the μ-OH-bridged dinuclear phosphanegold(i) cation. The POM anion in 1-PMo12 was successfully exchanged with a smaller PF6(-) anion by the use of an anion-exchange resin. POM-free, colorless block crystals of [{(AuLCl)3(μ3-O)}2](PF6)2·4CH2Cl2 (2-PF6) were obtained by vapor diffusion in 14.1% yield. During the synthesis of 2-PF6, a compound with mixed counteranions (one POM and one PF6(-) anion), i.e. [{(AuLCl)4(μ4-O)}]2[α-PMo12O40]PF6 (3-PMo12PF6), was obtained in 66.4% yield. Both products were characterized by elemental analysis, TG/DTA, FT-IR, (31)P{(1)H} NMR, (1)H NMR, and X-ray crystallography. X-ray crystallography revealed that the countercation in 2-PF6 was the dimeric cation of the μ3-O-bridged tris{phosphanegold(i)} species, whereas that in 3-PMo12PF6 consisted of an unusual μ4-O-bridged tetragonal-pyramidal tetrakis{phosphanegold(i)} cation. Therefore, we concluded that the POM anion significantly contributed to the stabilization of these countercations (parallel-edged arrangement in 1-PMo12 and μ4-O-bridged tetragonal-pyramid in 3-PMo12PF6). Moreover, the previously reported yellow crystals of [{(AuLF)2(μ-OH)}2]3[PMo12O40]2·3

  14. First examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands

    NASA Astrophysics Data System (ADS)

    Wang, La-Mei; Fan, Yong; Wang, Yan; Xiao, Li-Na; Hu, Yang-Yang; Peng, Yu; Wang, Tie-Gang; Gao, Zhong-Min; Zheng, Da-Fang; Cui, Xiao-Bing; Xu, Ji-Qing

    2012-07-01

    Two new organic-inorganic compounds based on polyoxometalates, metal halide clusters and organic ligands: [BW12O40]2[Cu2(Phen)4Cl](H24, 4'-bpy)4·H3O·5H2O (1) and [HPW12O40][Cd2(Phen)4Cl2](4, 4'-bpy) (2) (Phen=1, 10-phenanthroline, bpy=bipyridine), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 is constructed from [BW12O40]5-, metal halide clusters [Cu2(Phen)4Cl]+and 4, 4'-bpy ligands, while compound 2 is constructed from [PW12O40]3-, metal halide cluster [Cd2(Phen)4Cl2]2+ and 4, 4'-bpy ligands. Compound 1 and compound 2 are not common hybrids based on polyoxometalates and metal halide clusters, they also contain dissociated organic ligands, therefore, compound 1 and 2 are the first examples of hybrids based on polyoxometalates, metal halide clusters and organic ligands.

  15. Rare-earth-transition-metal organic-inorganic hybrids based on Keggin-type polyoxometalates and pyrazine-2,3-dicarboxylate.

    PubMed

    Zhang, Shaowei; Zhao, Junwei; Ma, Pengtao; Niu, Jingyang; Wang, Jingping

    2012-05-01

    Five rare-earth-transition-metal (RE-TM) heterometal organic-inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2·n H2O (n≈4; RE=YIII (1), DyIII (2), YbIII (3), and LuIII (4)) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}·n H2O (5; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1-5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210- subunits linked by H2pzda ligands. Interestingly, 1-4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1-5 represent the first monovacant Keggin-type silicotungstates containing both RE-TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3-5 are attributable to the H2pzda ligands.

  16. Polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds: syntheses and molecular structures of silanol- and/or siloxane bond-containing species grafted on mono- and tri-lacunary Keggin POMs.

    PubMed

    Aoki, Shotaro; Kurashina, Takayuki; Kasahara, Yuhki; Nishijima, Tadashi; Nomiya, Kenji

    2011-02-14

    Using 3-mercaptopropyltrimethoxysilane (HS(CH₂)₃Si(OMe)₃) as a silane-coupling agent (SCA), mono- and tri-lacunary Keggin polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds, (Et₄N)₃[α-PW₁₁O₃₉{(HS(CH₂)₃Si)₂O}] EtN-1 (the 1 : 2 complex of a POM unit and organosilyl groups), (Bu₄N)₃[A-PW₉O₃₄(HS(CH₂)₃SiOH)₃] BuN-2 (the 1 : 3 complex) and (Bu₄N)₃[A-α-PW₉O₃₄(HS(CH₂)₃SiO)₃(Si(CH₂)₃SH)] BuN-3 (the 1 : 4 complex) were synthesized and unequivocally characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state (²⁹Si and ³¹P) CPMAS NMR, solution (²⁹Si, ³¹P, ¹H and ¹³C) NMR, and X-ray crystallography. [Note: The moieties of their polyoxoanions are abbreviated simply as 1-3, respectively.] The X-ray molecular structures of EtN-1 and BuN-3 were determined. In EtN-1, two organic groups connected through a siloxane bond (-Si-O-Si- bond) were grafted on a mono-lacunary site of a Keggin POM, whereas in BuN-3 four organic groups connected through siloxane bonds were grafted on a tri-lacunary site of a Keggin POM. In BuN-2, three organic groups were grafted in the form of silanol (-SiOH) on a tri-lacunary site, i.e., in BuN-2 there was no siloxane bond. BuN-3 was synthesized as BuN-3a and BuN-3b by two methods, respectively; (1) BuN-3a was obtained by a 1 : 1 molar-ratio reaction of BuN-2 and an SCA in CH₃CN, and (2) BuN-3b was prepared by a direct 1 : 4 molar-ratio reaction of a tri-lacunary Keggin POM and SCA in water-CH₃CN. X-Ray crystallography revealed that BuN-3a is the same as BuN-3b. It is probable that BuN-2 is an intermediate in the formation of BuN-3. Terminal -SH groups in 1-3, as well as -OH groups in 2, can be utilized for immobilization of POMs and, also, as building blocks for the formation of novel hybrid compounds.

  17. Composite Hybrid Cluster Built from the Integration of Polyoxometalate and a Metal Halide Cluster: Synthetic Strategy, Structure, and Properties.

    PubMed

    Li, Xin-Xiong; Ma, Xiang; Zheng, Wen-Xu; Qi, Yan-Jie; Zheng, Shou-Tian; Yang, Guo-Yu

    2016-09-06

    A step-by-step synthetic strategy, setting up a bridge between the polyoxometalate (POM) and metal halide cluster (MHC) systems, is demonstrated to construct an unprecedented composite hybrid cluster built up from one high-nuclearity cationic MHC [Cu8I6](2+) and eight Anderson-type anionic POMs [HCrMo6O18(OH)6](2-) cross-linked by a tripodal alcohol derivative.

  18. Combination between lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: first (3,6)-connected framework constructed from sandwich-type polyoxometalate building blocks containing a novel (Cu8) cluster.

    PubMed

    Zhao, Jun-Wei; Zhang, Jie; Zheng, Shou-Tian; Yang, Guo-Yu

    2008-02-07

    An unprecedented (3,6)-connected 3-D framework constructed from sandwich-type polyoxometalate building blocks containing a (Cu8) cluster, [Cu(H(2)O)(2)]H(2)[Cu(8)(dap)(4)(H(2)O)(2)(alpha-B-GeW(9)O(34))(2)] (dap = 1,2-diaminopropane) has been hydrothermally made, which provides a novel topological structure in transition metal substituted polyoxometalates.

  19. Two 3D networks based on sandwich-type polyoxometalate units linked by Sr-O clusters: Synthesis, structure, and magnetic property

    SciTech Connect

    Yu Yang; Zhou Baibin; Yu Kai; Zhang Yunan

    2010-08-15

    Two 3D hybrid sandwich-type polyoxometalates, [{l_brace}Sr(H{sub 2}O){sub 5}Sr(H{sub 2}O){sub 6}Sr{sub 0.5}(H{sub 2}O){sub 7{r_brace}2}Mn{sub 4}(H{sub 2}O){sub 2}({alpha}-PW{sub 9}O{sub 34}){sub 2}].6H{sub 2}O (1) and [{l_brace}Sr(H{sub 2}O){sub 6}[Sr(H{sub 2}O){sub 8}]{sub 2}Sr(H{sub 2}O){sub 4{r_brace}2}Mn{sub 4}(H{sub 2}O){sub 2}({alpha}{beta}{beta}{alpha}-P{sub 2}W{sub 15}O{sub 56}){sub 2}].5H{sub 2}O (2), have been obtained by the routine synthetic reactions in aqueous solution and characterized by IR, elemental analysis, thermal analysis, and X-ray single-crystal diffraction. The 3D hybrid framework of 1 and 2 are built by tetra-Mn{sup II} substituted sandwich-type polyoxotungstates modified by fourteen Sr(H{sub 2}O){sub x} (x=4-8) units acting as bridges, forming centrosymmetric sandwich structures. The magnetic property of compound 1 has been studied by measuring its magnetic susceptibility in the temperature range of 2-300 K, which indicates predominant ferromagnetic interactions between the Mn{sup II}-O-Mn{sup II} bridge unit. Additionally, the electrochemical behaviours have been detected on solid bulk modified carbon paste electrodes of compounds (CPEs) and three redox couples are detected. - Graphical abstract: Two compounds based on Keggin(a) and Wells-Dawson(b) polyoxometalates modified by 14 Sr-O clusters.

  20. Mesoporous polyoxometalate cluster-crosslinked organosilica frameworks delivering exceptionally high photocatalytic activity.

    PubMed

    Koutsouroubi, Eirini D; Xylouri, Alexandra K; Armatas, Gerasimos S

    2015-03-14

    Mesoporous framework materials comprising lacunary [SiW11O39](8-) polyoxometalate clusters covalently connected by ethane-bridged silsesquioxane linkers were synthesized through a block copolymer-templated cross-linking polymerization of 1,2-bis(triethoxysilyl)ethane in acid solution. These new hybrid materials, which exhibit a high density of catalytic sites, large pore surface and ordered pore structure, are shown to be highly effective in the photocatalytic oxidation of aryl alcohols with molecular oxygen.

  1. Effects of isolobal heteroatoms in divanadium-substituted γ-Keggin-type polyoxometalates on (OV)2(μ-OH)2 diamond and (OV)2(μ-O) core structures and the transformation.

    PubMed

    Uehara, Kazuhiro; Taketsugu, Tatsuya; Yonehara, Kazuhiro; Mizuno, Noritaka

    2013-01-18

    Effects of isolobal heteroatoms in divanadium-substituted γ-Keggin-type polyoxometalates, (TBA)(4)[γ-XV(2)W(10)O(38)(μ-OH)(2)] 1(X) and (TBA)(4)[γ-XV(2)W(10)O(38)(μ-O)] 2(X) (where X = Ge or Si), on (OV)(2)(μ-OH)(2) and (OV)(2)(μ-O) core structures and transformations from 2(X) to 1(X) have been investigated. X-ray crystallography of 1(X) and 2(X) reveals that larger Ge (covalent radius 1.22 Å; covalent radius of Si 1.11 Å) induces (a) expansion of (OV)(2)(μ-OH)(2) and (OV)(2)(μ-O) cores, (b) expansion of lacunary sites, and (c) deep location of divanadium cores inside their lacunary sites. Density functional theory (DFT) calculations for anionic moieties of 1(X) and 2(X) reveal that energy levels of the highest occupied molecular orbital (HOMO)-1 in 1(Ge) and HOMO in 2(Ge) are lower than those in 1(Si) and 2(Si), respectively, because of smaller contribution of p(z) orbitals of oxygen atoms in 1(Ge) and 2(Ge), which would result from shorter V···O(-Ge) distances. Compound 2(Ge) reacts with water vapor to form (TBA)(4)[γ-GeV(2)W(10)O(38)(μ-OH)(2)] 1'(Ge) via a crystal-to-crystal transformation, and the water dissociation proceeds heterolytically. DFT calculations reveal that the reaction proceeds through (1) coordination of water on a coordinatively unsaturated site of vanadium in the lowest unoccupied molecular orbital (LUMO), followed by (2) proton transfer to the bridging oxo moiety. The order is different from that in 2(Si), which would result from the lower energy level of HOMO of 2(Ge) (i.e., lower nucleophilicity toward a proton of water) than that of 2(Si).

  2. Polyoxometalate-stabilized, water dispersible Fe2Pt magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Seemann, K. M.; Bauer, A.; Kindervater, J.; Meyer, M.; Besson, C.; Luysberg, M.; Durkin, P.; Pyckhout-Hintzen, W.; Budisa, N.; Georgii, R.; Schneider, C. M.; Kögerler, P.

    2013-02-01

    Magnetic Fe2Pt core-shell nanoparticles with 2 nm cores were synthesized with a monolayer coating of silicotungstate Keggin clusters. The core-shell composition is substantiated by structural analysis performed using high-resolution scanning transmission electron microscopy (HR-STEM) and small angle X-ray scattering (SAXS) in a liquid suspension. The molecular metal oxide cluster shell introduces an enhanced dispersibility of the magnetic Fe-Pt core-shell nanoparticles in aqueous media and thereby opens up new routes to nanoparticle bio-functionalization, for example, using pre-functionalized polyoxometalates.Magnetic Fe2Pt core-shell nanoparticles with 2 nm cores were synthesized with a monolayer coating of silicotungstate Keggin clusters. The core-shell composition is substantiated by structural analysis performed using high-resolution scanning transmission electron microscopy (HR-STEM) and small angle X-ray scattering (SAXS) in a liquid suspension. The molecular metal oxide cluster shell introduces an enhanced dispersibility of the magnetic Fe-Pt core-shell nanoparticles in aqueous media and thereby opens up new routes to nanoparticle bio-functionalization, for example, using pre-functionalized polyoxometalates. Electronic supplementary information (ESI) available: Details of materials, methods and experiments. See DOI: 10.1039/c3nr33374d

  3. X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

    DOE PAGES

    Yin, Panchao; Wu, Bin; Mamontov, Eugene; ...

    2016-02-05

    A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types of water molecules,more » the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.« less

  4. Crystallographic Studies on the Mechanisms of the Cluster Formation and the Higher Order Structure Evolution of Mixed-valence Polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ozeki, Tomoji

    The advantages of the use of synchrotron radiation for single crystal X-ray diffraction experiments were exploited to obtain a deeper understanding of the chemistry of polyoxometalates through structural investigations. The pH dependence of the structures of {Mo154-x} mixed-valence oxomolybdate clusters were investigated by analyzing the structures of systematically prepared compounds containing wheel-shaped mixed-valence polyoxometalates with 138, 142, 148, 150, or 152 molybdenum atoms. Direct correlation was observed between the nuclearity of the clusters with the pH of the mother liquor. On the other hand, the geometries of extended structures do not show apparent correlation with the pH. They turned out to be determined by the structures of the constituent polyoxometalate. The pH of the mother liquor exerts influence on the extended structure through the structures of the constituent clusters. Such systematic preparation—structure determination study was enabled by the use of synchrotron radiation.

  5. Preparation, structural characterization, and ion-exchange properties of two new zeolite-like 3D frameworks constructed by ε-Keggin-type polyoxometalates with binding metal ions, H11.4[ZnMo12O40Zn2]1.5- and H7.5[Mn0.2Mo12O40Mn2]2.1-.

    PubMed

    Zhang, Zhenxin; Sadakane, Masahiro; Murayama, Toru; Sakaguchi, Norihito; Ueda, Wataru

    2014-07-21

    Two new ε-Keggin-type polyoxometalate-based 3D frameworks, Na1.5H11.4[ε-Zn(II)Mo(V)10.9Mo(VI)1.1O40{Zn(II)}2] and (NH4)2.1H7.5[ε-Mn(II)0.2Mo(V)6Mo(VI)6O40{Mn(II)}2], are prepared, and their structures are determined by powder X-ray diffraction, Fourier transform infrared, Raman spectroscopy, and elemental analysis. ε-Keggin-type polyoxomolybdate units, [ε-ZnMo12O40] and [ε-Mn0.2Mo12O40], are linked with Zn(2+) and Mn(2+), respectively, in a tetrahedral fashion to form 3D frameworks. They show zeolite-like ion-exchange properties and redox properties. The ε-Keggin-based 3D framework shows high chemical composition diversity and can incorporate different elements in the framework.

  6. New optical supramolecular compound constructed from a polyoxometalate cluster and an organic substrate.

    PubMed

    Xie, Yi-Ming; Zhang, Qi-Sheng; Zhao, Zhen-Guo; Wu, Xiao-Yuan; Chen, Shan-Ci; Lu, Can-Zhong

    2008-09-15

    A new optical supramolecular compound constructed from a polyoxometalate cluster and an organic substrate [(H3O)(C12H10N3)2(PW12O40)] (1) has been synthesized via a hydrothermal reaction and has been structurally characterized by X-ray diffraction. The solid-state diffuse reflectance, IR, and photoluminescence spectra of the title compound indicate that there is an interaction between the alpha-PW12O40 and the organic substrate. The light-yellow title compound shows a certain second-order nonlinear optical response of I(2omega) = 2I(KDP)(2omega).

  7. Facile assembly of hybrid materials containing polyoxometalate cluster anions and organic dye cations: crystal structures and initial spectral characterization.

    PubMed

    Xie, Jingli; Abrahams, Brendan F; Wedd, Anthony G

    2008-02-07

    Salts of the pararosaniline dye cation and four polyoxometalate cluster anions have been isolated under both ambient and hydrothermal conditions; structural and initial spectroscopic data are consistent with significant perturbation of ion electronic states induced by charge-assisted N-H---O hydrogen bonds.

  8. Syntheses and characterizations of two novel networks formed by Keggin clusters and copper organonitrogen complexes

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Xiao, Dongrong; Fan, Linlin; Wang, Enbo; Liu, Jia

    2007-10-01

    Two novel heteropolytungstates, [Cu 3Cl(4,4'-bpy) 3] 2[α-SiW 12O 40] · 4H 2O 1 and {Cu 3(4,4'-bpy) 2(2,2'-bpy) 3}{Cu(2,2'-bpy) 2}{α-SiW 12O 40} · 0.5(H 2O) · 0.5(2,2'-bpy) 2 (4,4'-bpy = 4,4'-bipyridine, 2,2'-bpy = 2,2'-bipyridine), have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Compound 1 has a unique 2D network, which is composed of cationic trinuclear Cu(I) coordination polymer chains and discrete [α-SiW 12O 40] 4- polyoxoanions as linkers. Notably, it is rarely that the Cu(I) coordination polymer chains are not isolated but connected together by chlorine atoms. Compound 2 exhibits an unusual 3-D network with sandglasslike 1-D channels, within which are located large spherical polyoxometalate anions [α-SiW 12O 40] 4-. The crystal data for two compounds are the following: 1, triclinic, space group P1¯, a = 10.904(2) Å, b = 15.087(3) Å, c = 15.303(3) Å, α = 116.23(3)°, β = 100.08(3)°, γ = 94.40(3)°, V = 2189.29(80) Å 3, Z = 1; 2, monoclinic, C2/c, a = 15.444(3) Å, b = 24.962(5) Å, c = 25.806(5) Å, β = 99.75(3)°, V = 9805(3) Å 3, Z = 4.

  9. Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.

    PubMed

    Robbins, Philip J; Surman, Andrew J; Thiel, Johannes; Long, De-Liang; Cronin, Leroy

    2013-03-07

    We present the high-resolution (HRES-MS) and ion-mobility (IMS-MS) mass spectrometry studies of icosahedral nanoscale polyoxometalate-based {L(30)}{(Mo)Mo(5)} Keplerate clusters, and demonstrate the use of IMS-MS to resolve and map intact nanoclusters, and its potential for the discovery of new structures, in this case the first gas phase observation of 'proto-clustering' of higher order Keplerate supramolecular aggregates.

  10. Polyoxometalate monolayers in Langmuir-Blodgett films.

    PubMed

    Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; Mingotaud, Christophe; Ravaine, Serge; Romualdo-Torres, Gemma; Delhaès, Pierre

    2005-06-20

    Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.

  11. 2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C{sub 2}H{sub 6}NO{sub 2}]{sub 3}[(PO{sub 4})Mo{sub 12}O{sub 36}].5H{sub 2}O

    SciTech Connect

    Alizadeh, M.H. Mirzaei, M.; Razavi, H.

    2008-03-04

    A new inorganic-organic hybrid material based on polyoxometallate, [L-C{sub 2}H{sub 6}NO{sub 2}]{sub 3}[(PO{sub 4})Mo{sub 12}O{sub 36}].5H{sub 2}O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2{sub 1}/c{sub ,} with a = 12.4938 (8) A, b = 19.9326 (12) A, c = 17.9270 (11) A, {beta} = 102.129 (1){sup o}, V = 4364.8 (5) A{sup 3}, Z = 4 and R{sub 1}(wR{sub 2}) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/{infinity} [(PO{sub 4})Mo{sub 12}O{sub 36}]{sup 3-}) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO{sub 4})Mo{sub 12}O{sub 36}]{sup 3-} appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 deg. C.

  12. Hafnium sulfate prenucleation clusters and the Hf(18) polyoxometalate red herring.

    PubMed

    Ruther, Rose E; Baker, Brenna M; Son, Jung-Ho; Casey, William H; Nyman, May

    2014-04-21

    In prior studies, aqueous Hf sulfate-peroxide solutions were spin-coated, dehydrated, patterned by electron-beam lithography, ion-exchanged (OH(-) for SO4(2-)), and finally converted to HfO2 hard masks via annealing. The atomic-level details of the underlying aqueous chemistries of these processes are complex and yet to be understood. Yet a thorough understanding of this specific chemical system will inspire development of design rules for other aqueous-precursor-to-solid-state metal oxide systems. Often-observed crystallization of the Hf18 polyoxometalate from aqueous Hf sulfate-peroxide precursor solutions has led us to believe that Hf18 may represent an important intermediate step in this process. However, via detailed solution studies described here (small-angle X-ray scattering, electrospray ionization mass spectrometry, and Raman spectroscopy), we ascertained that Hf18 is in fact not a prenucleation cluster of Hf sulfate coatings. Rather, the Hf tetramers, pentamers, and hexamers that are the core building blocks of Hf18 are robustly persistent over variable compositions and aging time of precursor solutions, and therefore they are likely the rudimentary building blocks of the deposited thin-film materials. These Hf clusters are capped and linked by sulfate and peroxide anions in solution, which probably prevents crystallization of Hf18 during the rapid dehydration process of spin-coating. In fact, crystallization of Hf18 from the amorphous gel coating would be detrimental to formation of a high-density conformal coating that we obtain from precursor solutions. Therefore, this study revealed that the well-known Hf18 polyoxometalate is not likely to be an important intermediate in the thin-film process. However, its subunits are, confirming the universal importance of deriving information from the solid state, albeit judiciously and critically, to understand the solution state.

  13. Development of Dodecaniobate Keggin Chain Materials as Alternative Sorbents for SR and Actinide Removal from High-Level Nuclear Waste Solutions

    SciTech Connect

    Nyman, May; Bonhomme, Francois

    2004-03-28

    The current baseline sorbent (monosodium titanate) for Sr and actinide removal from Savannah River Site's high level wastes has excellent adsorption capabilities for Sr but poor performance for the actinides. We are currently investigating the development of alternative materials that sorb radionuclides based on chemical affinity and/or size selectivity. The polyoxometalates, negatively-charged metal oxo clusters, have known metal binding properties and are of interest for radionuclide sequestration. We have developed a class of Keggin-ion based materials, where the Keggin ions are linked in 1- dimensional chains separated by hydrated, charge-balancing cations. These Nb-based materials are stable in the highly basic nuclear waste solutions and show good selectivity for Sr and Pu. Synthesis, characterization and structure of these materials in their native forms and Sr-exchanged forms will be presented.

  14. Bioresponsive Polyoxometalate Cluster for Redox-Activated Photoacoustic Imaging-Guided Photothermal Cancer Therapy.

    PubMed

    Ni, Dalong; Jiang, Dawei; Valdovinos, Hector F; Ehlerding, Emily B; Yu, Bo; Barnhart, Todd E; Huang, Peng; Cai, Weibo

    2017-05-10

    Although various types of imaging agents have been developed for photoacoustic (PA) imaging, relatively few imaging agents exhibit high selectivity/sensitivity to the tumor microenvironment for on-demand PA imaging and therapy. Herein, molybdenum-based polyoxometalate (POM) clusters with the highest oxidation state of Mo(VI) (denoted as Ox-POM) were designed as novel agents for redox-activated PA imaging-guided photothermal therapy. Capable of escaping from recognition and capture by the liver and spleen, these renal clearable clusters with ultrasmall size (hydrodynamic size: 1.9 nm) can accumulate in the tumor, self-assemble into larger nanoclusters at low pH, and are reduced to NIR absorptive agents in the tumor microenvironment. Studies in 4T1 tumor-bearing mice indicated that these clusters could be employed for bioresponsive PA imaging-guided tumor ablation in vivo. Our finding is expected to establish a new physicochemical paradigm for the design of PA imaging agents based on clusters, bridging the conventional concepts of "molecule" and "nano" in the bioimaging field.

  15. Time-resolved assembly of cluster-in-cluster {Ag₁₂}-in-{W₇₆} polyoxometalates under supramolecular control.

    PubMed

    Zhan, Caihong; Cameron, Jamie M; Gao, Jing; Purcell, Jamie W; Long, De-Liang; Cronin, Leroy

    2014-09-22

    We report the time-resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one-pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self-organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}-in-{W76} cluster-in-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI-MS. Further, control experiments demonstrate the crucial role that TeO3(2-), Cl(-), and Ag(+) play in the self-assembly of compounds 1-3. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Identification of a nonanuclear {Co(II)9} polyoxometalate cluster as a homogeneous catalyst for water oxidation.

    PubMed

    Goberna-Ferrón, Sara; Vigara, Laura; Soriano-López, Joaquín; Galán-Mascarós, José Ramón

    2012-11-05

    The polyanion of formula {Co(9)(H(2)O)(6)(OH)(3)(HPO(4))(2)(PW(9)O(34))(3)}(16-) (Co(9)) contains a central nonacobalt core held together by hydroxo and hydrogen phosphate bridges and supported by three lacunary Keggin-type polyphosphotungstate ligands. Our data demonstrate that Co(9) is a homogeneous catalyst for water oxidation. Catalytic water electrolysis on fluorine-doped tin oxide coated glass electrodes occurs at reasonable low overpotentials and rates when Co(9) is present in a sodium phosphate buffer solution at neutral pH. We carried out our experiments with an excess of 2,2'-bipyridyl as the chelating agent for free aqueous Co(II) ions, in order to avoid the formation of a cobalt oxide film on the electrode, as observed for other polyoxometalate catalysts. In these conditions, no heterogeneous catalyst forms on the anode, and it does not show any deposited material or significant catalytic activity after a catalytic cycle. Co(9) is also an extremely robust catalyst for chemical water oxidation. It is able to continuously catalyze oxygen evolution during days from a buffered sodium hypochlorite solution, maintaining constant rates and efficiencies without any significant apparition of fatigue.

  17. Polyoxometalate clusters integrated into peptide chains and as inorganic amino acids: solution- and solid-phase approaches.

    PubMed

    Yvon, Carine; Surman, Andrew J; Hutin, Marie; Alex, Jennifer; Smith, Brian O; Long, De-Liang; Cronin, Leroy

    2014-03-24

    General synthetic methods for the grafting of peptide chains onto polyoxometalate clusters by the use of general activated precursors have been developed. Using a solution-phase approach, pre-synthesized peptides can be grafted to a metal oxide cluster to produce hybrids of unprecedented scale (up to 30 residues). An adapted solid-phase method allows the incorporation of these clusters, which may be regarded as novel hybrid unnatural amino acids, during the peptide synthesis itself. These methods may open the way for the automated synthesis of peptides and perhaps even proteins that contain "inorganic" amino acids. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Design and fabrication of memory devices based on nanoscale polyoxometalate clusters

    NASA Astrophysics Data System (ADS)

    Busche, Christoph; Vilà-Nadal, Laia; Yan, Jun; Miras, Haralampos N.; Long, De-Liang; Georgiev, Vihar P.; Asenov, Asen; Pedersen, Rasmus H.; Gadegaard, Nikolaj; Mirza, Muhammad M.; Paul, Douglas J.; Poblet, Josep M.; Cronin, Leroy

    2014-11-01

    Flash memory devices--that is, non-volatile computer storage media that can be electrically erased and reprogrammed--are vital for portable electronics, but the scaling down of metal-oxide-semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core-shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core-shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(IV)O3)2]4- as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(V)2O6]2- moiety containing a {Se(V)-Se(V)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call `write-once-erase'. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

  19. Design and fabrication of memory devices based on nanoscale polyoxometalate clusters.

    PubMed

    Busche, Christoph; Vilà-Nadal, Laia; Yan, Jun; Miras, Haralampos N; Long, De-Liang; Georgiev, Vihar P; Asenov, Asen; Pedersen, Rasmus H; Gadegaard, Nikolaj; Mirza, Muhammad M; Paul, Douglas J; Poblet, Josep M; Cronin, Leroy

    2014-11-27

    Flash memory devices--that is, non-volatile computer storage media that can be electrically erased and reprogrammed--are vital for portable electronics, but the scaling down of metal-oxide-semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core-shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core-shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(IV)O3)2](4-) as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(v)2O6](2-) moiety containing a {Se(V)-Se(V)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call 'write-once-erase'. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

  20. X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

    SciTech Connect

    Yin, Panchao; Wu, Bin; Mamontov, Eugene; Daemen, Luke L.; Cheng, Yongqiang; Li, Tao; Seifert, Soenke; Hong, Kunlun; Bonnesen, Peter V.; Keum, Jong Kahk; Ramirez-Cuesta, Anibal J.

    2016-02-05

    A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.

  1. Hydrothermal syntheses and structures of two novel polyoxometalate-based 3-D supramolecular architectures

    NASA Astrophysics Data System (ADS)

    Yi, Zhi-Hui; Cui, Xiao-Bing; Zhang, Xiao; Yang, Guang-Di; Xu, Ji-Qing; Yu, Xiao-Yang; Yu, Hai-Hui; Duan, Wei-Jie

    2008-11-01

    Two supramolecular architectures based on polyoxometalates: [4,4'-Hbpy] 2[Ni(4,4'-bpy) 2(H 2O) 4][AsW VI11W VO 40]·4H 2O ( 1) and [4,4'-H 2bpy] 2[PMo VI9Mo V3O 40]·2H 3O ( 2) (4,4'-bpy = 4,4'-bipyridine) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, XPS spectra and single crystal X-ray diffraction analyses. The two compounds consist of 4,4'-bpy units with different polyoxometalates, α-Keggin [AsW VI11W VO 40] 4- and pseudo-Keggin [PMo VI9Mo V3O 40] 6-, respectively. No direct interactions occur among polyoxoanions in these two compounds, but the clusters together with metal-organic units or organic 4,4'-bpy units and/or water molecules construct the high-dimensional supramolecular networks through hydrogen bonds. The crystal structure analyses reveal that the organic 4,4'-bpy units have a major influence on the packing arrangements of crystals.

  2. Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism.

    PubMed

    Winter, Ross S; Yan, Jun; Busche, Christoph; Mathieson, Jennifer S; Prescimone, Alessandro; Brechin, Euan K; Long, De-Liang; Cronin, Leroy

    2013-02-25

    Two near isomeric clusters containing a novel {Mn(8)W(4)} Keggin cluster within a [W(36)Mn(10)Si(4)O(136)(OH)(4)(H(2)O)8](24-) cluster are reported: K(10)Li(14)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8)] (1) and K(10)Li1(3.5)Mn(0.25)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8) ] (1'). Bulk characterization of the clusters has been carried out by single crystal X-ray structure analysis, ICP-MS, TGA, ESI-MS, CV and SQUID-magnetometer analysis. X-ray analysis revealed that 1' has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two "intermediate" types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X-ray analysis and revealed to be novel clusters K(4)Li(22)[W(36)Si(4)Mn(7)O(136)(H(2)O)(8)]·56H(2)O (2) and Mn(2)K(8)Li(14)[W(36)Si(4)Mn(7)O(136)(H(2)O)(8)]·45H(2)O (3). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X-ray crystallography directly facilitated understanding the means by which a POM assembled. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials.

    PubMed

    Moussawi, Mhamad Aly; Leclerc-Laronze, Nathalie; Floquet, Sébastien; Abramov, Pavel A; Sokolov, Maxim N; Cordier, Stéphane; Ponchel, Anne; Monflier, Eric; Bricout, Hervé; Landy, David; Haouas, Mohamed; Marrot, Jérôme; Cadot, Emmanuel

    2017-09-13

    Herein, we report on a three-component supramolecular hybrid system built from specific recognition processes involving a Dawson-type polyoxometalate (POM), [P2W18O62](6-), a cationic electron-rich cluster [Ta6Br12(H2O)6](2+), and γ-cyclodextrin (γ-CD). Such materials have been investigated using a bottom-up approach by studying the specific interactions between γ-CD and both types of inorganic units. Their ability to interact has been investigated in the solid state by single-crystal X-ray diffraction (XRD) and in solution using multinuclear NMR methods (including DOSY, EXSY, and COSY), electrospray ionization mass and UV-vis spectroscopies, electrochemistry, and isothermal titration calorimetry experiments. Single-crystal XRD analysis reveals that POM:γ-CD constitutes a highly versatile system which gives aggregates with 1:1, 1:2, and 1:3 stoichiometry. Surprisingly, these arrangements exhibit a common feature wherein the γ-CD moiety interacts with the Dawson-type POMs through its primary face. We present also the first structural model involving an octahedral-type metallic cluster with γ-CD. XRD study reveals that the cationic [Ta6Br12(H2O)6](2+) ion is closely embedded within two γ-CD units to give a supramolecular ditopic cation, suitable to be used as a linker within extended structure. Solution study demonstrates clearly that pre-associations exist in solution, for which binding constants and thermodynamic parameters have been determined, giving preliminary arguments about the chaotropic nature of the inorganic ions. Finally, both building blocks, i.e., the ditopic supramolecular cation {[Ta6Br12(H2O)6]@2CD}(2+) and the Dawson-type anion, react together to give a three-component, well-ordered hybrid material derived either as a supramolecular hydrogel or single crystals. The solid-state structure shows an unprecedented helicoidal tubular chain resulting from the periodic alternation of POM and supramolecular cation, featuring short hydrogen

  4. Inter-cluster distance dependence of electrical properties in single crystals of a mixed-valence polyoxometalate.

    PubMed

    Tsunashima, Ryo; Nakamura, Ippei; Oue, Rika; Koga, Seiya; Oki, Hirofumi; Noro, Shin-Ichiro; Nakamura, Takayoshi; Akutagawa, Tomoyuki

    2017-09-26

    The electrical conductivity of mixed-valence [MoMoO54(SO3)2](6-) tetraalkylammonium salts was investigated through dependence on the inter-cluster distance that is controlled by tetraethylammonium, tetrapropylammonium, and tetrabutylammonium cations. The crystallographic analysis of single crystals revealed that the inter-cluster distances are dependent on the chain length of the alkyl groups on the counter cations. In addition, the electrical conductivities of the single crystals were found to be dependent on both temperature and chain length. Mixed-valence polyoxometalate (POM) clusters are considered to be a molecular particle of Mo bronze by which highly ordered networks will be developed using single crystals, where POMs are rather small and have a well-organized structure compared to colloidal nanostructures.

  5. Iontophoretic transport of associates based on porous Keplerate-type cluster polyoxometalate Mo72Fe30 and containing biologically active substances

    NASA Astrophysics Data System (ADS)

    Ostroushko, A. A.; Gagarin, I. D.; Tonkushina, M. O.; Grzhegorzhevskii, K. V.; Danilova, I. G.; Gette, I. F.; Kim, G. A.

    2017-09-01

    The possibility of iontophoretic transport through the native membranes of biologically active substances (vitamin B1 and insulin) associated with porous clusters Mo72Fe30 polyoxometalate of the Keplerate type is demonstrated for the first time in an experimental setup. The diffusion coefficient is estimated. The possibility of transferring Keplerate ions with a protective coating of biocompatible polymer polyvinylpyrrolidone is also shown.

  6. Cation Translocation around Single Polyoxometalate-Organic Hybrid Cluster Regulated by Electrostatic and Cation-π Interactions.

    PubMed

    Li, Dong; Liu, Zhuonan; Song, Jie; Li, Hui; Zhang, Baofang; Yin, Panchao; Zheng, Zhaoxiong Norm; Roberts, James E; Tsige, Mesfin; Hill, Craig L; Liu, Tianbo

    2017-03-13

    We report herein an interesting dynamic translocation process of countercations around one polyoxometalate(POM)-organic hybrid anionic cluster at various concentrations and temperatures. It was found that both electrostatic interactions and cation-π interactions regulate the position of small countercations around single clusters. The dynamic geometry and the symmetry of the hybrid macroions are largely affected by the type of counterions, as shown by nuclear magnetic resonance (NMR) spectroscopy studies and all-atom molecular dynamics simulation. It is also shown that electrostatic interactions dominate over cation-π interactions in determining the locations of the counterions in the current system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Self-assembly of four new extended architectures based on reduced polyoxometalate clusters and cadmium complexes

    SciTech Connect

    Ma Ying; Li Yangguang; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Lu Ying; Wang Xinlong; Xu Xinxin

    2006-08-15

    report four new extended architectures based on reduced polyoxometalate clusters and cadmium complexes. Compounds 1-4 are built of Cd[P{sub 4}Mo{sub 6}]{sub 2} dimers as the basic structural motif and Cd-4,4'-bpy, Cd-phen and Cd-2,2'-bpy complexes as the linkers to constructed novel 2D layer structure.

  8. Morphogenesis of polyoxometalate cluster-based materials to microtubular network architectures.

    PubMed

    Boulay, Antoine G; Cooper, Geoffrey J T; Cronin, Leroy

    2012-05-25

    Pressed pellets of polyoxometalate (POM)-based materials are shown to undergo morphogenesis to produce microtubular network architectures without the need for a large single crystal precursor. The compression of the POM material into a pellet lowers the solubility sufficiently to allow tube initiation and growth from POMs that would otherwise be too soluble in their native crystalline state, thus yielding hollow, highly controllable, tubes of diameter 10-100 μm. This journal is © The Royal Society of Chemistry 2012

  9. Controlled assembly of two new bicapped bisupporting Keggin-polyoxometalate derivatives: [M(2,2'-bpy){sub 2}(H{sub 2}O)]{sub 2}[SiMo{sup VI}{sub 8}Mo{sup V}{sub 4}V{sup IV}{sub 2}O{sub 42}] (M=Co, Zn)

    SciTech Connect

    Shi Zhenyu; Gu Xiaojun; Peng Jun. E-mail: jpeng@nenu.edu.cn; Chen Yanhui

    2005-06-15

    Two new neutral bicapped bisupporting Keggin-polyoxometalate derivatives: [M(2,2'-bpy){sub 2}(H{sub 2}O)]{sub 2}[SiMo{sup VI}{sub 8}Mo{sup V}{sub 4}V{sup IV}{sub 2}O{sub 42}] (M=Co 1, Zn 2; 2,2'-bpy=2,2'-bipyridine), have been synthesized under hydrothermal conditions by directly using H{sub 4}SiMo{sub 12}O{sub 40} as starting materials. Crystal data for compound 1: C{sub 40}H{sub 36}Co{sub 2}Mo{sub 12}N{sub 8}O{sub 44}SiV{sub 2}, triclinic, space group P1-bar , a=11.884(2)A, b=12.459(3)A, c=12.652(3)A, {alpha}=71.02(3){sup o}, {beta}=74.51(3){sup o}, {gamma}=86.74(3){sup o}, V=1706.3(6)A{sup 3}, Z=1; for compound 2, C{sub 40}H{sub 36}Mo{sub 12}N{sub 8}O{sub 44}SiV{sub 2}Zn{sub 2}, triclinic, space group P1-bar , a=11.879(2)A, b=12.469(3)A, c=12.635(3)A, {alpha}=71.28(3){sup o}, {beta}=74.78(3){sup o}, {gamma}=86.60(3){sup o}, V=1709.6(6)A{sup 3}, Z=1. The studies of the electrochemical property of compounds 1 and 2 exhibit similar redox behavior to the parent [(C{sub 4}H{sub 9}){sub 4}N]{sub 4}SiMo{sub 12}O{sub 40}, undergoing three two-electron reversible reductions. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.

  10. Mixed-valence polyoxometalate clusters. II. Delocalization of electronic pairs in 18-site heteropoly blues with Wells-Dawson structure

    NASA Astrophysics Data System (ADS)

    Borrás-Almenar, J. J.; Clemente, J. M.; Coronado, E.; Tsukerblat, B. S.

    1995-06-01

    The problem of delocalization of two electrons in the 18-site Wells-Dawson polyoxometalate is examined from a general approach that takes into account both single- and double-transfer processes, as well as the Coulomb interactions between the two delocalized electrons. The electronic energy levels of this mixed-valence cluster are calculated and the conditions giving rise to the stabilization of a singlet ground spin state for the electronic pair are elucidated. It is shown that the spin pairing results from the simultaneous effects of single- and double-electron transfer processes, which are operative even when the two delocalized electrons are fairly widely separated in the Wells-Dawson structure.

  11. Synthesis and characterization of Lanthanide Aluminotungstates and Rhenium Polyoxometalates: Potential Application in Molecular Information Storage Devices

    NASA Astrophysics Data System (ADS)

    Bian, Fang

    2011-12-01

    Polyoxometalates (abbreviated as POMs) are metal-oxide clusters with frameworks built from group 5 or 6 transition metals linked by shared oxide ions. The Keggin structure is one of the most famous structural forms of POMs. Keggin anions have a general formula of [XM12O40 ]n-, where X is a p-block atom and M is a transition metal atom such as W or Mo. Upon removal of one MO4+ unit from the Keggin anion, the monovacant structure [XM11O39] n- is formed. Those POMs that have lost one or more metal center are called lacunary POMs, which are very nice building blocks for the fabrication of coordination polymers. My research focuses on two facets of POM chemistry: 1) Lanthanide chemistry of aluminum tungstate monovacant Keggin and 2) Rhenium chemistry of aluminum tungstate Keggin and Wells-Dawson POM alpha1 -P2W17O61. In lanthanide POM research area, we obtained the following results: 1) The starting material aluminum tungstate monovacant Keggin α-K 9AlW12O39 was synthesized. Its single crystal was firstly identified by multinuclear NMR and X-ray crystallography. Its redox properties on the nano-scale solid state were determined by Conducting Electrostatic Force Mode (EFM) probes. It is well known that for POMs, a number of varies redox states are normally stable and reversible. Thus we estimated that POMs can potentially be used in molecular information storage applications, which we refer to as "redox disk drives". 2) Eight lanthanide aluminum tungstate Keggin complexes were synthesized. In their molecular structures (identified by multinuclear NMR and X-ray crystallography), each α-AlW11O39 is connected by lanthanide (III) cations to form 1D and 2D networks. All AlW11O39 Keggin POMs are regularly aligning on a flat plane. Microscopic data also verified that there is layer-by-layer morphology in this series of compounds. Overall, we postulate that aluminum tungstate Keggin POMs are a very promising materials for making future information storage device because they

  12. Arsenicum-centered Molybdenum Vanadium polyoxometalates bearing transition metal complexes: Hydrothermal syntheses, crystal structures and magnetic properties

    NASA Astrophysics Data System (ADS)

    Li, Fengyan; Xu, Lin; Wei, Yongge; Wang, Xinlong; Wang, Wenju; Wang, Enbo

    2005-10-01

    The tetra-capped Keggin anion-supported Cobalt-Phenanthroline complex [Co 2(phen) 2(OH) 2(H 2O) 4] 0.5[{Co(phen) 2(H 2O)} 2AsMo 6VIMo 2VV 8IVO 44]·2H 2O ( 1) and the bicapped Keggin anion-based Nickel-phenanthroline compound [Ni(phen) 2H 2O] 2[AsMo 11VIMo VO 40(V IVO 2) 0.5].2H 2O( 2), have been hydrothermally synthesized and structurally characterized by elemental analyses, single crystal X-ray diffraction, IR and X-ray photoelectron spectrum. The interesting structural feature of 1 is that there are two types of free complex cation [Co 2(phen) 2(OH) 2(H 2O) 4] 2+ in different orientations in the crystal structure of 1, and these free complex cations coexist in the space between polyoxometalate clusters. The structure of compound 2 is very like compound 1 except that the Keggin unit is bi-capped instead of tetra-capped. Compounds 1 and 2 are examples that Arsenicum-centered vanadomolybdate anion acts as an active building block in the fabrication of polyoxometalates-supported hybrid solids. Then, the magnetic characteristic of 1 is typical of a dominant ferromagnetic interactions in the 6-300 K temperature range and a succedent antiferromagnetic interactions in the very low temperature range (2-6 K), while the magnetic behavior for 2 is characteristic of a dominant ferromagnetic interactions in the 6-300 K temperature range and succedent antiferromagnetic interactions in the very low temperature range (2-6 K).

  13. Exploring the Molecular Growth of Two Gigantic Half‐Closed Polyoxometalate Clusters {Mo180} and {Mo130Ce6}

    PubMed Central

    Xuan, Weimin; Pow, Robert; Long, De‐Liang

    2017-01-01

    Abstract Understanding the process of the self‐assembly of gigantic polyoxometalates and their subsequent molecular growth, by the addition of capping moieties onto the oxo‐frameworks, is critical for the development of the designed assembly of complex high‐nuclearity cluster species, yet such processes remain far from being understood. Herein we describe the molecular growth from {Mo150} and {Mo120Ce6} to afford two half‐closed gigantic molybdenum blue clusters {Mo180} (1) and {Mo130Ce6} (2), respectively. Compound 1 features a hat‐shaped structure with the parent wheel‐shaped {Mo150} being capped by a {Mo30} unit on one side. Similarly, 2 exhibits an elliptical lanthanide‐doped wheel {Mo120Ce6} that is sealed by a {Mo10} unit on one side. Moreover, the observation of the parent uncapped {Mo150} and {Mo120Ce6} clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150} and {Mo120Ce6} in solution, respectively. PMID:28508585

  14. A Polyoxometalate Cluster Paradigm with Self-Adaptive Electronic Structure for Acidity/Reducibility-Specific Photothermal Conversion.

    PubMed

    Zhang, Chen; Bu, Wenbo; Ni, Dalong; Zuo, Changjing; Cheng, Chao; Li, Qing; Zhang, Linlin; Wang, Zheng; Shi, Jianlin

    2016-07-06

    Photothermal conversion is one of the most important keys in the fields of solar collection, photo-hyperthermia, etc., and its performance is highly dependent on the photothermal conversion materials used. Especially in cancer photo-hyperthermia, the presently available small-molecule- or nanomaterial-based agents still suffer from numerous drawbacks, such as nonspecific accumulation and inevitable side effects on normal tissues. Here we identify a Mo-based polyoxometalate cluster that can change its dimension from small (1 nm) to big (tens of nanometer), favoring its intratumoral accumulation, and enhance photothermal conversion in response to the intratumoral acidity and reducibility, demonstrating a previously unrealized tumor-specific photo-hyperthermia. Distinct from the well-researched nano-based agents, a unique electronic structure of this cluster has been identified as the origin of the observed acidity-induced self-assembly and reduction-promoted NIR absorbance. In addition to providing a promising clinical agent, this finding is expected to establish a new physicochemical paradigm for photothermal materials design based on clusters.

  15. Exploring the Molecular Growth of Two Gigantic Half-Closed Polyoxometalate Clusters {Mo180 } and {Mo130 Ce6 }.

    PubMed

    Xuan, Weimin; Pow, Robert; Long, De-Liang; Cronin, Leroy

    2017-08-07

    Understanding the process of the self-assembly of gigantic polyoxometalates and their subsequent molecular growth, by the addition of capping moieties onto the oxo-frameworks, is critical for the development of the designed assembly of complex high-nuclearity cluster species, yet such processes remain far from being understood. Herein we describe the molecular growth from {Mo150 } and {Mo120 Ce6 } to afford two half-closed gigantic molybdenum blue clusters {Mo180 } (1) and {Mo130 Ce6 } (2), respectively. Compound 1 features a hat-shaped structure with the parent wheel-shaped {Mo150 } being capped by a {Mo30 } unit on one side. Similarly, 2 exhibits an elliptical lanthanide-doped wheel {Mo120 Ce6 } that is sealed by a {Mo10 } unit on one side. Moreover, the observation of the parent uncapped {Mo150 } and {Mo120 Ce6 } clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150 } and {Mo120 Ce6 } in solution, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Creating Quasi Two-Dimensional Cluster-Assembled Materials through Self-Assembly of a Janus Polyoxometalate-Silsesquioxane Co-Cluster.

    PubMed

    Wu, Han; Zhang, Yu-Qi; Hu, Min-Biao; Ren, Li-Jun; Lin, Yue; Wang, Wei

    2017-05-30

    Clusters are an important class of nanoscale molecules or superatoms that exhibit an amazing diversity in structure, chemical composition, shape, and functionality. Assembling two types of clusters is creating emerging cluster-assembled materials (CAMs). In this paper, we report an effective approach to produce quasi two-dimensional (2D) CAMs of two types of spherelike clusters, polyhedral oligomeric silsesquioxanes (POSS), and polyoxometalates (POM). To avoid macrophase separation between the two clusters, they are covalently linked to form a POM-POSS cocluster with Janus characteristics and a dumbbell shape. This Janus characteristics enables the cocluster to self-assemble into diverse nanoaggregates, as conventional amphiphilic molecules and macromolecules do, in selective solvents. In our study, we obtained micelles, vesicles, nanosheets, and nanoribbons by tuning the n-hexane content in mixed solvents of acetone and n-hexane. Ordered packing of clusters in the nanosheets and nanoribbons were directly visualized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) technique. We infer that the increase of packing order results in the vesicle-to-sheet transition and the change in packing mode causes the sheet-to-ribbon transitions. Our findings have verified the effectivity of creating quasi 2D cluster-assembled materials though the cocluster self-assembly as a new approach to produce novel CAMs.

  17. Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals

    PubMed Central

    Otobe, Saki; Fujioka, Natsumi; Hirano, Takuro; Ishikawa, Eri; Naruke, Haruo; Fujio, Katsuhiko; Ito, Takeru

    2015-01-01

    Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10) had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions. PMID:25894221

  18. Decisive interactions between the heterocyclic moiety and the cluster observed in polyoxometalate-surfactant hybrid crystals.

    PubMed

    Otobe, Saki; Fujioka, Natsumi; Hirano, Takuro; Ishikawa, Eri; Naruke, Haruo; Fujio, Katsuhiko; Ito, Takeru

    2015-04-16

    Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10) had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions.

  19. Breaking the Gordian Knot in the Structural Chemistry of Polyoxometalates: Copper(II)-Oxo/Hydroxo Clusters.

    PubMed

    Kondinski, Aleksandar; Monakhov, Kirill Yu

    2017-06-12

    This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class of polyoxometalate (POM)-like architectures featuring low-to-high nuclearity copper(II)-oxo/hydroxo skeletons. POCus have been identified to adopt the structural principles of classical POMs consisting of early transition metals. Their potential to afford motifs of the noble-metal-based POMs is exploited. "Cross-structural topological transformation" is introduced to generalize skeletal relationships between POCus and POMs. The study opens up strategies toward the brand-new structural chemistry of POCus with relevance to homogeneous photocatalysis, medicinal chemistry, molecular magnetism, and quantum computing. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Polyoxometalates as spin qubits

    NASA Astrophysics Data System (ADS)

    Gaita-Ariño, A.; Aldamen, M.; Clemente-Juan, J.-M.; Coronado, E.; Lehmann, J.; Loss, D.; Stamp, P.

    2008-03-01

    Polyoxometalates (POMs) are discrete fragments of metal oxides, clusters of regular MOn polyhedra. POMs show a remarkable flexibility in composition, structure and charge state, and thus can be designed according to specific electric and magnetic needs. The two localized spins with S = 1/2 on the V atoms in [PMo12O40(VO)2]^q- can be coupled through the delocalized electrons of the central core. This system was recently used for a theoretical scheme involving two-qubit gates and readout: the electrical manipulation of the molecular redox potential changes the charge of the core and thus the effective magnetic exchange between the qubits. Polyoxometalates can encapsulate magnetic ions, protecting them by a diamagnetic shell of controlled geometry. A great potential of POMs as spin qubits is that they can be constructed using only even elements, such as O, W, Mo and/or Si. Thus, there is a high abundance of polyoxometalate molecules without any nuclear spin, which could result in unusually low decoherence rates. There is currently an effort involving highly anisotropic, high magnetic moment, lanthanide@polyoxometalate molecules acting as spin qubits.

  1. A decacobalt(ii) cluster with triple-sandwich structure obtained by partial reductive hydrolysis of a pentacobalt(ii/iii) Weakley-type polyoxometalate.

    PubMed

    Duan, Yan; Clemente-Juan, Juan M; Fierro, José L G; Giménez-Saiz, Carlos; Coronado, Eugenio

    2016-11-03

    Partial reductive hydrolysis of a penta-Co(II/III) cluster [Co(H2O)2(Co(III)W9O34)(PW9O34)](12-) (1) leads to the formation of [Co2{Co3(H2O)(Co(OH)2W7O26)(PW9O34)}2](22-) (2). This polyoxometalate is made up of two capping [PW9O34](9-) units and two bridging [W7O26](10-) units that assemble to encapsulate a novel deca-Co(II) cluster core comprising octahedral and tetrahedral Co(II) ions.

  2. Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

    SciTech Connect

    Yan Bangbo; Hodsdon, Samantha A.; Li Yanfen; Carmichael, Christopher N.; Cao Yan; Pan Weiping

    2011-12-15

    Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy){sub 3}]{sub 2}[H{sub 2}W{sub 12}O{sub 40}]{center_dot}8H{sub 2}O (1), the [Ru(bpy){sub 3}]{sup 2+} (bpy=2,2 Prime -bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} linked through {l_brace}KO{sub 7}{r_brace} and {l_brace}NaO{sub 6}{r_brace} polyhedra, while in K{sub 6}[Ru(pzc){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] Bullet 12H{sub 2}O (2), the [Ru(pzc){sub 3}]{sup -} (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW{sub 12}O{sub 40}]{sup 4-} clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion Midline-Horizontal-Ellipsis {pi} interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature. - Graphical abstract: Two three-dimensional framework solids are constructed from polyoxoanions and ruthenium-organic complexes through noncovalent interactions. Highlights: Black-Right-Pointing-Triangle Ru complexes form hybrid solids with polyoxometalates. Black-Right-Pointing-Triangle Anion Midline-Horizontal-Ellipsis {pi} interaction between polyoxometalates and metal complexes was observed. Black-Right-Pointing-Triangle Noncovalent interactions play an important role in the assembly of solids. Black-Right-Pointing-Triangle The hybrid solid shows luminescence properties.

  3. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    SciTech Connect

    DIETZ,M.L.; RICKERT, P.G.; ANTONIO, M.R.; FIRESTONE, M.A.; WISHART, J.F.; SZREDER, T.

    2007-11-30

    The pairing of a Lindqvist or Keggin polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation, [R{sub 3}R{prime}P]{sup +}, has been shown to yield an original family of ionic liquids (POM-ILs), among them salts liquid at or near ambient temperature. The physicochemical properties of several such 'inorganic liquids', in particular their thermal properties, suggests the possible application of these compounds as robust, thermally-stable solvents for liquid-liquid extraction. A preliminary evaluation of the potential of POM-ILs in this application is presented.

  4. Redox chemistry of the Keggin heteropolyoxotungstate anion in ionic liquids.

    SciTech Connect

    Chiang, M.-H.; Dzielawa, J. A.; Dietz, M. L.; Antonio, M. R.; Chemistry

    2004-06-01

    The solid salts of the 1-ethyl-3-methylimidazolium and the 1-n-pentyl-3-methylimidazolium cations, abbreviated [C{sub 2}mim]{sup +} and [C{sub 5}mim]{sup +}, respectively, of the Keggin heteropolyanion, {alpha}-[PW{sub 12}O{sub 40}]{sup 3-}, were prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements of both [C{sub n}mim]{sub 3}[{alpha}-PW{sub 12}O{sub 40}] salts (for n=2 and 5) were performed in acetonitrile containing either tetra-n-butylammonium hexafluorophosphate, abbreviated TBAPF{sub 6}, or the corresponding [C{sub n}mim]BF{sub 4} ionic liquids (ILs) as electrolytes. The results are compared with the corresponding data obtained in the neat [C{sub n}mim]BF{sub 4} ILs without addition of other electrolytes. The effects of countercation and supporting electrolyte on the voltammetry of the Keggin ion {alpha}-[PW{sub 12}O{sub 40}]{sup 3-} are interpreted as resulting from an amalgamation of isomerization, ion-association, and redox processes. The combination of the unique solvent/electrolyte properties of ILs with the well-known electrochemistry of molecular polyoxometalates (POMs) like the Keggin aanion leads to redox behavior that may have impact on the research and technology of catalytic and energy-storage phenomena.

  5. [Ag(70)(PW(9)O(34))(2)((t)BuC[triple bond, length as m-dash]C)(44)(H(2)O)(2)](8+): ionothermal synthesis of a silver cluster encapsulating lacunary polyoxometalate ions.

    PubMed

    Jiang, Zhan-Guo; Shi, Kang; Lin, Yu-Mei; Wang, Quan-Ming

    2014-03-04

    A silver alkynyl cluster containing a Ag70 shell and two lacunary [PW9O34](9-) templating ions was synthesized by an ionothermal approach. Fast core-shell electronic communication between silver(i) centers and polyoxometalates was verified via cyclic voltammetry studies in [BMIm]BF4.

  6. Cluster-controlled dimerisation in supramolecular ruthenium photosensitizer-polyoxometalate systems.

    PubMed

    Heussner, Kirsten; Peuntinger, Katrin; Rockstroh, Nils; Rau, Sven; Streb, Carsten

    2015-01-07

    A supramolecular reaction system is reported where a labile molecular metal oxide cluster enables the unprecedented dimerisation of ruthenium photosensitizers [Ru(L)2(tmbiH2)](2+) (L = 4,4'-di-tert-butyl-2,2'-bipyridine (1a) or 2,2'-bipyridine (1b); tmbiH2 = 5,5',6,6'-tetramethyl-2,2'-bibenzimidazole). In the presence of [Mo8O26](4-) clusters (2) the dimerisation is triggered by the in situ conversion of [Mo8O26](4-) to [Mo6O19](2-) which results in the release of hydroxide ions. Simultaneous deprotonation of the pH-sensitive tmbiH2-ligands starts the dimerisation, resulting in the formation of the dinuclear complex [(Ru(L)2)2(tmbi)](2+) (L = 4,4'-di-tert-butyl-2,2'-bipyridine (3) or 2,2'-bipyridine (4)). The dimerisation reaction can be suppressed when 2 is replaced by a stable polyoxomolybdate cluster, [Mo5O15(PhPO3)2](4-) (5) and the reaction between 1a and 5 leads to the formation of hydrogen-bonded supramolecular aggregates 6. The solution and solid-state interactions in these systems were investigated using a range of spectroscopic and crystallographic techniques and compounds 3, 4 and 6 were characterized using single-crystal XRD.

  7. A silver-alkynyl cluster encapsulating a fluorescent polyoxometalate core: enhanced emission and fluorescence modulation.

    PubMed

    Song, Chao-Yu; Chai, Dong-Feng; Zhang, Rui-Ren; Liu, Hong; Qiu, Yun-Feng; Guo, Hua-Dong; Gao, Guang-Gang

    2015-03-07

    A new silver(I)-alkynyl cluster with a [Eu(W5O18)2](9-) polyoxoanionic core of [Ag42{Eu(W5O18)2}((t)BuC≡C)28Cl4] [OH]·H2O (1) has been designed and synthesized. The [Eu(W5O18)2](9-) polyoxoanion acts as a template to induce the formation of the surrounding 42-core Ag(I) cage. Due to the hydrophobic silver(I)-alkynyl shell, 1 features an unusual fluorescence enhancement as compared to the precursor of the [Eu(W5O18)2](9-) polyoxoanionic core. Interestingly, the silver ions in the shell silver(I)-alkynyl cage can only be reduced to silver atoms by irradiation with high energy UV light (2 kW). Upon high UV irradiation, fluorescence quenching of 1 has been observed. Moreover, the solution fluorescence of 1 can be modulated by addition of S(2-) ions into the system, which also leads to the fluorescence quenching phenomenon. The successful synthesis of 1 demonstrates a new route to the detection of high energy UV irradiation or S(2-) ions by elaborate design of fluorescence quenching of silver(I)-alkynyl clusters.

  8. The key role of -CH3 steric hindrance in bis(pyrazolyl) ligand on polyoxometalate-based compounds.

    PubMed

    Tian, Ai-xiang; Yang, Yang; Ying, Jun; Li, Na; Lin, Xiao-ling; Zhang, Ju-wen; Wang, Xiu-li

    2014-06-14

    Through using two kinds of bis(pyrazolyl) ligands, four polyoxometalate (POM)-based compounds were hydrothermally synthesized and structurally characterized, [Ag3(Hbhpe)2(H2O)(H2PMo12O40)]·H2O (1), [Ag(H2bdpm)2(H2PW12O40)]·4H2O (2), [Ag6(H2bdpm)6(HPW(VI)8W(V)4O40)]·2H2O (2) and [Ag4(H2bdpm)4(H2P2W18O62)]·3H2O (4) (H2bhpe = 1,2-bis(1-H-pyrazolate)ethane, H2bdpm = 1,1'-bis(3,5-dimethyl-1H-pyrazolate)methane). In compound 1, the Ag-Hbhpe subunit is a 2D layer containing large penta-membered cycles and small tri-nuclear Ag(I) clusters. The Keggin anions covalently float on the large cycles. In compound 2, the Keggin anions are fused by [Ag(H2bdpm)2](+) subunits to form a 1D chain. Compound contains hexa-membered metal-organic cycles, which are further linked by Keggin anions to build a 1D chain. Adjacent chains share the Ag(I) ions to construct a 3D framework of 3. Compound 4 exhibits a wavy double-track chain structure, with the Wells-Dawson anions covalently suspended up and down this chain. The steric hindrance of -CH3 groups in H2bdpm leads to the formation of mono-nuclear Ag(I) subunits in 2 - 4. The influence of -CH3 steric hindrance in bis(pyrazolyl) ligands on the structures of 1 - 4 is discussed. The electrochemical and photocatalytic properties of the title compounds have been studied.

  9. Self-assembly of four new extended architectures based on reduced polyoxometalate clusters and cadmium complexes

    NASA Astrophysics Data System (ADS)

    Ma, Ying; Li, Yangguang; Wang, Enbo; Lu, Ying; Wang, Xinlong; Xu, Xinxin

    2006-08-01

    Four new [P 4Mo 6] cluster-based extended structures containing cadmium complexes, [Cd 3(4,4'-Hbpy) 2(4,4'-bpy) 2(H 2O) 8][Cd(H 2PO 4) 2(HPO 4) 4(PO 4) 2(MoO 2) 12(OH) 6]·7H 2O 1, (4,4'-Hbpy) 2[Cd(4,4'-bpy) 3(H 2O) 3][Cd(4,4'-bpy)(H 2O)] 2[Cd(H 2PO 4) 2(HPO 4) 4 (PO 4) 2(MoO 2) 12(OH) 6]·H 2O 2, [Cd 4(phen) 2(H 2O) 4][Cd(phen)(H 2O)] 2[Cd(HPO 4) 4 (HPO 4) 4(MoO 2) 12(OH) 6]·5H 2O 3 and [Cd 4(2,2'-bpy) 2(H 2O) 4][Cd(2,2'-bpy)(H 2O)] 2 [Cd(HPO 4) 4(HPO 4) 4(MoO 2) 12(OH) 6]·3H 2O 4 (4,4'-bpy=4,4'-bpyridine, phen=1,10-phenanthroline, 2,2'-bpy=2,2'-bpyridine), have been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The structure of compound 1 is constructed from the Cd[P 4Mo 6] 2 dimers linked by [Cd 3(4,4'-Hbpy) 2(4,4'-bpy) 2(H 2O) 8] subunits to generate a plane layer. Compound 2 consists of the positive 2D sheets that constructed from Cd[P 4Mo 6] 2 dimers linked by [Cd(4,4'-bpy)(H 2O)] complexes, then the 2D sheets are further linked up together to form a 3D supramolecular framework via extensive hydrogen-bonding interactions among the [P 4Mo 6] clusters, free 4,4'-bpy molecules, dissociated [Cd(4,4'-bpy) 3(H 2O) 3] 2+ complexes and water molecules. Compounds 3 and 4 show new 2D layered structure, with Cd[P 4Mo 6] 2 building blocks connected by tetra-nuclear [Cd 4{(phen) 2/(2,2'-bpy) 2}(H 2O) 4] clusters and [Cd(phen/2,2'-bpy)(H 2O)] complexes. The fluorescent activities of compounds 3 and 4 are reported.

  10. Polyoxometalate-Based Gels and Nanostructured Materials for Decontamination Under Ambient Conditions

    DTIC Science & Technology

    2003-11-19

    features will be addressed. This work was and is supported by Army Research Office. Transition-metal oxygen anion clusters ( polyoxometalates or... Polyoxometalate -based gels and nanostructured materials for decontamination under ambient conditions Craig L. Hill, Wade Neiwert, Nelya Okun...2003 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Polyoxometalate -based gels and nanostructuredmaterials for

  11. Polyoxometalate-based solar cells for water splitting

    NASA Astrophysics Data System (ADS)

    Cronin, Leroy; Molina, Pedro I.; Miras, Haralampos N.

    2011-10-01

    The design and assembly of redox active polyoxometalate clusters, and their potential as water oxidation catalysts is discussed. The activity of the clusters is placed into context with comparisons to other systems and routes to the design and solution control of the assembly of novel polyoxometalate clusters with the correct characteristics for catalysis is also presented. Building on these features, a potential new polyoxometalate-based device architecture is presented that combines redox active polyoxometalate clusters, using systems that have been shown to be good water oxidation catalysts or structural models for photosystem II, with large cationic dyes to produce microtubular architectures that can be deposited on transparent substrates. The combination of a range of highly redox and catalytically active polyoxometalates with a range of possible cationic dye candidates allows the development of modular device architectures that can be screened and developed as potential new solar fuel cells.

  12. An X-ray and Neutron Scattering Study of the Formation of Core-Shell Type Polyoxometalates

    SciTech Connect

    Yin, Panchao; Wu, Bin; Mamontov, Eugene; Daemen, Luke L.; Cheng, Yongqiang; Li, Tao; Seifert, Soenke; Hong, Kunlun; Bonnesen, Peter V.; Keum, Jong Kahk; Ramirez-Cuesta, Anibal J.

    2016-03-02

    A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalatetemplated growth of a layer of spherical shell structure of {Mo72Fe30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Timeresolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with customed physical models, which provide more convincing, objective, and completed data interpretation. Quasielastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.

  13. Hydrothermal synthesis and characterization of the tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate: {PW 4VIW 5VV 3IVO 40(V IVO) 3[Cu(en) 2]} 6-

    NASA Astrophysics Data System (ADS)

    Liu, Jian; Xu, Jia-Ning; Liu, Ya-Bing; Lu, Yu-Kun; Song, Jiang-Feng; Zhang, Xiao; Cui, Xiao-Bing; Xu, Ji-Qing; Wang, Tie-Gang

    2007-12-01

    A novel polyoxometalate [Cu(phen) 2] 3{PW 4VIW 5VV 3IVO 40(V IVO) 3[Cu(en) 2]}ṡ4H 2O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {PW 4VIW 5VV 3IVO 40(V IVO) 3[Cu(en) 2]} 6-, three [Cu(phen) 2] 2+ cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and π- π stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure.

  14. Mixed addenda polyoxometalate "solutions" for stationary energy storage.

    PubMed

    Pratt, Harry D; Anderson, Travis M

    2013-11-28

    A series of redox flow batteries utilizing mixed addenda (vanadium and tungsten), phosphorus-based polyoxometalates (A-α-PV3W9O40(6-), B-α-PV3W9O40(6-), and P2V3W15O62(9-)) were prepared and tested. Cyclic voltammetry and bulk electrolysis experiments on the Keggin compounds (A-α-PV3W9O40(6-) and B-α-PV3W9O40(6-)) established that the vanadium centers of these compounds could be used as the positive electrode (PV(IV)3W(VI)9O40(9-)/PV(V)3W(VI)9O40(6-)), and the tungsten centers could be used as the negative electrode (PV(IV)3W(VI)9O40(9-)/PV(IV)3W(V)3W(VI)6O40(12-)) since these electrochemical processes are separated by about 1 V. The results showed that A-α-PV3W9O40(6-) (where A indicates adjacent, corner-sharing vanadium atoms) had coulombic efficiencies (charge in divided by charge out) above 80%, while the coulombic efficiency of B-α-PV3W9O40(6-) (where B indicates adjacent edge-sharing vanadium atoms) fluctuated between 50% and 70% during cycling. The electrochemical yield, a measurement of the actual charge or discharge observed in comparison with the theoretical charge, was between 40% and 50% for A-α-PV3W9O40(6-), and (31)P NMR showed small amounts of PV2W10O40(5-) and PVW11O40(4-) formed with cycling. The electrochemical yield for B-α-PV3W9O40(6-) decreased from 90% to around 60% due to precipitation of the compound on the electrode, but there were no decomposition products detected in the solution by (31)P NMR, and infrared data on the electrode suggested that the cluster remained intact. Testing of P2V3W15O62(9-) (Wells-Dawson structure) suggested higher charge density clusters were not as suitable as the Keggin structures for a redox flow battery due to the poor stability and inaccessibility of the highly reduced materials.

  15. Molecule-Based Water-Oxidation Catalysts (WOCs): Cluster-Size-Dependent Dye-Sensitized Polyoxometalates for Visible-Light-Driven O2 Evolution

    PubMed Central

    Gao, Junkuo; Cao, Shaowen; Tay, Qiuling; Liu, Yi; Yu, Lingmin; Ye, Kaiqi; Mun, Peter Choon Sze; Li, Yongxin; Rakesh, Ganguly; Loo, Say Chye Joachim; Chen, Zhong; Zhao, Yang; Xue, Can; Zhang, Qichun

    2013-01-01

    From atomic level to understand the cluster-size-dependant behavior of dye-sensitized photocatalysts is very important and helpful to design new photocatalytic materials. Although the relationship between the photocatalytic behaviors and particles' size/shape has been widely investigated by theoretical scientists, the experimental evidences are much less. In this manuscript, we successfully synthesized three new ruthenium dye-sensitized polyoxometalates (POM-n, n relate to different size clusters) with different-sized POM clusters. Under visible-light illumination, all three complexes show the stable O2 evolution with the efficient order POM-3 > POM-2 > POM-1. This cluster-size-dependent catalytic behavior could be explained by the different numbers of M = Ot (terminal oxygen) bonds in each individual cluster because it is well-known that Mo = Ot groups are the catalytically active sites for photooxidation reaction. The proposed mechanism of water oxidation for the dye-sensitized POMs is radical reaction process. This research could open up new perspectives for developing new POM-based WOCs. PMID:23676701

  16. Assembly of Cu/Ag-quinoxaline-polyoxotungstate hybrids: Influence of Keggin and Wells-Dawson polyanions on the structure

    NASA Astrophysics Data System (ADS)

    Chi, Ying-Nan; Cui, Feng-Yun; Lin, Zheng-Guo; Xu, Yan; Ma, Xiao-Yu; Shen, Pan-Pan; Huang, Kun-Lin; Hu, Chang-Wen

    2013-03-01

    In order to investigate the influence of Keggin and Wells-Dawson polyoxometalates on the resultant structure, four new organic-inorganic hybrid compounds [Cu4(qx)5(SiW12O40)] (1), [Cu6(qx)6(P2W18O62)(H2O)1.5]·4.5H2O (2), [Ag4(qx)4(SiW12O40)(H2O)]·H2O (3), [Ag6(qx)6(P2W18O62)]·8H2O (4) (qx=quinoxaline) were synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, the 2D layers are linked by the SiW12O404- (SiW12) anions to construct a 3D framework. When the Wells-Dawson type P2W18O626- (P2W18) is used, 2 is prepared, in which the 1D helical chains are connected by P2W18 to form a 3D network. In 3, two kinds of 1D metal-organic chains are connected by SiW12 clusters to construct a 3D framework. In 4, there are also two kinds of 1D chains one kind of 1D chain combines with P2W18 by the AgO weak interaction and the other kind is just metal-organic chain. In addition, the electrochemistry properties of compounds 1-4 have been studied.

  17. Efficient visible-light photocatalytic activity by band alignment in mesoporous ternary polyoxometalate-Ag2S-CdS semiconductors.

    PubMed

    Kornarakis, I; Lykakis, I N; Vordos, N; Armatas, G S

    2014-08-07

    Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster anions with different reduction potentials, such as PW12O40(3-), SiW12O40(4-) and PMo12O40(3-), were employed as electron acceptors in these ternary heterojunction photocatalysts. Characterization by small-angle X-ray scattering, X-ray diffraction, transmission electron microscopy and N2 physisorption measurements showed hexagonal arrays of POM-Ag2S-CdS hybrid nanorods with large internal BET surface areas and uniform mesopores. The Keggin structure of the incorporated POM clusters was also verified by elemental X-ray spectroscopy microanalysis, infrared and diffuse-reflectance ultraviolet-visible spectroscopy. These new porous materials were implemented as visible-light-driven photocatalysts, displaying exceptional high activity in aerobic oxidation of various para-substituted benzyl alcohols to the corresponding carbonyl compounds. Our experiments show that the spatial separation of photogenerated electrons and holes at CdS through the potential gradient along the CdS-Ag2S-POM interfaces is responsible for the increased photocatalytic activity.

  18. New Perspectives for Old Clusters: Anderson-Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d-4 f Species.

    PubMed

    Artetxe, Beñat; Reinoso, Santiago; San Felices, Leire; Lezama, Luis; Gutiérrez-Zorrilla, Juan M; Vicent, Cristian; Haso, Fadi; Liu, Tianbo

    2016-03-18

    A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8](17-) heterometallic anions (Ln3M2; Ln=La-Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs-type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ɛ-Keggin cluster. It is shown, for the first time, that classical Anderson-Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk-shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left- or right-handed orientations. Their ability to self-associate in blackberry-type vesicles in solution has been assessed for the Ce3Co2 derivative. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A polyoxometalate flow battery

    SciTech Connect

    Pratt, Harry D.; Hudak, Nicholas S.; Fang, Xikui; Anderson, Travis M.

    2013-08-01

    A redox flow battery utilizing two, three-electron polyoxometalate redox couples (SiVV3WVI9O407–/SiVIV3WVI9O4010- and SiVIV3WVI9O4010-/SiVIV3WV3WVI6O4013-) was investigated for use in stationary storage in either aqueous or non-aqueous conditions. The aqueous battery had coulombic efficiencies greater than 95% with relatively low capacity fading over 100 cycles. Infrared studies showed there was no decomposition of the compound under these conditions. The non-aqueous analog had a higher operating voltage but at the expense of coulombic efficiency. The spontaneous formation of these clusters by self-assembly facilitates recovery of the battery after being subjected to reversed polarity. Polyoxometalates offer a new approach to stationary storage materials because they are capable of undergoing multi-electron reactions and are stable over a wide range of pH values and temperatures.

  20. Exploring the utility of organo-polyoxometalate hybrids to inhibit SOX transcription factors

    PubMed Central

    2014-01-01

    Background SOX transcription factors constitute an attractive target class for intervention with small molecules as they play a prominent role in the field of regenerative biomedicine and cancer biology. However, rationally engineering specific inhibitors that interfere with transcription factor DNA interfaces continues to be a monumental challenge in the field of transcription factor chemical biology. Polyoxometalates (POMs) are inorganic compounds that were previously shown to target the high-mobility group (HMG) of SOX proteins at nanomolar concentrations. In continuation of this work, we carried out an assessment of the selectivity of a panel of newly synthesized organo-polyoxometalate hybrids in targeting different transcription factor families to enable the usage of polyoxometalates as specific SOX transcription factor drugs. Results The residual DNA-binding activities of 15 different transcription factors were measured after treatment with a panel of diverse polyoxometalates. Polyoxometalates belonging to the Dawson structural class were found to be more potent inhibitors than the Keggin class. Further, organically modified Dawson polyoxometalates were found to be the most potent in inhibiting transcription factor DNA binding activity. The size of the polyoxometalates and its derivitization were found to be the key determinants of their potency. Conclusion Polyoxometalates are highly potent, nanomolar range inhibitors of the DNA binding activity of the Sox-HMG family. However, binding assays involving a limited subset of structurally diverse polyoxometalates revealed a low selectivity profile against different transcription factor families. Further progress in achieving selectivity and deciphering structure-activity relationship of POMs require the identification of POM binding sites on transcription factors using elaborate approaches like X-ray crystallography and multidimensional NMR. In summary, our report reaffirms that transcription factors are

  1. {Mo24Fe12} macrocycles: anion templation with large polyoxometalate guests.

    PubMed

    Fang, Xikui; Hansen, Laura; Haso, Fadi; Yin, Panchao; Pandey, Abhishek; Engelhardt, Larry; Slowing, Igor; Li, Tao; Liu, Tianbo; Luban, Marshall; Johnston, David C

    2013-09-27

    POM and circumstance: Nanometer-sized polyoxometalates (POMs) bring a new direction to anion-templated supramolecular chemistry. The Keggin (left) and Dawson-type (right) polyoxoanions direct the assembly of giant metallomacrocycles through an array of weak hydrogen-bonding interactions. The concerted action of multiple hydrogen bonds keeps the templating guests embedded within the hosts, even in the solution state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Questioning the paradigm of metal complex promoted phosphodiester hydrolysis: [Mo7O24](6-) polyoxometalate cluster as an unlikely catalyst for the hydrolysis of a DNA model substrate.

    PubMed

    Cartuyvels, Els; Absillis, Gregory; Parac-Vogt, Tatjana N

    2008-01-07

    The first example of a phosphodiester bond cleavage promoted by a highly negatively charged polyoxometalate cluster has been discovered: the hydrolysis of the phosphodiester bond in a DNA model substrate bis(p-nitrophenyl)phosphate (BNPP) is promoted by the heptamolybdate anion [Mo7O24](6-) with rates which represent an acceleration of nearly four orders of magnitude compared to the uncatalyzed cleavage.

  3. Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.

    SciTech Connect

    Rickert, P. G.; Antonio, M. P.; Firestone, M. A.; Kubatko, K.-A.; Szreder, T.; Wishart, J. F.; Dietz, M. L.; Chemistry; Univ. of Notre Dame; BNL

    2007-01-01

    Pairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature 'liquid POM' comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.

  4. Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity-hydrophobicity balance and supramolecularity.

    PubMed

    Raj, Gijo; Swalus, Colas; Arendt, Eglantine; Eloy, Pierre; Devillers, Michel; Gaigneaux, Eric M

    2014-01-01

    The hybridization of polyoxometalates (POMs) through an organic-inorganic association offers several processing advantages in the design of heterogeneous catalysts. A clear understanding of the organization of these hybrid materials on solid surfaces is necessary to optimise their properties. Herein, we report for the first time the organization of Keggin phosphotungstic [PW12O40](3-) and Wells-Dawson (WD) phosphomolybdic [P2Mo18O62](6-) anions deposited on mica (hydrophilic), and highly oriented pyrolytic graphite (HOPG) (hydrophobic) surfaces. Next, the supramolecular organization of the organic-inorganic hybrid materials formed from the association of POM anions and dimethyldioctadecylammonium bromide (DODA) is investigated as a function of the hydrophilic or hydrophobic nature of the surfaces. The height of the Keggin-POM anions, measured with tapping mode (TM-AFM) is always in good agreement with the molecular dimension of symmetric Keggin-POM anions (ca. 1 nm). However, the asymmetric WD-POM anions form monolayer assemblies on the surfaces with the orientation of their long molecular axis (ca. 1.6 nm) depending on the hydrophilic or hydrophobic properties of the substrate. Namely, the long axis is parallel on mica, and perpendicular on HOPG. When hybridized with DODA, the organization of the hybrid material is dictated by the interaction of the alkyl side chains of DODA with the substrate surface. On HOPG, the DODA-POM hybrid forms small domains of epitaxially arranged straight nanorod structures with their orientation parallel to each other. Conversely, randomly distributed nanospheres are formed when the hybrid material is deposited on freshly cleaved mica. Finally, a UV-ozone treatment of the hybrid material allows one to obtain highly dispersed isolated POM entities on both hydrophilic and hydrophobic surfaces. The hybridization strategy to prevent the clustering of POMs on various supports would enable to develop highly dispersed POM-based heterogeneous

  5. Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity–hydrophobicity balance and supramolecularity

    PubMed Central

    Swalus, Colas; Arendt, Eglantine; Eloy, Pierre; Devillers, Michel

    2014-01-01

    Summary The hybridization of polyoxometalates (POMs) through an organic–inorganic association offers several processing advantages in the design of heterogeneous catalysts. A clear understanding of the organization of these hybrid materials on solid surfaces is necessary to optimise their properties. Herein, we report for the first time the organization of Keggin phosphotungstic [PW12O40]3− and Wells–Dawson (WD) phosphomolybdic [P2Mo18O62]6− anions deposited on mica (hydrophilic), and highly oriented pyrolytic graphite (HOPG) (hydrophobic) surfaces. Next, the supramolecular organization of the organic–inorganic hybrid materials formed from the association of POM anions and dimethyldioctadecylammonium bromide (DODA) is investigated as a function of the hydrophilic or hydrophobic nature of the surfaces. The height of the Keggin-POM anions, measured with tapping mode (TM-AFM) is always in good agreement with the molecular dimension of symmetric Keggin-POM anions (ca. 1 nm). However, the asymmetric WD-POM anions form monolayer assemblies on the surfaces with the orientation of their long molecular axis (ca. 1.6 nm) depending on the hydrophilic or hydrophobic properties of the substrate. Namely, the long axis is parallel on mica, and perpendicular on HOPG. When hybridized with DODA, the organization of the hybrid material is dictated by the interaction of the alkyl side chains of DODA with the substrate surface. On HOPG, the DODA–POM hybrid forms small domains of epitaxially arranged straight nanorod structures with their orientation parallel to each other. Conversely, randomly distributed nanospheres are formed when the hybrid material is deposited on freshly cleaved mica. Finally, a UV–ozone treatment of the hybrid material allows one to obtain highly dispersed isolated POM entities on both hydrophilic and hydrophobic surfaces. The hybridization strategy to prevent the clustering of POMs on various supports would enable to develop highly dispersed POM

  6. Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

    PubMed

    Hoshino, Takahiro; Isobe, Rina; Kaneko, Takuya; Matsuki, Yusuke; Nomiya, Kenji

    2017-08-21

    A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca6(CO3)(μ3-OH)(OH2)18}(P2W15Ti3O61)3Ca(OH2)3](19-) (Ca7Ti9Trimer), was obtained as the Na7Ca6 salt (NaCa-Ca7Ti9Trimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[P2W15Ti3O59(OH)3](9-)" (Ti3Monomer). Ti3Monomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH2)3 groups and an encapsulated Cl(-) ion, [{P2W15Ti3O59(OH)3}4{μ3-Ti(H2O)3}4Cl](21-) (Ti16Tetramer). The Na7Ca6 salt of Ca7Ti9Trimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution (183)W and (31)P NMR spectroscopy. X-ray crystallography revealed that the [Ca6(CO3)(μ3-OH)(OH2)18](9+) cluster cation was composed of six calcium cations linked by one μ6-carbonato anion and one μ3-OH(-) anion. The cluster cation was assembled, together with one calcium ion, on a trimeric species composed of three tri-Ti(IV)-substituted Wells-Dawson subunits linked by Ti-O-Ti bonds. Ca7Ti9Trimer is an unprecedented POM species containing an alkaline-earth-metal cluster cation and is the first example of alkaline-earth-metal ions clustered around a titanium(IV)-substituted POM.

  7. Chemical Stabilization and Electrochemical Destabilization of the Iron Keggin Ion in Water

    SciTech Connect

    Sadeghi, Omid; Falaise, Clément; Molina, Pedro I.; Hufschmid, Ryan; Campana, Charles F.; Noll, Bruce C.; Browning, Nigel D.; Nyman, May

    2016-10-18

    The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular non-classical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2]3+ and [Bi6FeO4Fe12O12(OH)12(CF3COO)12]1+. Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pH 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi3+-cations and the trifluoroacetate ligands that respectively bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster metal oxide conversion processes in detail.

  8. Chemical Stabilization and Electrochemical Destabilization of the Iron Keggin Ion in Water.

    PubMed

    Sadeghi, Omid; Falaise, Clément; Molina, Pedro I; Hufschmid, Ryan; Campana, Charles F; Noll, Bruce C; Browning, Nigel D; Nyman, May

    2016-11-07

    The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular, nonclassical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated as [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2](3+) (Kegg-1) and [Bi6FeO4Fe12O12(OH)12(CF3COO)12](1+) (Kegg-2). Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pH 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi(3+) cations and the trifluoroacetate ligands that, respectively, bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster to metal oxide conversion processes in detail.

  9. Formation, isomerization, and derivatization of keggin tungstoaluminates.

    Treesearch

    Jennifer J. Cowan; Alan J. Bailey; Robert A. Heintz; Bao T. Do; Kenneth I. Hardcastle; Craig L. Hill; Ira A. Weinstock

    2001-01-01

    Trends in the stability of ¥á and ©¬-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-...

  10. Highly Dispersed Polyoxometalate-Doped Porous Co3 O4 Water Oxidation Photocatalysts Derived from POM@MOF Crystalline Materials.

    PubMed

    Lan, Qing; Zhang, Zhi-Ming; Qin, Chao; Wang, Xin-Long; Li, Yang-Guang; Tan, Hua-Qiao; Wang, En-Bo

    2016-10-17

    Rational design of earth-abundant photocatalysts is an important issue for solar energy conversion and storage. Polyoxometalate (POM)@Co3 O4 composites doped with highly dispersive molecular metal-oxo clusters, synthesized by loading a single Keggin-type POM cluster into each confined space of a metal-organic framework (MOF), exhibit significantly improved photocatalytic activity in water oxidation compared to the pure MOF-derived nanostructure. The systematic synthesis of these composite nanocrystals allows the conditions to be tuned, and their respective water oxidation catalytic performance can be efficiently adjusted by varying the thermal treatment temperature and the feeding amount of the POM. This work not only provides a modular and tunable synthetic strategy for preparing molecular cluster@TM oxide (TM=transition metal) nanostructures, but also showcases a universal strategy that is applicable to design and construct multifunctional nanoporous metal oxide composite materials. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.

    PubMed

    Takashima, Yohei; Miras, Haralampos N; Glatzel, Stefan; Cronin, Leroy

    2016-06-14

    We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integrity is retained after the surface modifications. In addition, the formation of polyoxometalate-based self-fabricating tubes by the dissolution of Keggin-based network crystals were also modulated by the polymers, allowing a new type of hybrid inorganic polymer with an organic coating to be fabricated.

  12. Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW9O34](10-) Polyoxometalate.

    PubMed

    Duval, Sylvain; Béghin, Sébastien; Falaise, Clément; Trivelli, Xavier; Rabu, Pierre; Loiseau, Thierry

    2015-09-08

    The reaction of Na10[α-SiW9O34] with tetravalent metallic cations such as 4f ((NH4)2Ce(NO3)6), 5d (HfCl4), or 5f (UCl4 and Th(NO3)4) in a pH 4.7 sodium acetate buffer solution leads to the formation of four sandwich-type polyoxometalates [Ce4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (1), [U4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (2), [Th3(μ(3)-O)(μ(2)-OH)3(SiW9O34)2](13-) (3), and [Hf3(μ(2)-OH)3(SiW9O34)2](11-) (4). All four compounds consist of a polynuclear cluster fragment stabilized by two [α-SiW9O34](10-) polyanions. Compounds 1 and 2 are isostructural with a tetranuclear core (Ce4, U4), while compound 3 presents a trinuclear Th3 core bearing a μ(3)-O-centered bridge. It is an unprecedented configuration in the case of the thorium(IV) cluster. Compound 4 also possesses a trinuclear Hf3 core but with the absence of the μ(3)-O bridge. The molecules have been characterized by single-crystal X-ray diffraction, (183)W and (29)Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis.

  13. A fluorophosphate-based inverse Keggin structure.

    PubMed

    Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kögerler, Paul

    2012-09-07

    An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

  14. A fluorophosphate-based inverse Keggin structure

    SciTech Connect

    Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kogerler, Paul

    2012-07-17

    An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

  15. Probing Frontier Orbital Energies of {Co9(P2W15)3} Polyoxometalate Clusters at Molecule-Metal and Molecule-Water Interfaces.

    PubMed

    Yi, Xiaofeng; Izarova, Natalya V; Stuckart, Maria; Guérin, David; Thomas, Louis; Lenfant, Stéphane; Vuillaume, Dominique; van Leusen, Jan; Duchoň, Tomáš; Nemšák, Slavomír; Bourone, Svenja D M; Schmitz, Sebastian; Kögerler, Paul

    2017-09-27

    Functionalization of polyoxotungstates with organoarsonate coligands enabling surface decoration was explored for the triangular cluster architectures of the composition [Co(II)9(H2O)6(OH)3(p-RC6H4As(V)O3)2(α-P(V)2W(VI)15O56)3](25-) ({Co9(P2W15)3}, R = H or NH2), isolated as Na25[Co9(OH)3(H2O)6(C6H5AsO3)2(P2W15O56)3]·86H2O (Na-1; triclinic, P1̅, a = 25.8088(3) Å, b = 25.8336(3) Å, c = 27.1598(3) Å, α = 78.1282(11)°, β = 61.7276(14)°, γ = 60.6220(14)°, V = 13888.9(3) Å(3), Z = 2) and Na25[Co9(OH)3(H2O)6(H2NC6H4AsO3)2(P2W15O56)3]·86H2O (Na-2; triclinic, P1̅, a = 14.2262(2) Å, b = 24.8597(4) Å, c = 37.9388(4) Å, α = 81.9672(10)°, β = 87.8161(10)°, γ = 76.5409(12)°, V = 12920.6(3) Å(3), Z = 2). The axially oriented para-aminophenyl groups in 2 facilitate the formation of self-assembled monolayers on gold surfaces and thus provide a viable molecular platform for charge transport studies of magnetically functionalized polyoxometalates. The title systems were isolated and characterized in the solid state, in aqueous solutions, and on metal surfaces. Using conducting tip atomic force microscopy, the energies of {Co9(P2W15)3} frontier molecular orbitals in the surface-bound state were found to directly correlate with cyclic voltammetry data in aqueous solution.

  16. Stepwise synthesis of two inorganic-organic hybrids based on the manganese monosubstituted Keggin polyanion chains

    NASA Astrophysics Data System (ADS)

    Zhang, Chun-Jing; Huang, Nan-Nan; Yang, Da-Yü; Chen, Ya-Guang; Pang, Hai-Jun

    2014-09-01

    Two new hybrid compounds based on the manganese monosubstituted Keggin polyanion chains, [H2bpy][Ag(bpy)]2[HPMnMo11O39] (1) and [H2bpy]2[Hbpy][PMnMo11O39]·H2O (2), (bpy = 4,4‧-bipyridine) have been stepwise synthesized under hydrothermal condition and characterized by elemental analyses, IR spectra, thermogravimetry, and single-crystal X-ray diffraction technique. Structural characterization reveals that although both 1 and 2 contain manganese monosubstituted Keggin polyanion chains, the polyanion chains are not in the full consistent way. In 1, the neighboring manganese monosubstituted Keggin clusters are connected via sharing the para position oxygen atoms of the clusters to form a linear polyanion chain in which the monosubstituted Keggin clusters are further grafted by silver coordination polymer chains forming a 2D network. Whereas the polyanion chain in 2 exhibits a zigzag structure, which is formed by sharing the metaposition terminal oxygen atoms of the clusters, rather than para position terminal oxygen atoms as that in 1. Each zigzag chain contacts with four adjacent chains along four directions through short interspecies contacts, forming a 3D supramolecular framework. The protonated Hbipy+ and H2bipy2+ molecules as the counter cations exist in voids of the supramolecular framework in 2. Furthermore, photocatalytic experiments indicate that 1 has good activities for photocatalytic degradation of RhB under UV irradiation.

  17. Oxidation catalysis by polyoxometalates fundamental electron-transfer phenomena

    Treesearch

    Yurii V. Geletii; Rajai H. Atalla; Alan J. Bailey; Laurent Delannoy; Craig L. Hill; Ira A. Weinstock

    2002-01-01

    Early transition-metal oxygen-anion clusters (polyoxometalates, POMs) are a large and rapidly growing class of versatile and tunable oxidation catalysts. All key molecular properties of these clusters (composition, size, shape, charge density, reduction potential, solubility, etc.) can be systematically altered, and the clusters themselves can serve as tunable ligands...

  18. High-field pulsed EPR spectroscopy for the speciation of the reduced [PV(2)Mo(10)O(40)](6-) polyoxometalate catalyst used in electron-transfer oxidations.

    PubMed

    Kaminker, Ilia; Goldberg, Hila; Neumann, Ronny; Goldfarb, Daniella

    2010-09-03

    An in-depth spectroscopic EPR investigation of a key intermediate, formally notated as [PV(IV)V(V)Mo(10)O(40)](6-) and formed in known electron-transfer and electron-transfer/oxygen-transfer reactions catalyzed by H(5)PV(2)Mo(10)O(40), has been carried out. Pulsed EPR spectroscopy have been utilized: specifically, W-band electron-electron double resonance (ELDOR)-detected NMR and two-dimensional (2D) hyperfine sub-level correlation (HYSCORE) measurements, which resolved (95)Mo and (17)O hyperfine interactions, and electron-nuclear double resonance (ENDOR), which gave the weak (51)V and (31)P interactions. In this way, two paramagnetic species related to [PV(IV)V(V)Mo(10)O(40)](6-) were identified. The first species (30-35 %) has a vanadyl (VO(2+))-like EPR spectrum and is not situated within the polyoxometalate cluster. Here the VO(2+) was suggested to be supported on the Keggin cluster and can be represented as an ion pair, [PV(V)Mo(10)O(39)](8-)[V(IV)O(2+)]. This species originates from the parent H(5)PV(2)Mo(10)O(40) in which the vanadium atoms are nearest neighbors and it is suggested that this isomer is more likely to be reactive in electron-transfer/oxygen-transfer reaction oxidation reactions. In the second (70-65 %) species, the V(IV) remains embedded within the polyoxometalate framework and originates from reduction of distal H(5)PV(2)Mo(10)O(40) isomers to yield an intact cluster, [PV(IV)V(V)Mo(10)O(40)](6-).

  19. Polyoxometalate flow battery

    DOEpatents

    Anderson, Travis M.; Pratt, Harry D.

    2016-03-15

    Flow batteries including an electrolyte of a polyoxometalate material are disclosed herein. In a general embodiment, the flow battery includes an electrochemical cell including an anode portion, a cathode portion and a separator disposed between the anode portion and the cathode portion. Each of the anode portion and the cathode portion comprises a polyoxometalate material. The flow battery further includes an anode electrode disposed in the anode portion and a cathode electrode disposed in the cathode portion.

  20. Efficient visible-light photocatalytic activity by band alignment in mesoporous ternary polyoxometalate-Ag2S-CdS semiconductors

    NASA Astrophysics Data System (ADS)

    Kornarakis, I.; Lykakis, I. N.; Vordos, N.; Armatas, G. S.

    2014-07-01

    Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster anions with different reduction potentials, such as PW12O403-, SiW12O404- and PMo12O403-, were employed as electron acceptors in these ternary heterojunction photocatalysts. Characterization by small-angle X-ray scattering, X-ray diffraction, transmission electron microscopy and N2 physisorption measurements showed hexagonal arrays of POM-Ag2S-CdS hybrid nanorods with large internal BET surface areas and uniform mesopores. The Keggin structure of the incorporated POM clusters was also verified by elemental X-ray spectroscopy microanalysis, infrared and diffuse-reflectance ultraviolet-visible spectroscopy. These new porous materials were implemented as visible-light-driven photocatalysts, displaying exceptional high activity in aerobic oxidation of various para-substituted benzyl alcohols to the corresponding carbonyl compounds. Our experiments show that the spatial separation of photogenerated electrons and holes at CdS through the potential gradient along the CdS-Ag2S-POM interfaces is responsible for the increased photocatalytic activity.Porous multicomponent semiconductor materials show improved photocatalytic performance due to the large and accessible pore surface area and high charge separation efficiency. Here we report the synthesis of well-ordered porous polyoxometalate (POM)-Ag2S-CdS hybrid mesostructures featuring a controllable composition and high photocatalytic activity via a two-step hard-templating and topotactic ion-exchange chemical process. Ag2S compounds and polyoxometalate cluster

  1. A Stable Polyoxometalate-Pillared Metal-Organic Framework for Proton-Conducting and Colorimetric Biosensing.

    PubMed

    Zhou, En-Long; Qin, Chao; Huang, Peng; Wang, Xin-Long; Chen, Wei-Chao; Shao, Kui-Zhan; Su, Zhong-Min

    2015-08-10

    A stable metal-organic framework pillared by Keggin-type polyoxometalate, Cu6 (Trz)10 (H2O)4 [H2 SiW12 O40 ]⋅8 H2O (Trz=1,2,4-triazole) (1), has been prepared under hydrothermal condition. The 2D layer structure with a 22-member ring was formed by Cu(2+) ions, which are connected with each other via the Trz ligands on the ab plane. Thus, the 2D layers are further interconnected through Keggin polyoxoanions to generate a 3D porous network with a small 1D channel. Moreover, the presence of polyoxoanions make it exhibit selective adsorption of water and proton-conducting properties. Additionally it showed efficient intrinsic peroxidase-like activity, providing a simple and sensitive colorimetric assay to detect H2O2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Planar {Ni6} cluster-containing polyoxometalate-based inorganic-organic hybrid compound and its extended structure.

    PubMed

    Wang, Xingquan; Liu, Shuxia; Liu, Yiwei; He, Danfeng; Li, Ning; Miao, Jun; Ji, Yujuan; Yang, Guoyu

    2014-12-15

    Two {Ni6} cluster-containing inorganic-organic hybrid compounds have been successfully synthesized in the presence of organic amine under hydrothermal conditions, and they were characterized by powder and single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and IR spectroscopy. Structural analysis indicates that [Ni0.5(H2O)3][{Ni6(μ3-OH)3en(H2O)10}(H2P2W15O56)]·10H2O (1, en = ethylenediamine) is a triangular inorganic {Ni6} cluster substituted polyoxotungstate with only one en to stabilize the {Ni6} cluster. However, [Ni(dap)2]{[Ni1.5(dap)1.5(H2O)3][Ni6(μ3-OH)3(dap)2(en)(H2O) {O2C(CH2)2CO2}0.5(CH3COO)(P2W15O56)]}·15H2O (2, dap = 1,2-diaminopropane) is a three-dimensional inorganic-organic hybrid compound linked by succinic acid. The magnetic properties of both compounds were studied. In addition, the adsorption properties of compound 2 have also been investigated.

  3. Construct Polyoxometalate Frameworks through Covalent Bonds.

    PubMed

    Chen, Hong; Zhao, Huishuang; Yu, Zheng-Bao; Wang, Lei; Sun, Licheng; Sun, Junliang

    2015-09-08

    An emerging strategy for exploring the application of polyoxometalates (POMs) is to assemble POM clusters into open-framework materials, especially inorganic-organic hybrid three-dimensional (3D) open-framework materials, via the introduction of different organic linkers between the POM clusters. This strategy has yielded a few 3D crystalline POMs of which a typical class is the group of polyoxometalate metal-organic frameworks (POMMOFs). However, for reported POMMOFs, only coordination bonds are involved between the linkers and POM clusters, and it has not yet produced any covalently bonded polyoxometalate frameworks. Here, the concept of "covalently bonded POMs (CPOMs)" is developed. By using vanadoborates as an example, we showed that the 3D CPOMs can be obtained by a condensation reaction through the oxolation mechanism of polymer chemistry. In particular, suitable single crystals were harvested and characterized by single-crystal X-ray diffraction. This work forges a link among polymer science, POM chemistry, and open-framework materials by demonstrating that it is possible to use covalent bonds according to polymer chemistry principles to construct crystalline 3D open-framework POM materials.

  4. Polyoxometalates: from inorganic chemistry to materials science.

    PubMed

    Casañ-Pastor, Nieves; Gómez-Romero, Pedro

    2004-05-01

    Polyoxometalates have been traditionally the subject of study of molecular inorganic chemistry. Yet, these polynuclear molecules, reminiscent of oxide clusters, present a wide range of structures and with them ideal frameworks for the deployment of a plethora of useful magnetic, electroionic, catalytic, bioactive and photochemical properties. With this in mind, a new trend towards the application of these remarkable species in materials science is beginning to develop. In this review we analyze this trend and discuss two main lines of thought for the application of polyoxometalates as materials. On the one hand, there is their use as clusters with inherently useful properties on themselves, a line which has produced fundamental studies of their magnetic, electronic or photoelectrochemical properties and has shown these clusters as models for quantum-sized oxides. On the other hand, the encapsulation or integration of polyoxometalates into organic, polymeric or inorganic matrices or substrates opens a whole new field within the area of hybrid materials for harnessing the multifunctional properties of these versatile species in a wide variety of applications, ranging from catalysis to energy storage to biomedicine.

  5. Reactive N-protonated isocyanate species stabilized by bis(μ-hydroxo)divanadium(IV)-substituted polyoxometalate.

    PubMed

    Uehara, Kazuhiro; Fukaya, Keisuke; Mizuno, Noritaka

    2012-07-27

    O- or N-protonated? The bis(μ-hydroxo)divanadium(IV)-substituted γ-Keggin-type polyoxometalate (see picture, left) (TBA)(4)[γ-SiV(IV)(2)W(10)O(36)(μ-OH)(4)] (TBA = tetra(n-butyl)ammonium) was synthesized and characterized by X-ray crystallography. Its reaction with phenyl isocyanate gave (TBA)(4)[γ-SiV(IV)(2)W(10)O(38)(μ-OH)(2)(PhNHCO)(2)], which contains two N-protonated phenyl isocyanate species and catalyzes the cyclotrimerization of phenyl isocyanate.

  6. Inorganic-organic hybrid polyoxometalate: Preparation, characterization and electrochemistry properties

    SciTech Connect

    Han Zhangang; Zhao Yulong; Peng Jun . E-mail: jpeng@nenu.edu.cn; Tian Aixiang; Feng Yuhua; Liu Qun

    2005-05-15

    The solid hybrid material (H{sub 3/4}pbpy){sub 4}[PMo{sub 12}O{sub 40}].1.25H{sub 2}O (1) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) has been prepared and characterized. A structural feature of compound 1 is that the polyoxometalate anions exhibit a one-dimensional inorganic double chain-like structure via weak interactions of O...O. The organic moiety exhibits regular packing with offset aromatic-aromatic interactions between the pbpys, leading to a compact supramolecular framework structure to accommodate the inorganic chains. Compound 1 was employed to fabricate the three-dimensional bulk-modified carbon paste electrode (1-CPE) to research on its electrochemistry properties. The results indicate that 1 retained Keggin molybdate anion electrocatalytic activities toward the reduction of chlorate, hydrogen peroxide and nitrite.

  7. A new hybrid constructed from Dawson-like polyoxometalates and dicopper coordination compounds containing a discrete tridecameric water cluster

    NASA Astrophysics Data System (ADS)

    Yang, Hongxun; Cao, Minna; Gao, Shuiying; Cao, Rong

    2014-01-01

    A new organic-inorganic hybrid polyoxotungstates, [Cu2Cl(H2O)3(phen)2]2[H3SbW18O60]·7H2O (phen = 1,10-phenanthroline, 1), has been synthesized and characterized by elemental analyses, FTIR, TG, UV-DRS, XRPD, magnetic property and X-ray single crystal diffraction. The structure analyses reveal that complex 1 based on Dawson-like polyoxoanions and dicopper coordination cations exhibits 3D supramolecular network via hydrogen bonding and π-π stacking containing a new discrete tridecameric water cluster. The magnetic property of 1 was also investigated between 2 and 300 K, indicating the existence of antiferromagnetic exchange interaction between the Cu(II) centres.

  8. Hydrothermal syntheses and crystal structures of two hybrid materials constructed from polyoxometalate clusters and metal dipyridine complexes

    NASA Astrophysics Data System (ADS)

    Li, Guangzhe; Salim, Chris; Hinode, Hirofumi

    2008-02-01

    Two organic-inorganic hybrid microporous compounds with formulas (4,4'-bipy) 2[Cu(4,4'-bipy) 2{Mo 5P 2O 21(OH) 2}]2(H 3O)·3(H 2O) 1 and (4,4'-bipy) 0.5[Cu 1.5(4,4'-bipy) 4{Mo 5P 2O 21(OH) 2}](H 3O)·2(H 2O) 2 have been hydrothermally prepared and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in a monoclinic system with space group C2/ c (no. 15), a = 17.667(3) Å, b = 13.669(3) Å, c = 25.067(5) Å, β = 107.479(3)°, V = 5774.2(18) Å 3, and Z = 4. Compound 2 crystallizes in a monoclinic system with space group P2 1/ n (no. 14), a = 13.9590(5) Å, b = 22.4850(7) Å, c = 19.1568(6) Å, β = 97.778(2)°, V = 5957.4(3) Å 3, and Z = 4. Compound 1 is three-dimensional (3D), constructed from {Mo 5P 2O 21(OH) 2} 4- cluster anions bridged through [Cu(4,4'-bipy) 2] n2 n+ layer sheets. In contrast, compound 2 is also three-dimensional, resulting from a complex connectivity pattern among {Mo 5P 2O 21(OH) 2} 4- cluster anions, [Cu(4,4'-bipy) 2] n2 n+ layer sheets and [Cu(4,4'-bipy) 4] n2 n+ complex subunits. Other characterizations by elemental analysis, IR, thermal analysis, and magnetic properties for the compounds are also given.

  9. Polyoxometalate ionic liquids as self-repairing acid-resistant corrosion protection.

    PubMed

    Herrmann, Sven; Kostrzewa, Monika; Wierschem, Andreas; Streb, Carsten

    2014-12-01

    Corrosion is a global problem for any metallic structure or material. Herein we show how metals can easily be protected against acid corrosion using hydrophobic polyoxometalate-based ionic liquids (POM-ILs). Copper metal disks were coated with room-temperature POM-ILs composed of transition-metal functionalized Keggin anions [SiW11 O39 TM(H2 O)](n-) (TM=Cu(II) , Fe(III) ) and quaternary alkylammonium cations (Cn H2 n+1 )4 N(+) (n=7-8). The corrosion resistance against acetic acid vapors and simulated "acid rain" was significantly improved compared with commercial ionic liquids or solid polyoxometalate coatings. Mechanical damage to the POM-IL coating is self-repaired in less than one minute with full retention of the acid protection properties. The coating can easily be removed and recovered by rinsing with organic solvents.

  10. A new supramolecular assembly based on triple-Dawson-type polyoxometalate and 3d-4f heterometallic cluster.

    PubMed

    Li, Yun-Wu; Li, Yang-Guang; Wang, Yong-Hui; Feng, Xiao-Jia; Lu, Ying; Wang, En-Bo

    2009-07-20

    The introduction of hexavacant Dawson-type precursor K(12)[H(2)P(2)W(12)O(48)] x 24 H(2)O into a HOAc/NaOAc (OAc(-) = acetate) buffer system containing (NH(4))(2)[Ce(IV)(NO(3))(6)] and Mn(II)(OAc)(2) x 4 H(2)O led to the isolation of a new compound, Na(20)[Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9)](2)[Mn(III)(2)P(2)W(16)O(60)](3) x 21 H(2)O (1). Compound 1 contains unusual triple-Dawson-type polyoxoanions [Mn(III)(2)P(2)W(16)O(60)](3)(24-) and bipyramid-like 3d-4f heterometallic clusters [Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9)](2+), which are arranged in a 3-D supramolecular assembly with 1-D channels. The Na(+) cations and solvent water molecules reside in the channels. Crystal data for 1 are as follows: hexagonal, P6(3)/mcm (No. 193), a = 24.959(4) A, c = 26.923(5) A, gamma = 120 degrees, V = 14525(4) A(3), and Z = 2. The electrochemical and electrocatalytic properties of compound 1 have been investigated.

  11. Functionalization of cotton fiber by partial etherification and self-assembly of polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework.

    PubMed

    Lange, Laura E; Obendorf, S Kay

    2015-02-25

    A combination of a Keggin-type polyoxometalate (POM), [CuPW11O39](5-), with a Cu3(BTC)2 metal-organic framework (MOF-199/HKUST-1; where BTC is benzene-1,3,5-tricarboxylate), was successfully self-assembled on a cellulose substrate (cotton) with a room-temperature process. Cotton fibers were functionalized by partial etherification. Cu3(BTC)2 metal-organic framework and polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework were self-assembled on the carboxymethylate ion sites initiated with copper nitrate using ethanol and water as solvents. Octahedral crystals were observed on both MOF-cotton and POM-MOF-cotton; both contained copper while the POM-MOF-cotton also contained tungsten. Occupancy of POM in MOF cages was calculated to be about 13%. Moisture content remained at 3 to 4 wt % similar to that of untreated cotton. Reactivity to both hydrogen sulfide and methyl parathion was higher for POM-MOF-cotton due to the Keggin polyoxometalate and the extra-framework cations Cu(2+) ions compensating the charges of the encapsulated Keggins. The POM-MOF material was found to effectively remove 0.089 mg of methyl parathion per mg of MOF from a hexane solution while MOF-cotton removed only 0.054 mg of methyl parathion per mg of MOF.

  12. Two types of tetranuclear phosphanegold(I) cations as dimers of dinuclear units, [{(Au{P(p-RPh)3})2(μ-OH)}2]2+ (R = Me, F), synthesized by polyoxometalate-mediated clusterization.

    PubMed

    Yoshida, Takuya; Matsunaga, Satoshi; Nomiya, Kenji

    2013-08-28

    Novel intercluster compounds [{(Au{P(p-RPh)3})2(μ-OH)}2]3[α-PM12O40]2·nEtOH (R = Me, M = W for 1; R = Me, M = Mo for 2; R = F, M = Mo for 3) were synthesized by the polyoxometalate (POM)-mediated clusterization of monomeric phosphanegold(I) complexes, and unequivocally characterized by elemental analysis, TG/DTA, FTIR, X-ray crystallography, and (1)H and (31)P{(1)H} NMR. In each cluster cation, two digold(I) units, {Au{P(p-RPh)3})2(μ-OH)}(+), dimerized to form the tetragold(I) cluster cation by interdimer aurophilic interactions, i.e., a dimer of dinuclear units, and these cations showed different forms of structural dimerization, i.e., a crossed-edge arrangement for 1 and 2 and a parallel-edge arrangement for 3, depending upon the substituent on the aryl group of triarylphosphanes. The dimerization of digold(I) cations was affected by not only the type of the POMs, but also the phosphane ligand of the monomeric phosphanegold(I) precursors.

  13. Hydrothermal synthesis and characterization of the tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate: {l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}{sup 6-}

    SciTech Connect

    Liu Jian; Xu Jianing; Liu Yabing; Lu Yukun; Song Jiangfeng; Zhang Xiao; Cui Xiaobing; Xu Jiqing Wang Tiegang

    2007-12-15

    A novel polyoxometalate [Cu(phen){sub 2}]{sub 3}{l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}.4H{sub 2}O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}{sup 6-}, three [Cu(phen){sub 2}]{sup 2+} cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and {pi}-{pi} stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure. - Graphical abstract: A novel complex [Cu(phen){sub 2}]{sub 3}{l_brace}PW{sub 4}{sup VI}W{sub 5}{sup V}V{sub 3}{sup IV}O{sub 40}(V{sup IV}O){sub 3}[Cu(en){sub 2}]{r_brace}.4H{sub 2}O, the first example of tri-capped and mono-supported highly reduced pseudo-Keggin-type tungstovanadophosphate was synthesized under hydrothermal condition. And the heteropolyanions are linked by water dimer and cation [Cu(phen){sub 2}]{sup 2+} through the hydrogen bond forming a three-dimensional (3D) supramolecular network. Interestingly, the water dimer and terminal oxygen of the polyanion cluster constitute a beautiful supramolecular helix chain.

  14. Smart polyoxometalate-based nitrogen monoxide sensors.

    PubMed

    Liu, Shaoqin; Volkmer, Dirk; Kurth, Dirk G

    2004-08-01

    An electrochemical sensor design for selective NO detection is presented based on a polyoxometalate (POM) cluster immobilized on an electrode through a polyelectrolyte matrix. It is suggested that the POM can electrocatalyze the reduction of NO. The reduction current is proportional to the NO concentration in the investigated concentration window ranging from 1 nM to 10 microM. The sensitivity of the device can be adjusted by the number of immobilized layers. The response to possible interfering reagents such as nitrate and nitrite can be controlled through the multilayer design. By a predominant negatively charged outer surface, the response to these ions is markedly reduced.

  15. Double sandwich polyoxometalate and its Fe(III) substituted derivative, [As2Fe5Mo21O82]17– and [As2Fe6Mo20O80(H2O)2]16–.

    PubMed

    Dong, Xiangqian; Zhang, Yanping; Liu, Bin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

    2012-02-20

    A double sandwich polyoxometalate and its Fe(III) substituted derivative, [As(2)Fe(5)Mo(21)O(82)](17-) (1) and [As(2)Fe(6)Mo(20)O(80)(H(2)O)(2)](16-) (2), were synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, fluorescent spectroscopy, UV spectra, thermogravimetry-differential scanning calorimetry analyses, electrospray ionization mass spectrometry, and magnetism measurements. The polyoxoanion is composed of a central fragment FeMo(7)O(28) for 1 (Fe(2)Mo(6)O(26)(H(2)O)(2) for 2) and two external AsMo(7)O(27) fragments linked together by two distinct edge-sharing dimeric clusters Fe(2)O(10) to lead to a C(2v) molecular symmetry. The central FeMo(7)O(28) fragment and external AsMo(7)O(27) fragment have a similar structure, and both of them can be viewed as a monocapped hexavacant α-Keggin subunit with a central FeO(4) group or a central AsO(3) group. Both of the polyoxoanions contain a oxo-bridged Fe(III)(5) magnetic core with the angles of Fe-O-Fe in the range of 96.4(4)-125.7(5)°, and magnetism measurements show an overall ferromagnetic interactions among the five-nuclearity cluster Fe(5) with the spin ground state S = 15/2.

  16. Selective oxidation of lignocellulosic biomass to formic acid and high-grade cellulose using tailor-made polyoxometalate catalysts.

    PubMed

    Albert, Jakob

    2017-06-27

    The main goal of this project was to identify and optimize tailor-made polyoxometalate catalysts for a fractionated oxidation of lignocellulosic biomass (i.e. wood and residues from sugar or paper industries) to produce formic acid (FA) and high-grade cellulose for further processing e.g. in white biotechnology to provide bio-ethanol. Homogeneous vanadium precursors like sodium metavanadate and vanadyl sulfate as well as Keggin-type polyoxometalates (POMs) and more exotic structures like Anderson-, Wells-Dawson- and Lindqvist-type POMs were screened for the desired catalytic performance. The most promising behaviour was found using the Lindqvist-type POM K5V3W3O19, showing for the first time in the literature a selective oxidation of only hemicellulose and lignin to formic acid, while the cellulose fraction was untrapped. However, this can only be a first step towards the project goal as low product yields were obtained.

  17. Rare Earth Polyoxometalates.

    PubMed

    Boskovic, Colette

    2017-09-05

    Longstanding and important applications make use of the chemical and physical properties of both rare earth metals and polyoxometalates of early transition metals. The catalytic, optical, and magnetic features of rare earth metal ions are well-known, as are the reversible multielectron redox and photoredox capabilities of polyoxomolybdates and polyoxotungstates. The combination of rare earth ions and polyoxometalates in discrete molecules and coordination polymers is of interest for the unique combination of chemical and physical properties that can arise. This Account surveys our efforts to synthesize and investigate compounds with rare earth ions and polyoxometalates (RE-POMs), sometimes with carboxylate-based organic coligands. Our general synthetic approach is "bottom-up", which affords well-defined nanoscale molecules, typically in crystalline form and amenable to single-crystal X-ray diffraction for structure determination. Our particular focus is on elucidation of the physical properties conferred by the different structural components with a view to ultimately being able to tune these properties chemically. For this purpose, we employ a variety of spectroscopic, magnetochemical, electrochemical, and scattering techniques in concert with theoretical modeling and computation. Studies of RE-POM single-molecule magnets (SMMs) have utilized magnetic susceptibility, inelastic neutron scattering, and ab initio calculations. These investigations have allowed characterization of the crystal field splitting of the rare earth(III) ions that is responsible for the SMM properties of slow magnetic relaxation and magnetization quantum tunneling. Such SMMs are promising for applications in quantum computing and molecular spintronics. Photophysical measurements of a family of hybrid RE-POMs with organic ligands have afforded insights into sensitization of Tb(III) and Eu(III) emission through both organic and polyoxometalate chromophores in the same molecule. Detailed

  18. Electrocatalytic performance of carbon supported Pd catalyst modified with Keggin type of Sn-substituted polyoxometalatate for formic acid oxidization

    NASA Astrophysics Data System (ADS)

    Ji, Yun; Shen, Liping; Wang, Anxing; Wu, Min; Tang, Yawen; Chen, Yu; Lu, Tianhong

    2014-08-01

    The carbon supported Pd(Pd/C) catalyst modified by the new polyoxometalate with Keggin type of Sn-Substituted structure K7CoIIW11O39SnIVOH (Pd/C-K7) catalyst is prepared with the simple impregnation-reduction method. This work investigates the effects of Pd/C-K7 catalyst for direct formic acid fuel cells (DFAFCs). The morphology, structure, size and composition of the Pd/C-K7 catalyst are characterized by transmission electron microscopy (TEM) energy dispersive spectrum (EDS), X-ray diffraction (XRD). Cyclic voltammetry, chronoamperometry and CO-stripping voltammetry tests demonstrate the Pd/C-K7 catalyst have higher electrocatalytic activity, better electrochemical stability, and higher resistance to CO poisoning over the unmodified Pd/C catalyst for the formic acid oxidation reaction (FAOR) owing to K7CoIIW11O39SnIVOH with Keggin structure. Therefore, the Pd/C-K7 catalyst could be used as the excellent anodic catalyst in DFAFCs.

  19. ZnO-based hollow microspheres with mesoporous shells: Polyoxometalate-assisted fabrication, growth mechanism and photocatalytic properties

    SciTech Connect

    Li Qiuyu; Chen Weilin; Ju Mingliang; Liu Lin; Wang Enbo

    2011-06-15

    With the assistance of Keggin-type polyoxometalate, ZnO hollow microspheres with mesoporous shells were synthesized via a simple solvothermal approach without any templates and surfactants. The observations of morphology and structure performed by field emission scanning electronic microscopy and transmission electron microscopy indicated that the shells of the ZnO hollow spheres were built from nanosheets which were composed of nanoparticles. The transformation of structure and composition of samples were investigated by X-ray diffraction, X-ray photoelectron spectrometry and fourier transform infrared absorption spectroscopy. The formation mechanism of the hollow spheres is proposed based on time-dependent experimental results. The ZnO hollow microspheres exhibited a high photocatalytic activity for decolorization of Rhodamine B under ultraviolet irradiation. - Graphical Abstract: ZnO hollow spheres with mesporous shells were synthesized by an one-pot polyoxometalate-assisted solvothermal route. The ZnO hollow microspheres exhibited a high photocatalytic activity for decolorization of Rhodamine B (RhB) under UV irradiation. Highlights: > ZnO hollow microspheres were synthesized via a solvothermal route with polyoxometalate. > The polyoxometalate was vital for the formation of the hollow microspheres. > The ZnO hollow microspheres exhibited excellent photocatalytic activity of Rhodamine B.

  20. A New Approach for the Modification of Paper Surface Properties Using Polyoxometalates

    PubMed Central

    Saraiva, Mikhail S.; Gamelas, José A. F.; Mendes de Sousa, António P.; Reis, Bruno M.; Amaral, José L.; Ferreira, Paulo J.

    2010-01-01

    A new approach for the chemical modification of the surface of paper based on the application of colloidal mixtures containing cationic starch and polyoxometalates on uncoated base paper is presented. Polyoxometalates with the Keggin-type structure and physical properties similar to those presented by coating pigments, namely H3PW12O40·23H2O, H4SiW12O40·24H2O, and K7PW11O39·9H2O, have been used in order to improve the quality of inkjet printing. The analysis of the different samples by FTIR-ATR spectroscopy showed the presence of the polyoxometalates (and the cationic starch) on the top surface of the paper. In addition, the determination of surface energy parameters, namely the polar component (σsp) and the dispersive component (σsd) of the surface energy, by contact angle measurements revealed that, for the new samples, the polar component level was much higher than that of the uncoated base paper. The quality of inkjet printing, evaluated by parameters such as the gamut area and the optical density, was considerably improved by these surface treatments.

  1. Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

    PubMed

    Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

    2017-03-06

    Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW11O39](7-) (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O2) oxidation of CO to CO2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O2 + H2O = CO2 + H2O2. After control experiments verified that the H2O2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H2O2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K(+) salts): 1, the Wells-Dawson ion [α-P2W18O62](6-) (2) and the monodefect Keggin anion [α-SiW11O39](8-) (3) revealed that binding energies of electrons in the Au 4f7/2 and 4f5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O2. Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

  2. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices.

  3. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.

    PubMed

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei

    2015-10-12

    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.

  4. Polyoxometalate-based Supramolecular Gel

    NASA Astrophysics Data System (ADS)

    He, Peilei; Xu, Biao; Liu, Huiling; He, Su; Saleem, Faisal; Wang, Xun

    2013-05-01

    Self-assemblyings of surfactant-encapsulated Wells-Dawson polyoxometalates (SEPs) nanobuilding blocks in butanone and esters yielded supramolecular gels showing thermo and photo responsive properties. The gels can be further polymerized if unsaturated esters were used and subsequently electrospinned into nanowires and non-woven mats. The as-prepared non-woven mats have a Young's modulus as high as 542.55 MPa. It is believed that this supramolecular gel is a good platform for polyoxometalates processing.

  5. Photochromic ordered mesoporous hybrid materials based on covalently grafted polyoxometalates.

    PubMed

    Luo, Xiujuan; Yang, Chun

    2011-05-07

    Novel polyoxometalate (POM)-grafting mesoporous hybrid silicas, XW(11)/MHS (X=P, Si) and TBAPW(11)Si(2)/MHS, have been prepared respectively by co-condensation and post-synthesis routes based on the employment of Keggin-type monovacant XW(11) or a Si-substituted compound TBAPW(11)Si(2) as POM precursors. Upon characterization of the samples by FT-IR, XRD, ICP-AES, TEM and N(2) adsorption-desorption measurement, it was found that Keggin units were retained perfectly in ordered hexagonal mesopore channels with SBA-15 architecture and immobilized by covalent linkages on the mesopore wall. These materials, especially the co-condensed samples, exhibited stable and reversible photochromic properties under UV irradiation although no special organic component was supplied additionally as an electron donor. An investigation of the photochromism revealed that the photochromic response depended on the centre atom of the POM species (i.e., the redox potential of the POM), the content of the POM and the synthetic route of the sample, while the bleaching process was correlated not only to the redox potential but also to the pore size of the sample. The photochromic mechanism was also studied in detail by cyclic voltammetry, ESR, FT-IR and XPS techniques. It was found that the remaining P123 template acted as a reducing agent and was oxidized during the photochromic process accompanied by the reduction of the POM to heteropolyblue. Thus, a close contact between the POM and the remaining P123 chain in the sample is necessary. Low close-contact degree results in poor photochromic behavior of the post-synthesized sample and impregnated samples.

  6. Two 3D networks based on sandwich-type polyoxometalate units linked by Sr-O clusters: Synthesis, structure, and magnetic property

    NASA Astrophysics Data System (ADS)

    Yu, Yang; Zhou, Bai-Bin; Yu, Kai; Zhang, Yu-Nan

    2010-08-01

    Two 3D hybrid sandwich-type polyoxometalates, [{Sr(H 2O) 5Sr(H 2O) 6Sr 0.5(H 2O) 7} 2Mn 4(H 2O) 2(α-PW 9O 34) 2]·6H 2O ( 1) and [{Sr(H 2O) 6[Sr(H 2O) 8] 2Sr(H 2O) 4} 2Mn 4(H 2O) 2(αββα-P 2W 15O 56) 2]·5H 2O ( 2), have been obtained by the routine synthetic reactions in aqueous solution and characterized by IR, elemental analysis, thermal analysis, and X-ray single-crystal diffraction. The 3D hybrid framework of 1 and 2 are built by tetra-Mn II substituted sandwich-type polyoxotungstates modified by fourteen Sr(H 2O) x ( x=4-8) units acting as bridges, forming centrosymmetric sandwich structures. The magnetic property of compound 1 has been studied by measuring its magnetic susceptibility in the temperature range of 2-300 K, which indicates predominant ferromagnetic interactions between the Mn II-O-Mn II bridge unit. Additionally, the electrochemical behaviours have been detected on solid bulk modified carbon paste electrodes of compounds (CPEs) and three redox couples are detected.

  7. Polyoxometalate immobilization in Cu{sup I}/Ag-pz porous coordination polymers: The influences of them on the structural properties of frameworks

    SciTech Connect

    Zhu, Min; Peng, Jun; Pang, Hai-Jun; Zhang, Peng-Peng; Chen, Yuan; Wang, Dan-Dan; Liu, Ming-Guan; Wang, Yong-Hui

    2011-05-15

    Three new high dimensional Cu{sup I}/Ag-pz porous coordination polymers (PCPs) with different Keggin polyoxometalate templates have been hydrothermally synthesized: [Cu{sup I}{sub 5}(pz){sub 6}Cl][HPMo{sup VI}{sub 10}Mo{sup V}{sub 2}O{sub 40}] (1) [Ag{sub 5}(pz){sub 7}(BW{sub 12}O{sub 40})] (2) and [Cu{sup I}{sub 5}(pz){sub 6}H(H{sub 2}W{sub 12}O{sub 40})].4H{sub 2}O (3) (pz=pyrazine). The choice of the particular Keggin POM templates is shown to influence the structural properties of the Cu/Ag PCPs. Compound 1 shows a Cl-bridged Cu-pz-Cl double layer, between which two kinds of [HPMo{sup VI}{sub 10}Mo{sup V}{sub 2}O{sub 40}]{sup 4-}(PMo{sub 12}) polyanions are located. Compound 2 presents a 3D Ag-pz framework with parallelogram-like voids, into which BW{sub 12}O{sub 40}{sup 5-} (BW{sub 12}) Keggin ions are incorporated. Compound 3 contains a Cu-pz cationic layer framework, between which are located [H(H{sub 2}W{sub 12}O{sub 40})]{sup 5-} (W{sub 12}) Keggin ions. Primary photocatalytic experiment indicates that compound 1 presents excellent photocatalytic activity. The photoluminescence properties and electrochemistry properties of the compounds are also discussed. -- Graphical abstract: The choice of the particular Keggin template is shown to influence the structural properties of the Cu/Ag PCPs. Their photocatalytic activities have been studied. Display Omitted highlights: > In this paper, three Keggin POM-templated metal-pyrazine frameworks are reported. > The choice of template can influence the structural properties of the frameworks. > Further, compound 1 exhibits excellent photocatalytic activity.

  8. Correlating Acid Properties and Catalytic Function: A First-Principles Analysis of Alcohol Dehydration Pathways on Polyoxometalates

    SciTech Connect

    Janik, Michael J.; Macht, Josef; Iglesia, Enrique; Neurock, Matthew

    2009-02-05

    Density functional theory calculations and reactivity data were used to examine the mechanism of alcohol dehydration on Keggin-type polyoxometalate (POM) catalysts and the influence of the POM composition and the degree of substitution of the alcohol on kinetically relevant elimination steps. Dehydration was found to proceed through E1 pathways in which the alcohol CsO bond is cleaved heterolytically via a carbeniumion transition state. Dehydration rates were found to depend on the elimination rate constant and the equilibrium constant for the formation of unreactive alcohol dimers. E2-type elimination transition states, involving concerted CsH and CsO bond cleavage, were not found. The extent of substitution at the R-carbon on the alcohol was found to lead to marked effects on elimination barriers, because substitution increases the proton affinity of the alcohol and the stability of the carbenium-ion transition state. Changes in the central and addenda atoms of the POM cluster and the presence of n-donors, a support, vicinal POM clusters, or charge-compensating cations were found to lead to changes in the deprotonation energy (DPE) of the POM cluster, activation barriers to dehydration, and the stability of the unreactive dimer. These effects are all captured in a general linear relation between activation barriers and deprotonation energy, a rigorous measure of acid strength. The explicit dependence of the E1 activation barrier on the acid deprotonation energy is much weaker than that on reactant proton affinity. This results from the more effective compensation between the acid deprotonation energy and the interaction energy between the cationic hydrocarbon fragment and the anionic POM cluster at the transition state. The direct interactions between the POM protons and the support, other POM clusters, n-donors, base probe molecules, and charge-compensating cations increased the negative charge of the oxide shell of the W12O40 conjugate base, which increased the

  9. An unusual 3D interdigitated architecture assembled from Keggin polyoxometalates and dinuclear copper(II) complexes

    SciTech Connect

    Pang, Haijun; Yang, Ming; Kang, Lu; Ma, Huiyuan; Liu, Bo; Li, Shaobin; Liu, Heng

    2013-02-15

    A novel organic-inorganic hybrid compound, [Cu{sub 2}(bipy){sub 3}({mu}{sub 1}-H{sub 2}O){sub 2}({mu}{sub 2}-H{sub 2}O)({mu}{sub 2}-OH)(H{sub 2}BW{sub 12}O{sub 40})]{center_dot}4 H{sub 2}O (1) (bipy=4,4 Prime -bipy), has been synthesized in hydrothermal condition and characterized by elemental analysis, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 possesses poly-pendant layered motifs composed of 12-tungstoborates and dinuclear copper(II) complexes, in which the mono-coordinated bipy molecules are orderly appended to both sides of the layer, respectively. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture. The variable-temperature magnetic susceptibility of 1 showed that there existed weak antiferromagnetic interaction in 1. Toward the reduction of hydrogen peroxide, 1 has good electrocatalytic activity and remarkable stability. - A new compound has been obtained, which represents the first interdigitated architecture assembled by POMs and dinuclear copper(II) complexes. Highlights: Black-Right-Pointing-Pointer The first example of interdigitated architecture assembled by POMs and dinuclear copper(II) complexes is observed. Black-Right-Pointing-Pointer A zipper-like pattern is observed in the structure. Black-Right-Pointing-Pointer The IR, TG, XRPD, magnetism and electrochemical property of the title compound were studied.

  10. A Filled-Honeycomb-Structured Crystal Formed by Self-Assembly of a Janus Polyoxometalate-Silsesquioxane (POM-POSS) Co-Cluster.

    PubMed

    Ma, Chi; Wu, Han; Huang, Zi-Han; Guo, Ruo-Hai; Hu, Min-Biao; Kübel, Christian; Yan, Li-Tang; Wang, Wei

    2015-12-21

    Clusters with diverse structures and functions have been used to create novel cluster-assembled materials (CAMs). Understanding their self-assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo-functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell-shaped Janus co-cluster. In a mixed solvent of acetonitrile and water, it self-assembles into a crystal with a honeycomb superstructure constructed by hexagonal close-packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse-grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano-architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis of polyoxometalate-loaded epoxy composites

    DOEpatents

    Anderson, Benjamin J

    2014-10-07

    The synthesis of a polyoxometalate-loaded epoxy uses a one-step cure by applying an external stimulus to release the acid from the polyoxometalate and thereby catalyze the cure reaction of the epoxy resin. Such polyoxometalate-loaded epoxy composites afford the cured epoxy unique properties imparted by the intrinsic properties of the polyoxometalate. For example, polyoxometalate-loaded epoxy composites can be used as corrosion resistant epoxy coatings, for encapsulation of electronics with improved dielectric properties, and for structural applications with improved mechanical properties.

  12. Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate.

    PubMed

    Liu, Fu-Ling; Kozlevčar, Bojan; Strauch, Peter; Zhuang, Gui-Lin; Guo, Ling-Yu; Wang, Zhi; Sun, Di

    2015-12-14

    The encapsulation of carbonate derived from atmospheric CO2 has resulted in an icosanuclear heteropolyoxocopperate, isolated as a metal-organic 1D chain, 2D sheet, or 3D framework, in which the Cu20 nanocluster represents the first eight-capped α-Keggin polyoxometalate with the late-transition-metal Cu(II) as the polyatom, CO3(2-) as the heteroanion, and OH(-) and suc(2-) or glu(2-) (H2suc=succinic acid; H2glu=glutaric acid) as the terminal ligands, which suggests a conceptual similarity to classical polyoxometalates. Even in the presence of competitive SO4(2-) in the assembly system, the CO3(2-) anion is still captured as a template to direct the formation of the Cu20 nanocluster, which indicates the stronger templation ability of CO3(2-) compared with SO4(2-). When other aliphatic dicarboxylates, such as glutaric acid, were used as ligands, the CO3(2-)-templated Cu20 nanocluster was maintained and acted as a cluster building unit (CBU) to be linked by two glutarate bridges to generate a distinct 1D metal-organic chain. This report presents not only a rare example of a huge anion-templated transition-metal cluster, but also its use as a robust CBU to construct novel coordination architectures. Variable-temperature magnetic susceptibility studies revealed that an antiferromagnetic interaction exists within the Cu20 nanocluster. The correlation between the coordination structure and the electron paramagnetic resonance spectra recorded of both powder and single-crystal samples are discussed in detail. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. New synthetic route for organic polyoxometallic clusters: synthetic and structural investigations on the first dumb-bell shaped polyoxozirconium hydroxide with the [Zr9(mu5-O)2(mu3-O)4(mu-O)4(mu-OH)8] core structure.

    PubMed

    Bai, Guangcai; Ma, Qingjun; Roesky, Herbert W; Vidovic, Denis; Herbst-Irmer, Regine

    2003-04-07

    A new route for organic polyoxometallic clusters describes the first dumb-bell-like organic polyoxozirconium hydroxide [[(Cp*Zr)4(mu5-O)(mu3-O)2(mu-OH)4]2Zr(mu-O)4] x 2C7H8 (2; Cp* = C5Me5) involving the treatment of the Brønsted acidic organozirconium hydroxide [(Cp*Zr)6(mu4-O)(mu-O)4(mu-OH)8] x 2C7H8 (1) with organozirconium compounds.

  14. Visible-light-driven hydrogen production in a dye sensitized polyoxometalate system without noble metals

    NASA Astrophysics Data System (ADS)

    Liu, Xing; Li, Yuexiang; Peng, Shaoqin; Lai, Hua; Yi, Zhengji

    2016-05-01

    In this work, a noble-metal-free homogeneous system was constructed in one step with Keggin-type polyoxometalate (POM) SiW12O404- as a catalyst, Eosin Y as a photosensitizer, and triethanolamine (TEOA) as a sacrificial electron donor for water splitting to produce hydrogen under visible-light irradiation. A two-electron reduced heteropoly blue SiW12O406- is produced by photosensitization under visible-light irradiation. The effect of various component concentrations and POMs with different central atoms (PW12O403-, GeW12O404-, etc.) on hydrogen production was discussed. This simple system made of earth-abundant elements is expected to contribute toward the development of functional and efficient artificial photosynthetic system.

  15. Adsorption of a catalytically accessible polyoxometalate in a mesoporous channel-type metal–organic framework

    DOE PAGES

    Buru, Cassandra T.; Li, Peng; Mehdi, B. Layla; ...

    2017-05-24

    A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

  16. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-11-01

    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  17. Synthesis of polyoxometalates-functionalized carbon nanotubes composites and relevant electrochemical properties study

    SciTech Connect

    Song Yanli; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Kang Zhenhui; Lan Yang; Tian Chungui

    2007-08-07

    Carbon nanotubes (CNTs)-based polyoxometalates (POMs)-functionalized nanocomposites were synthesized by simply functionalizing CNTs with Keggin and Dawson-type POMs. The positively charged polyelectrolyte poly (diallyldimethylammonium chloride) (PDDA) was introduced to assemble negatively charged POMs and CNTs. The composition, structure and morphology were investigated by UV-visible (UV-vis), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Cyclic voltammetry (CV) was employed to investigate the electrochemical properties of the resulting nanocomposites. The cyclic voltammograms indicate that the electrochemical properties of POMs are fully maintained. Functionalizing CNTs with POMs not only retains the unique properties of nanotubes, but also endows CNTs with the reversible redox activity of POMs.

  18. Polyoxometalate-based Supramolecular Gel

    PubMed Central

    He, Peilei; Xu, Biao; Liu, Huiling; He, Su; Saleem, Faisal; Wang, Xun

    2013-01-01

    Self-assemblyings of surfactant-encapsulated Wells-Dawson polyoxometalates (SEPs) nanobuilding blocks in butanone and esters yielded supramolecular gels showing thermo and photo responsive properties. The gels can be further polymerized if unsaturated esters were used and subsequently electrospinned into nanowires and non-woven mats. The as-prepared non-woven mats have a Young's modulus as high as 542.55 MPa. It is believed that this supramolecular gel is a good platform for polyoxometalates processing. PMID:23666013

  19. Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}.

    PubMed

    Miras, Haralampos N; Ochoa, M Nieves Corella; Long, De-Liang; Cronin, Leroy

    2010-11-21

    The reaction of molybdate with vanadium(V) in the presence of sulfite anions is explored showing how, via cation control, stepwise assembly through the {Mo(11)V(7)} cluster yields a {M(25)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(μ(9)-SO(3))(Mo(VI)(6)V(V)O(22))](10-) (1a), which was first discovered using cryospray mass spectrometry, whereas switching the cation away from ammonium allows the direct formation of the spherical 'Keplerate' {Mo(72)V(30)} cluster.

  20. Ionic liquid polyoxometalates as light emitting materials

    SciTech Connect

    Ortiz-acosta, Denisse; Del Sesto, Rico E; Scott, Brian; Bennett, Bryan L; Purdy, Geraldine M; Muenchausen, Ross E; Mc Kigney, Edward; Gilbertson, Robert

    2008-01-01

    The low melting point, negligible vapor pressure, good solubility, and thermal and chemical stability make ionic liquids useful materials for a wide variety of applications. Polyoxometalates are early transition metal oxygen clusters that can be synthesized in many different sizes and with a variety of heterometals. The most attractive feature of POMs is that their physical properties, in particular electrical, magnetic, and optical properties, can be easily modified following known procedures. It has been shown that POMs can exhibit cooperative properties, as superconductivity and energy transfer. POM ionic liquids can be obtained by selecting the appropliate cation. Different alkyl ammonium and alkyl phosphonium salts are being used to produce new POM ionic liquids together with organic or inorganic luminescent centers to design light emitting materials. Ammonium and phosphonium cations with activated, polymerizable groups are being used to further polymerize the ionic liquid into transparent, solid materials with high metal density.

  1. Highly stable crystalline catalysts based on a microporous metal-organic framework and polyoxometalates.

    PubMed

    Sun, Chun-Yan; Liu, Shu-Xia; Liang, Da-Dong; Shao, Kui-Zhan; Ren, Yuan-Hang; Su, Zhong-Min

    2009-02-11

    A series of remarkable crystalline compounds [Cu(2)(BTC)(4/3)(H(2)O)(2)](6)[H(n)XM(12)O(40)].(C(4)H(12)N)(2) (X = Si, Ge, P, As; M = W, Mo) were obtained from the simple one-step hydrothermal reaction of copper nitrate, benzentricaboxylate (BTC), and different Keggin polyoxometalates (POMs). In these compounds, the catalytically active Keggin polyanions were alternately arrayed as noncoordinating guests in the cuboctahedral cages of a Cu-BTC-based metal-organic framework (MOF) host matrix. X-ray crystallographic analyses, TG, FT-IR, UV-vis, N(2) adsorption studies, and acid-base titration demonstrated their high stability and toleration for thermal and acid-base conditions. No POM leaching or framework decomposition was observed in our study. The representative acid catalytic performance of a compound containing PW(12) species was assessed through the hydrolysis of esters in excess water, which showed high catalytic activity and can be used repeatedly without activity loss. Moreover, catalytic selectivity, which is dependent on the molecular size of substrates, and substrate accessibility for the pore surface were observed. It is the first time that the well-defined, crystalline, MOF-supported POM compound has behaved as a true heterogeneous acid catalyst. The unique attributes of MOF and well-dispersed level of POMs prohibited the conglomeration and deactivation of POMs, which allowed for the enhancement of their catalytic properties.

  2. Polyoxometalate nanotubes from layer-by-layer coating and thermal removal of electrospun nanofibres

    NASA Astrophysics Data System (ADS)

    Ding, Bin; Gong, Jian; Kim, Jinho; Shiratori, Seimei

    2005-06-01

    We have recently fabricated Keggin-type polyoxometalate (H4SiW12O40) nanotubes by calcining layer-by-layer (LBL) structured ultrathin hybrid film coated electrospun fibrous mats. The hybrid film coated electrospun fibrous mats were obtained from the alternate deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged H4SiW12O40 on the surface of negatively charged cellulose acetate (CA) nanofibres using the electrostatic LBL self-assembly technique. The fibrous mats were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FT-IR) spectroscopy, and wide-angle x-ray diffraction (WAXD). It was found that the morphology of hybrid PAH/H4SiW12O40 film coated fibrous mats was strongly influenced by the number of deposition bilayers and the pH of dipping solutions. The fibrous mats were contracted and H4SiW12O40 nanotubes with a wall thickness of about 50 nm can be fabricated after calcination at high temperature. Additionally, the FT-IR and WAXD results indicated that the pure H4SiW12O40 nanotubes were obtained with a Keggin structure.

  3. Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

    PubMed

    Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G

    2016-11-23

    Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP(4+) ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P2 Mo18 O62(6-) and P2 W18 O62(6-) anions, and one Keplerate {Mo132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP(4+) sensitization in relation to the direct photoreduction of those compounds; (b) the P2 Mo18 O62(6-) anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P2 W18 O62(6-) anion; and (c) the high nuclearity Keplerate {Mo132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied.

  4. Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions α-[PM12O40]3- (M = Mo, W) in the Gas Phase

    SciTech Connect

    Waters, Tom; Huang, Xin; Wang, Xue B.; Woo, Hin-koon; O'Hair, Richard Aj; Wedd, Anthony G.; Wang, Lai S.

    2006-09-21

    Two polyoxometalate Keggin-type anions, a-PM12O403- (M = Mo, W), were transferred to the gas phase by electrospray; their electronic structure and stability were probed by photoelectron spectroscopy. These triply charged anions were found to be highly stable in the gas phase with large adiabatic electron detachment energies of 1.7 and 2.1 eV for M = Mo and W, respectively. The magnitude of the repulsive Coulomb barrier was measured as ~3.4 eV for both anions, providing an experimental estimate for the intramolecular Coulomb repulsion present in these highly charged anions. Density functional theory calculations were carried out and compared with the experimental data, providing insight into the electronic structure and valence molecular orbitals of the two Keggin anions. The calculations indicated that the highest occupied molecular orbital and other frontier orbitals for PM12O403- are localized primarily on the u2-oxo bridging ligands of the polyoxometalate framework, consistent with the reactivity on the u2-oxo sites observed in solution. It was shown that the HOMO of PW12O403- is stabilized relative to that of PMo12O403- by ~0.35 eV. The experimental adiabatic electron detachment energies of PM12O403- (i.e., the electron affinities of PM12O402-) are combined with recent calculations on the proton affinity of PM12O403- to yield O-H bond dissociation energies in PM12O39(OH)2- as ~5.1 eV

  5. Polymers incorporating covalently attached organoimido polyoxometalates

    DOEpatents

    Maatta, Eric A.; Moore, Aaron R.

    2004-03-16

    New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

  6. Aqueous tantalum polyoxometalate reactivity with peroxide.

    PubMed

    Fullmer, Lauren B; Malmberg, Christopher E; Fast, Dylan B; Wills, Lindsay A; Cheong, Paul Ha-Yeon; Dolgos, Michelle R; Nyman, May

    2017-07-04

    Peroxide ligation of aqueous metal-oxo clusters provides rich speciation and structural diversity, radiation sensitivity for manipulation with light, and both broadens and shifts pH-range stability. Here we demonstrate peroxide ligation of the polyoxometalate (POM) [Ta6O19](8-). We study in detail solution speciation of the peroxide-substituted cluster, and benchmark it to the peroxide-ligated niobate analogue, [Nb6O10(OH)3(O2)6](5-), whose solid-state structure has been reported. Raman and electrospray ionization mass spectroscopy do not detect any significant differences between the two analogues. However, small and wide-angle and total X-ray scattering strongly indicate that peroxide promotes linking of the hexameric tantalate clusters, rather than terminating and capping the clusters, as observed for the niobate analogue. We used computational studies to identify Raman peak positions, determine the energetics of exchange of oxo-ligands for peroxo-ligands, and provide models to help explain the X-ray scattering data. Understanding the solution speciation of peroxide-substituted polyoxotantalates is an important step towards its use in solution processed thin film materials, as well as developing new Ta-POM chemistry.

  7. Dye-polyoxometalate composite films: self-assembly, thermal and photochemical properties.

    PubMed

    Gao, Shuiying; Cao, Rong; Yang, Chunpeng

    2008-08-01

    A series of dye-polyoxometalate composite films were prepared by alternately depositing cationic dye molecules and anionic polyoxometalates such as Keggin-type [BW(12)O(40)](5-) and the sandwich complex [Co(4)(H(2)O)(2)(PW(9)O(34))(2)](10-)via layer-by-layer (LbL) self-assembly method. These cationic dye molecules (MB, AA, TH, BB3, BCB and NB) are heterocyclic planar and rigid phenothiazine and phenoxazine dye molecules with different substituting groups in the side chains. The self-assembly of the films was studied by UV-vis and IR spectra. The results show that the substituting groups of dye molecules such as NH(2) and CH(2)CH(3) have influence on the self-assembly properties. The continuous and regular growth of the films was also dependent upon hydrogen bonding (NHO) formed between the amino groups of dye molecules and oxygen atoms of POMs as well as electrostatic interactions. The investigation of thermal and photochemical treatments of the composite films is also presented. The thermal stability experiments indicate that the composite films of TH with two NH(2) substitute groups and NB with more pi-conjugated system exhibit high thermal stability, whereas the sunlight irradiation results indicate that the composite films of TH have good photochemical stability.

  8. Electrochemical oxygen reduction reaction by Pt nanoparticles on carbon support stabilized by polyoxometalates.

    PubMed

    Kishore, Pilli Satyananda; Viswanathan, Balasubramanian; Varadarajan, Thirukkallam Kanthadai

    2009-09-01

    The abilities of Keggin type polyoxometalate, silicotungstic acid (STA) to reduce metal ions by electron transfer and to modify carbon surface by strong adsorption have been explored for the preparation of Pt nanoparticles supported on carbon composites (20% Pt/STA-C). The prepared composites were characterized by Transmission electron microscopy (TEM and HRTEM)), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The electrocatalytic activities of the prepared nanocomposites were examined by using Cyclic voltammetry (CV) for oxygen reduction reaction which takes place at cathode in fuel cells. The prepared composite (20% Pt/STA-C) proved efficient compared to STA free 20% Pt/C, prepared by hydrogen reduction method. H2O2 intermediate formation is a serious concern as it reduces the activity of Pt sites during oxygen reduction. The composites prepared by polyoxometalate reduction method (20% Pt/STA-C) showed better reduction ability towards H2O2 compared to STA free 20% Pt/C composite and thus showed better performance as cathode electrocatalyst for fuel cells.

  9. Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface.

    PubMed

    Zhang, Junyong; Chang, Shaoqing; Suryanto, Bryan H R; Gong, Chunhua; Zeng, Xianghua; Zhao, Chuan; Zeng, Qingdao; Xie, Jingli

    2016-06-06

    Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O (1) was obtained in a reasonable yield (13% based on IrCl3·H2O). Compound 1 was characterized by Fourier transform IR, UV-visible, (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. (31)P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K14[(IrCl4)KP2W20O72] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2'-bipyridine [Ru(bpy)3](2+/3+). The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)3](3+/2+) and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. "S"-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure.

  10. Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

    SciTech Connect

    Chai, Feng; Chen, YiPing; You, ZhuChai; Xia, ZeMin; Ge, SuZhi; Sun, YanQiong; Huang, BiHua

    2013-06-01

    Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atoms in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.

  11. Two-dimensional layer architecture assembled by Keggin polyoxotungstate, Cu(II)-EDTA complex and sodium linker: Synthesis, crystal structures, and magnetic properties

    SciTech Connect

    Liu Hong; Xu Lin Gao Guanggang; Li Fengyan; Yang Yanyan; Li Zhikui; Sun Yu

    2007-05-15

    Reaction of Keggin polyoxotungstate with copper(II)-EDTA (EDTA=ethylenediamine tetraacetate) complex under mild conditions led to the formation of hybrid inorganic-organic compounds Na{sub 4}(OH)[(Cu{sub 2}EDTA)PW{sub 12}O{sub 40}].17H{sub 2}O (1) and Na{sub 4}[(Cu{sub 2}EDTA)SiW{sub 12}O{sub 40}].19H{sub 2}O (2). The single-crystal X-ray diffraction analyses reveal their two structural features: (1) one-dimensional chain structure consisting of Keggin polyoxotungstate and copper(II)-EDTA complex; (2) Two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker. The results of magnetic measurements in the temperature range 300-2 K indicated the existence of ferromagnetic exchange interactions between the Cu{sup II} ions for both compounds. In addition, TGA analysis, IR spectra, and electrochemical properties were also investigated to well characterize these two compounds. - Graphical abstract: Two new polyoxometalate-based hybrids, Na{sub 4}(OH)[Cu{sub 2}(EDTA)PW{sub 12}O{sub 40}].17H{sub 2}O (1) and Na{sub 4}[Cu{sub 2}(EDTA)SiW{sub 12}O{sub 40}].19H{sub 2}O (2), have been synthesized and structurally characterized, which consist of one-dimensional chain structure assembled by Keggin polyoxotungstate and copper(II)-EDTA complex. The chains are further connected to form two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker.

  12. Assembly of Tungsten-Oxide-Based Pentagonal Motifs in Solution Leads to Nanoscale {W48}, {W56}, and {W92} Polyoxometalate Clusters.

    PubMed

    Zhan, Cai-Hong; Winter, Ross S; Zheng, Qi; Yan, Jun; Cameron, Jamie M; Long, De-Liang; Cronin, Leroy

    2015-11-23

    We report an approach to synthesize molecular tungsten-oxide-based pentagonal building blocks, in a new {W21 O72} unit, and show how this leads to a family of gigantic molecular architectures including [H12W48O164](28-) {W48}, [H20W56O190](24-) {W56}, and [H12W92O311](58-) {W92}. The {W48} and {W56} clusters are both dimeric species incorporating two {W21} units and the {W56} species is the first example of a molecular metal oxide cluster containing a chiral "double-stranded" motif which is stable in solution as confirmed by mass spectrometry. The {W92} anion having four {W21} units is one of the largest transition metal substituted isopolyoxotungstates known. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Keggin polyoxoanion supported organic-inorganic trinuclear lutetium cluster, {Na(H2O)3[Lu(pydc)(H2O)3]3}[SiW12O40]·26.5H2O.

    PubMed

    Li, Suzhi; Zhang, Dongdi; Guo, Yuan Yuan; Ma, Pengtao; Qiu, Xiaoyang; Wang, Jingping; Niu, Jingyang

    2012-09-07

    A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.

  14. Fate of a giant {Mo72Fe30}-type polyoxometalate cluster in an aqueous solution at higher temperature: understanding related Keplerate chemistry, from molecule to material.

    PubMed

    Mekala, Raju; Supriya, Sabbani; Das, Samar K

    2013-09-03

    When the giant icosahedral {Mo72Fe30} cluster containing compound [Mo72Fe30O252(CH3COO)12{Mo2O7(H2O)}2{H2Mo2O8(H2O)}(H2O)91]·150H2O (1) is refluxed in water for 36 h, it results in the formation of nanoiron molybdate, Fe2(MoO4)3, in the form of a yellow precipitate; this simple approach not only generates nanoferric molybdate at a moderate temperature but also helps to understand the stability of {Mo72Fe30} in terms of the linker-pentagon complementary relationship.

  15. [Mn(III)Mn(IV)2Mo14O56](17-): A Mixed-Valence Meso-Polyoxometalate Anion Encapsulated by a 64-Nuclearity Silver Cluster.

    PubMed

    Wang, Jian-Yu; Liu, Kuan-Guan; Guan, Zong-Jie; Nan, Zi-Ang; Lin, Yu-Mei; Wang, Quan-Ming

    2016-07-18

    A 64-nuclearity silver cluster encapsulating a unique POM anion [Mn(III)Mn(IV)2Mo14O56](17-) has been synthesized. The formation of the templating core performs a reassembly process for increasing nuclearities from {MnMo9} to {Mn3Mo14}. It represents a rare inorganic meso anion containing mixed-valent Mn that is built up by d-{Mn(IV)Mo7} and l-{Mn(IV)Mo7} units connecting together through a {Mn(III)} fragment.

  16. A polyoxometalate-based single-molecule magnet with an S = 21/2 ground state.

    PubMed

    Fang, Xikui; Kögerler, Paul; Speldrich, Manfred; Schilder, Helmut; Luban, Marshall

    2012-01-30

    Ligand modification transforms a polyoxometalate-anchored cubane-type [Mn(III)(3)Mn(IV)O(4)] core into a centrosymmetric [Mn(III)(6)Mn(IV)O(8)] di-cubane cluster, and restores the slow magnetization relaxation characteristics typical for [Mn(4)O(4)] cubane-based single-molecule magnets.

  17. Chiral Dawson-Type Hybrid Polyoxometalate Catalyzes Enantioselective Diels-Alder Reactions.

    PubMed

    Xuan, Wen-Jing; Botuha, Candice; Hasenknopf, Bernold; Thorimbert, Serge

    2015-11-09

    Can achiral organocatalysts linked to chiral polyanionic metal oxide clusters provide good selectivity in enantioselective C-C bond formations? The answer to this question is investigated by developing a new active hybrid polyoxometalate-based catalyst for asymmetric Diels-Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows Diels-Alder cycloaddition products to be obtained with good yields and high enantioselectivities when using cyclopentadiene and acrylaldehydes as partners. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Zeolitic polyoxometalate-based metal-organic frameworks (Z-POMOFs): computational evaluation of hypothetical polymorphs and the successful targeted synthesis of the redox-active Z-POMOF1.

    PubMed

    Rodriguez-Albelo, L Marleny; Ruiz-Salvador, A Rabdel; Sampieri, Alvaro; Lewis, Dewi W; Gómez, Ariel; Nohra, Brigitte; Mialane, Pierre; Marrot, Jérôme; Sécheresse, Francis; Mellot-Draznieks, Caroline; Ngo Biboum, Rosa; Keita, Bineta; Nadjo, Louis; Dolbecq, Anne

    2009-11-11

    The targeted design and simulation of a new family of zeolitic metal-organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and epsilon-type Keggin polyoxometalates (POMs) as building units, named here Z-POMOFs, have been performed. A key feature is the use of the analogy between the connectivity of silicon in dense minerals and zeolites with that of the epsilon-type Keggin POMs capped with Zn(II) ions. Handling the epsilon-Keggin as a building block, a selection of 21 zeotype structures, together with a series of dense minerals were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like structure was predicted to be the most stable structure. This prediction has been experimentally validated by the targeted synthesis of the first experimental Z-POMOF structure, which was strikingly found to possess the cristobalite topology, with three interpenetrated networks. Crystals of [NBu(4)](3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)(BDC)(2)].2H(2)O (Z-POMOF1) have been isolated under hydrothermal conditions from the reduction of ammonium heptamolybdate in the presence of phosphorous acid and Zn(II) ions. Tetrabutylammonium cations play the role of counterions and space-filling agents in this tridimensional interpenetrated framework. Moreover, the electrochemistry of the epsilon-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.

  19. Keggin-Type PMo11V as a P-type Dopant for Enhancing the Efficiency and Reproducibility of Perovskite Solar Cells.

    PubMed

    Dong, Guohua; Xia, Debin; Yang, Yulin; Shenga, Li; Ye, Tengling; Fan, Ruiqing

    2017-01-25

    The conventional perovskite solar cells (PSCs) with 2,2',7,7'-tetrakis(N,N-dimethoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) as a hole transporting material commonly suffer from poor stability and reproducibility mainly due to the process of placing the devices in air and illumination for oxidizing the spiro-OMeTAD. Herein, Keggin-type polyoxometalates (POMs)-phosphovanadomolybdate (H4PMo11V·nH2O, denoted as PMo11V) is for the first time employed as a p-type dopant for promoting the oxidation of spiro-OMeTAD. Thereby, without illumination and air, the conductivity and hole extraction efficiency of the PMo11V doped spiro-OMeTAD with assistance of lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and 4-tert-butylpyridine (TBP) can be dramatically enhanced. On the basis of this strategy, the corresponding PSCs exhibit substantially improved photovoltaic performance and good reproducibility. The best performing device yields a power conversion efficiency (PCE) of 14.05%. This work indicates a great potential of polyoxometalates for further applications in solar cells and other optoelectronics devices.

  20. POLYOXOMETALATES FOR RADIOACTIVE WASTE TREATMENT

    SciTech Connect

    Pope, Michael T.

    2000-06-01

    The research project has two major goals: (1) the selective sequestration of lanthanide (Ln) and actinide (An) cations, and technetium species, from tank waste solutions, using radiation-resistant and thermally-stable polyoxometalate anions as complexants, and (2) the conversion of complexed Ln/An/Tc to reduced oxide bronzes (e.g. MxWO3) under relatively mild conditions, and evaluation of the use of such bronzes as waste forms.

  1. Polyoxometalates for Radioactive Waste Treatment

    SciTech Connect

    Pope, Michael T.; Bryan, Jeffrey

    1999-06-01

    The research project has two major goals: (1) the selective sequestration of lanthanide (Ln) and actinide (An) cations, and technetium species, from tank waste solutions, using radiation-resistant and thermally-stable polyoxometalate anions as complexants, and (2) the conversion of complexed Ln/An/Tc to reduced oxide bronzes (e.g. MxWO3) under relatively mild conditions, and evaluation of the use of such bronzes as waste forms.

  2. Experimental and theoretical investigations of the sulfite-based polyoxometalate cluster redox series: alpha- and beta-[Mo(18)O(54)(SO(3))(2)](4-/5-/6-).

    PubMed

    Baffert, Carole; Boas, John F; Bond, Alan M; Kögerler, Paul; Long, De-Liang; Pilbrow, John R; Cronin, Leroy

    2006-11-15

    The synthesis, isolation and structural characterization of the sulfite polyoxomolybdate clusters alpha-(D(3h))(C(20)H(44)N)(4){alpha-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN and beta-(D(3d))(C(20)H(44)N)(4){beta-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN is presented. Voltammetric studies in acetonitrile (0.1 M Hx(4)NClO(4), Hx(4)N=tetra-n-hexylammonium) reveal the presence of an extensive series of six one-electron reduction processes for both isomers. Under conditions of bulk electrolysis, the initial [Mo(18)O(54)(SO(3))(2)](4-/5-) and [Mo(18)O(54)(SO(3))(2)](5-/6-) processes produce stable [Mo(18)O(54)(SO(3))(2)](5-) and [Mo(18)O(54)(SO(3))(2)](6-) species, respectively, and the same reduced species may be produced by photochemical reduction. Spectroelectrochemical data imply that retention of structural form results upon reduction, so that both alpha and beta isomers are available at each of the 4-, 5-, and 6-redox levels. However, the alpha isomer is the thermodynamically favored species in both the one- and two-electron-reduced states, with beta-->alpha isomerization being detected in both cases on long time scales (days). EPR spectra also imply that increasing localization of the unpaired electron occurs over the alpha- and beta-[Mo(18)O(54)(SO(3))(2)](5-) frameworks as the temperature approaches 2 K where the EPR spectra show orthorhombic symmetry with different g and hyperfine values for the alpha and beta isomers. Theoretical studies support the observation that it is easier to reduce the alpha cluster than the beta form and also provide insight into the driving force for beta-->alpha isomerization in the reduced state. Data are compared with that obtained for the well studied alpha-[Mo(18)O(54)(SO(4))(2))](4-) sulfate cluster.

  3. Cryogenic luminescent thermometers based on multinuclear Eu(3+)/Tb(3+) mixed lanthanide polyoxometalates.

    PubMed

    Kaczmarek, A M; Liu, J; Laforce, B; Vincze, L; Van Hecke, K; Van Deun, R

    2017-05-09

    Here, the excellent thermal sensing capability of a multinuclear lanthanide polyoxometalate in the cryogenic region (<100 K) is presented for the first time. Up till now, no lanthanide polyoxometalates have been studied for their use as ratiometric luminescent thermometers. The investigated Tb(3+) polyoxometalate cluster is doped with 1.6% (P1) and 8.4% (P2) of Eu(3+) ions. When excited into the Mo-O charge transfer bands, at room temperature only the emission of the Eu(3+) ions is observed suggesting a very efficient energy transfer between Mo-O→Tb(3+)→Eu(3+). Only in the cryogenic region the emission of Tb(3+) is also witnessed.

  4. Synthesis, crystal structure, and properties of a 1-D terbium-substituted monolacunary Keggin-type polyoxotungstate.

    PubMed

    Ma, Pengtao; Si, Yanan; Wan, Rong; Zhang, Shaowei; Wang, Jingping; Niu, Jingyang

    2015-03-05

    A new 1-D linear chainlike terbium-substituted polyoxometalate [Tb(H2O)2(α-PW11O39)](4-) (1) has been synthesized in aqueous solution and characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, electrospray ionization mass spectrometry (ESI-MS), and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 displays a 1-D linear chain containing [Tb(H2O)2(α-PW11O39)](4-) moieties. The Tb(III) cation incorporated into the monolacunary Keggin-type [α-PW11O39](7-) unit resides in a distorted monocapped triangular prismatic geometry and acts as a linker to join two adjacent [α-PW11O39](7-) units to form a 1-D chain structure. Solid-state photoluminescent property of 1 has been investigated at room temperature and the photoluminescent emission mainly results from the synergistic effect of the Tb(III) cation and the Na7[α-PW11O39] precursor. The ESI-MS spectrum of 1 confirms that the polyanion [Tb(H2O)(HPW11O39)](3-) is stable in aqueous solution.

  5. Synthesis, crystal structure, and properties of a 1-D terbium-substituted monolacunary Keggin-type polyoxotungstate

    NASA Astrophysics Data System (ADS)

    Ma, Pengtao; Si, Yanan; Wan, Rong; Zhang, Shaowei; Wang, Jingping; Niu, Jingyang

    2015-03-01

    A new 1-D linear chainlike terbium-substituted polyoxometalate [Tb(H2O)2(α-PW11O39)]4- (1) has been synthesized in aqueous solution and characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, electrospray ionization mass spectrometry (ESI-MS), and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 displays a 1-D linear chain containing [Tb(H2O)2(α-PW11O39)]4- moieties. The Tb(III) cation incorporated into the monolacunary Keggin-type [α-PW11O39]7- unit resides in a distorted monocapped triangular prismatic geometry and acts as a linker to join two adjacent [α-PW11O39]7- units to form a 1-D chain structure. Solid-state photoluminescent property of 1 has been investigated at room temperature and the photoluminescent emission mainly results from the synergistic effect of the TbIII cation and the Na7[α-PW11O39] precursor. The ESI-MS spectrum of 1 confirms that the polyanion [Tb(H2O)(HPW11O39)]3- is stable in aqueous solution.

  6. Mesomorphic structures of protonated surfactant-encapsulated polyoxometalate complexes.

    PubMed

    Yin, Shengyan; Li, Wen; Wang, Jinfeng; Wu, Lixin

    2008-04-03

    Keggin-type heteropolyanions, H(3)PW(12)O(40) (HPW), Na(3)PW(12)O(40) (NaPW), H(4)SiW(12)O(40) (HSiW) and K(4)SiW(12)O(40) (KSiW), were encapsulated by a cationic surfactant, di[12-(4'-octyloxy-4-azophenyl)dodecyloxy]dimethylam monium bromide (L), through the replacement of counterions. The resulting surfactant-encapsulated polyoxometalate complexes were characterized by UV-vis, Raman, and NMR spectra in detail. The measurement results indicated that some azobenzene groups of the surfactant were protonated in the complexes HL/HPW (HL is the abbreviation of the protonated surfactant), HL/NaPW, and HL/HSiW during the process of encapsulation, whereas the protonation was not observed in L/KSiW. The thermotropic liquid crystal properties of these complexes were investigated by differential scanning calorimetry, polarized optical microscopy and variable-temperature X-ray diffraction. Interestingly, different smectic mesophases were observed between the protonated HL/HSiW and the non-protonated L/KSiW, which suggests that the protonation of azobenzene groups in HL/HSiW plays a key role in the liquid crystalline organization. However, protonated HL/HPW and HL/NaPW exhibit a similar smectic B phase to that of the de-protonated one, L/HPW. A competitive balance between the phase separation and the volume minimization of surfactants was proposed to explain the self-organized liquid crystal structures of these protonated and non-protonated complexes. To the best of our knowledge, the present investigation provides a specific example for protonated hybrid materials with stable liquid crystal properties.

  7. Synthesis and energy band characterization of hybrid molecular materials based on organic–polyoxometalate charge-transfer salts

    SciTech Connect

    Tan, Chunxia; Bu, Weifeng

    2014-11-15

    A cationic amphiphilic molecule was synthesized and employed to encapsulate Lindqvist ([M{sub 6}O{sub 19}]{sup 2−}) and Keggin polyoxometalates ([SiM{sub 12}O{sub 40}]{sup 4−}, M=Mo, W) to form hybrid molecules through electrostatic interaction. The X-ray diffraction results illustrate that the former hybrids possess lamellar nanostructures in their solid states, while the latter hybrids show a cubic Im3m packing model with low intensities and poor long-range order. These hybrids have clear charge-transfer characters as shown in their deeper colors and UV–vis diffuse reflectance spectra. According to the reported reduction potentials of the POM acceptors and the band gaps deduced from their diffuse reflectance spectra, we have calculated the theoretical values of the lowest unoccupied molecular orbital (LUMO) position similar to the electron affinity (E{sub A}) of solid materials. Such energy level parameters are comparable to those of electroluminescence and electron-transport materials commonly used in organic electroluminescence devices. These organic–polyoxometalate charge-transfer salts have more advantages, such as higher decomposition temperatures, easier film fabrication and better electron affinities, which presumably would be used for electron-transport materials in the area of the electroluminescence. - Graphical abstract: Hybrid molecular materials with charge-transfer characters formed by a positively charged donor L and acceptors of the Lindqvist-type and Keggin-type POMs have lamellar and cubic structures in their solid state. - Highlights: • Charge-transfer salts are obtained by self-assembling POMs with an anthracene cation. • Their energy parameters are comparable to those of optoelectronic materials in OLEDs. • These POM-based hybrids could be applied in the area of optoelectronic devices.

  8. Self-Assembly of a Giant Tetrahedral 3 d-4 f Single-Molecule Magnet within a Polyoxometalate System.

    PubMed

    Ibrahim, Masooma; Mereacre, Valeriu; Leblanc, Nicolas; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

    2015-12-14

    A giant tetrahedral heterometallic polyoxometalate (POM) [Dy30 Co8 Ge12 W108 O408 (OH)42 (OH2 )30 ](56-) , which shows single-molecule magnet (SMM) behavior, is described. This hybrid contains the largest number of 4f ions of any polyoxometalate (POM) reported to date and is the first to incorporate two different 3d-4f and 4f coordination cluster assemblies within same POM framework.

  9. Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

    DOEpatents

    Hill, Craig L.; Gueletii, Iourii V.; Song, Jie; Lv, Hongjin; Musaev, Djamaladdin; Luo, Zhen

    2017-08-22

    This disclosure relates to photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts. In certain embodiments, the disclosure relates to compositions comprising water, a complex of a tetra-metal oxide cluster and VW.sub.9O.sub.34 ligands, and a photosensitizer. Typically, the metal oxide cluster is Co. In certain embodiments, the disclosure relates to electrodes and other devices comprising water oxidation catalysts disclosed herein and uses in generating fuels and electrical power from solar energy.

  10. Polyoxometalate-Incorporated Metallapillararene/Metallacalixarene Metal-Organic Frameworks as Anode Materials for Lithium Ion Batteries.

    PubMed

    Yang, Xi-Ya; Wei, Tao; Li, Ji-Sen; Sheng, Ning; Zhu, Pei-Pei; Sha, Jing-Quan; Wang, Tong; Lan, Ya-Qian

    2017-07-17

    A series of remarkable crystalline compounds containing metallapillararene/metallacalixarene metal-organic frameworks (MOFs), [Ag5(pyttz)3·Cl·(H2O)][H3SiMo12O40]·3H2O (1), [Ag5(trz)6][H5SiMo12O40] (2), [Ag5(trz)6][H5GeMo12O40] (3), and [Ag5(trz)6][H4PW12O40] (4) (pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, trz = 1,2,4-triazole), have been obtained by using a simple one-step hydrothermal reaction of silver nitrate, pyttz for 1 and trz for 2-4, and Keggin type polyoxometalates (POMs). Crystal analysis reveals that Keggin POMs have been successfully incorporated in the windows of the metallapillararene/metallacalixarene MOFs in compounds 1-4. In addition, the Keggin silicomolybdenate-based hybrid compounds 1 and 2 were used as anode materials in lithium ion batteries (LIBs), which exhibited promising electrochemical performance with the first discharge capacities of 1344 mAh g(-1) for 1 and 1452 mAh g(-1) for 2, and this stabilized at 520 mAh g(-1) for 1 and 570 mAh g(-1) for 2 after 100 cycles at a current density of 100 mA g(-1). The performances are better than that of (NBu4)4[SiMo12O40] matrix and commercial graphite anodes.

  11. Self‐Templating and In Situ Assembly of a Cubic Cluster‐of‐Clusters Architecture Based on a {Mo24Fe12} Inorganic Macrocycle

    PubMed Central

    Xuan, Weimin; Surman, Andrew J.; Zheng, Qi; Long, De‐Liang

    2016-01-01

    Abstract Engineering self‐templating inorganic architectures is critical for the development of bottom‐up approaches to nanoscience, but systems with a hierarchy of templates are elusive. Herein we describe that the cluster‐anion‐templated (CAT) assembly of a {CAT}⊂{Mo24Fe12} macrocycle forms a giant ca. 220 nm3 unit cell containing 16 macrocycles clustered into eight face‐shared tetrahedral cluster‐of‐clusters assemblies. We show that {CAT}⊂{Mo24Fe12} with different CATs gives the compounds 1–4 for CAT=Anderson {FeMo6} (1), Keggin {PMo12} (2), Dawson {P2W18} (3), and {Mo12O36(HPO3)2} (4) polyoxometalates. “Template‐free” assembly can be achieved, whereby the macrocycle components can also form a template in situ allowing template to macrocycle to superstructure formation and the ability to exchange the templates. Furthermore, the transformation of template clusters within the inorganic macrocycle {Mo24Fe12} allows the self‐generation of an uncapped {Mo12O36(HPO3)2} in compound 4. PMID:27358195

  12. Study on the Keggin zinctungstates based hybrid compound with like DNA spiral chain

    NASA Astrophysics Data System (ADS)

    Li, Liang; Sha, Jing-Quan; Zong, Xi-Ming; Liu, Cui-Juan; Zhang, Qian-Nan; Wang, Dong-Wen; Yang, Xiao-Ning; Wang, Yu

    2014-05-01

    A new compound based on polyoxometalates (POMs) and the quinolone antibacterial pipemidic acid (HPPA), {[Zn(HPPA)2H2O]2[H2ZnW12O40]}ṡ9H2O (1), was hydrothermally synthesized and characterized by elemental analyses, IR and XPRD. Single-crystal X-ray diffraction analysis reveals that the [ZnW12O40 ] 6 - clusters and Zn-HPPA complexes constructed both right- and left-double-stranded like DNA helical chains in the title compound, and these helical chains are further connected together forming the fascinating quadruple-stranded helices via sharing the ZnW12 clusters. Note that the compound 1 represents the first example of zinctungstate POMs modified by antibacterial drugs. In addition, the antibacterial properties of the compound 1 were investigated.

  13. Ternary Porphyrinato Hf(IV) and Zr(IV) - Polyoxometalate Complexes

    PubMed Central

    Falber, Alexander; Burton-Pye, Benjamin P.; Radivojevic, Ivana; Todaro, Louis; Saleh, Raihan; Francesconi, Lynn; Drain, Charles Michael

    2010-01-01

    We report a facile, high yield synthesis and characterization of discrete, ternary porphyrin-metal-polyoxometalate (Por-M-POM) complexes where a group (IV) transition metal ion is bound both to the porphyrin core and to the lacunary site of a Keggin POM, PW11O39−7. The remarkably robust complexes exploit the fact that Hf(IV) and Zr(IV) are 7–8 coordinate and reside outside the plane of the porphyrin macrocycle, thus enabling the simultaneous coordination to meso-tetraphenylporphyrin (TPP) or meso-tetra(4-pyridyl)porphyrin (TPyP) and to the defect site in the Keggin framework. The physical properties of the (TPP)Hf(PW11O39)[TBA]5, (TPyP)Hf(PW11O39)[TBA]5, and (TPP)Zr(PW11O39)[TBA]5 complexes are similar because the metal ions have similar oxidation states, and coordination chemistry. This architecture couples the photonic properties of the porphyrin to the POM because the metal ion is incorporated into both frameworks. Thus the ternary complexes can serve as a basis for the characterization of Hf(IV) and Zr(IV) porphyrins bound to oxide surfaces via the group (IV) metal ions. The Hf(Por) and Zr(Por) bind strongly to TiO2 nanoparticles and indium tin oxide (ITO) surfaces, but significantly less binds to crystalline SiO2 or TiO2 surfaces. Together, the strong binding of the metalloporphyrins to the POM, nanoparticles, and the ITO surfaces, and paucity of binding to crystalline surfaces, suggests that the 3–4 open coordination sites on the Hf(Por) and Zr(Por) are predominantly bound at surface defect sites. PMID:20543903

  14. Synthesis and energy band characterization of hybrid molecular materials based on organic-polyoxometalate charge-transfer salts

    NASA Astrophysics Data System (ADS)

    Tan, Chunxia; Bu, Weifeng

    2014-11-01

    A cationic amphiphilic molecule was synthesized and employed to encapsulate Lindqvist ([M6O19]2-) and Keggin polyoxometalates ([SiM12O40]4-, M=Mo, W) to form hybrid molecules through electrostatic interaction. The X-ray diffraction results illustrate that the former hybrids possess lamellar nanostructures in their solid states, while the latter hybrids show a cubic Im3m packing model with low intensities and poor long-range order. These hybrids have clear charge-transfer characters as shown in their deeper colors and UV-vis diffuse reflectance spectra. According to the reported reduction potentials of the POM acceptors and the band gaps deduced from their diffuse reflectance spectra, we have calculated the theoretical values of the lowest unoccupied molecular orbital (LUMO) position similar to the electron affinity (EA) of solid materials. Such energy level parameters are comparable to those of electroluminescence and electron-transport materials commonly used in organic electroluminescence devices. These organic-polyoxometalate charge-transfer salts have more advantages, such as higher decomposition temperatures, easier film fabrication and better electron affinities, which presumably would be used for electron-transport materials in the area of the electroluminescence.

  15. Polyoxometalate-based metal organic frameworks (POMOFs): structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction.

    PubMed

    Nohra, Brigitte; El Moll, Hani; Rodriguez Albelo, L Marleny; Mialane, Pierre; Marrot, Jérôme; Mellot-Draznieks, Caroline; O'Keeffe, Michael; Ngo Biboum, Rosa; Lemaire, Joël; Keita, Bineta; Nadjo, Louis; Dolbecq, Anne

    2011-08-31

    The grafting of the triangular 1,3,5-benzene tricarboxylate linkers (denoted trim) on tetrahedral ε-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)][C(6)H(3)(COO)(3)](4/3)·6H(2)O (ε(trim)(4/3)) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. ε(trim)(4/3) is a novel (3,4)-connected net, named ofp for open-framework polyoxometalate, and computer simulations have been used to evaluate its relative stability in comparison with ctn- and bor-like polymorphs, showing the stability of this novel phase directly related to its greatest density. A computational study was also undertaken with the aim of locating TBA molecules, the positions of which could not be deduced from single crystal X-ray diffraction, and further rationalizes their structure directing role. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)] (ε(2)(trim)(2)), the building unit is not the molecular Keggin but a dimerized form of this POM. Their connection via trim linkers generates a 3D framework with channels filled by TBA cations. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)]·8H(2)O ([ε(trim)](∞)), zigzag chains are connected via the organic linkers, forming 2D grids. Modified electrodes were fabricated by direct adsorption of the POMOFs on glassy carbon or entrapment in carbon paste (CPE). A remarkable electrocatalytic hydrogen evolution reaction (HER) was detected with a yield greater than 95%, and a turnover number as high as 1.2 × 10(5) was obtained after 5 h. The reported POMOF-based electrodes are more active than platinum, with a roughly 260 mV anodic shift. Finally, the electrocatalytic activities of ε(trim)(4/3)/CPE electrodes in various XCl (X = Li, Na, K, Cs) media have been studied

  16. Polyoxometalate (POM) Macroion Decorated Polymersomes

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Connor, Erin; Zhu, Y. Elaine

    2014-03-01

    Polymersomes as one of the common self-assembled forms of amphiphilic block copolymers have been widely developed for applications from drug delivery to mirco/nanoreactors. The tunability of their materials properties, such as mechanical strength and permeability often relies on the chemistry of the selected polymer in a liquid medium. We have recently employed the emergent polyoxometalate (POM) nanoclusters as macroions to control their interaction and assembly with different polymersomes. For both neutral and cationic polymersomes decorated with highly charged anionic POM nanoclusters, the dispersion stability and mechanic strength can be significantly enhanced. AFM and TEM characterization further confirms the encapsulation of POM macroions into polymersomes to form inorganic-organic hybrid complexes, which lead to new potential applications in anticancer and antibacterial medicines and catalysts.

  17. New Vistas for Functionalized Polyoxometalates

    SciTech Connect

    Maatta, Eric A.

    2006-04-21

    Polyoxometalates (POMs) - the multimetallic oxoanions [MxOyXz]n? formed by Mo, W, and, to a lesser extent, V, Nb and Ta ? have been described as "a class of inorganic compounds that is unmatched in terms of molecular and electronic structural versatility, reactivity, and relevance". The remarkable breadth of POM chemistry, which extends to areas as diverse as catalysis, medicine, imaging, photo- and electrochromism, and magnetic materials, derives from the confluence of the species' attractive intrinsic characteristics and their extraordinary compositional range. While many of these systems are easy to prepare, it is often difficult to modify POMs in a rational manner. Our goal is to provide for the intrinsic modifcation of POM systems so as to enable their further utility: our approach has provided many examples of fundamentally new types of polyoxometalates in which their ubiquitous oxo [O]2? ligands have been replaced by other isoelectronic entities including organoimido [N-R]2? and diazoalkane [NNCR2]2?ligands. These nitrogenous POM derivatives retain the attractive attributes typical of the class but with altered and tunable characteristics including their redox behavior and electronic absorption patterns. The organoimido and diazoalkane species provide the ability to couple remote and useful functionality via the appended substituents R. We also are now engaged in the preparation and study of nitrido-POM systems: these unprecedented inorganic complexes offer the possibility of effecting various types of nitrido-based transformations (such as nitrogen transfer) which could benefit from the superior oxidative and thermal stability of the POM ligation environment.

  18. A novel single-side azobenzene-grafted Anderson-type polyoxometalate for recognition-induced chiral migration.

    PubMed

    Zhang, Bin; Yue, Liang; Wang, Yang; Yang, Yang; Wu, Lixin

    2014-09-25

    A three-component supramolecular hybrid system based on host-guest recognition and electrostatic interaction has been developed for a consecutive chiral transfer from an alpha-cyclodextrin to cationic dyes via the bridge of a new azobenzene-grafted Anderson-type polyoxometalate cluster.

  19. Polyoxometalate complexes for oxidative kinetic resolution of secondary alcohols: unique effects of chiral environment, immobilization and aggregation.

    PubMed

    Shi, Lei; Wang, Yizhan; Li, Bao; Wu, Lixin

    2014-06-28

    In this paper, the chiral surfactants bearing two long alkyl chains with hydroxyl groups at their terminals were synthesized and employed to encapsulate a catalytically efficient polyoxometalate through electrostatic interaction. The obtained chiral surfactant-encapsulated polyoxometalate complexes, in which a defined chiral microenvironment surrounds the inorganic cluster, were covalently immobilized into the silica matrix via a sol-gel process. Kinetic resolution of racemic aromatic alcohols was selected as the model reaction to evaluate the chiral supramolecular hybrid catalysts. Up to 89% enantiomeric excess was obtained by varying the reaction conditions. Importantly, the change of loading values of the chiral surfactant-encapsulated polyoxometalates leads to mutative inner microstructures ranging from uniform dispersion to subsequent formation of nanocrystalline domains in the silica matrix. Such a structural evolution differentiates the density and stability of the chiral microenvironment, resulting in a regular change of enantioselectivity of the prepared asymmetric catalysts. Moreover, the fixation of the chiral microenvironment surrounding the polyoxometalates by covalent immobilization was proved to have a promoting effect on enantioselectivity. The present research uncovers the unique effect of immobilization on the kinetic resolution. The strategy helps to understand the influencing factors of enantioselectivity, and provides a convenient and efficient approach for the construction of supramolecular asymmetric catalysts based on chiral surfactant-encapsulated polyoxometalate complexes.

  20. Investigation of the formation process of zeolite-like 3D frameworks constructed with ε-Keggin-type polyoxovanadomolybdates with binding bismuth ions and preparation of a nano-crystal.

    PubMed

    Zhang, Zhenxin; Sadakane, Masahiro; Murayama, Toru; Ueda, Wataru

    2014-09-28

    Reaction conditions for the synthesis of an ε-Keggin-type polyoxometalate-based 3D framework, (NH4)2.8H0.9[ε-VMo9.4V2.6O40Bi2]·7.2H2O (denoted as Mo-V-Bi oxide), are studied. It is found that the reaction time, temperature, pH of the solution, and starting compounds affect the production of Mo-V-Bi oxide. The crystal size of Mo-V-Bi oxide is controllable by changing bismuth compounds. Nanometer-sized Mo-V-Bi oxide is produced using a water-soluble bismuth compound, Bi(NO3)3·5H2O, whereas micrometer to submicrometer-sized Mo-V-Bi oxide is produced using Bi(OH)3, which is less soluble in water. The particle size of the material affects the properties of the material, such as surface area and catalysis. The investigation of the formation process of the material is carried out with Raman spectroscopy, which indicates that mixing (NH4)6Mo7O24·4H2O, VOSO4·5H2O, and bismuth ions in water produces the ε-Keggin polyoxovanadomolybdate together with a ball-shaped polyoxovanadomolybdate, [Mo72V30O282(H2O)56(SO4)12](36-) (denoted as {Mo72V30}). By heating the reaction mixture, the ε-Keggin polyoxovanadomolybdate assembles with bismuth ions to form Mo-V-Bi oxide, whereas {Mo72V30} assembles with other vanadium and molybdenum ions to form orthorhombic Mo-V oxide.

  1. Lithium intercalation reaction into the Keggin type polyoxomolybdates

    NASA Astrophysics Data System (ADS)

    Sonoyama, Noriyuki; Suganuma, Yoshiaki; Kume, Tomohiro; Quan, Zhen

    The electrochemical property of Keggin type hetero polyoxomolybdate K 3[PMo 12O 40] (KPM) as the cathode electrode material for lithium battery was examined. KPM showed charge-discharge performance in the potential region from 4.2 V to 1.5 V with capacity of over 200 mAh g -1. From the result of the ex situ XRD measurement, it is presumed that the electrochemical reaction of KPM proceeds via the lithium (de-)intercalation. The cycle performance of KPM is largely dependent on the charge-discharge potential range. The capacity fade caused by deep discharging seems to be concerned to the < to ® isomerization of KPM.

  2. Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

    PubMed

    Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

    2015-01-01

    A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

  3. High-field (95) Mo and (183) W static and MAS NMR study of polyoxometalates.

    PubMed

    Haouas, Mohamed; Trébosc, Julien; Roch-Marchal, Catherine; Cadot, Emmanuel; Taulelle, Francis; Martineau-Corcos, Charlotte

    2017-10-01

    The potential of high-field NMR to measure solid-state (95) Mo and (183) W NMR in polyoxometalates (POMs) is explored using some archetypical structures like Lindqvist, Keggin and Dawson as model compounds that are well characterized in solution. NMR spectra in static and under magic angle spinning (MAS) were obtained, and their analysis allowed extraction of the NMR parameters, including chemical shift anisotropy and quadrupolar coupling parameters. Despite the inherent difficulties of measurement in solid state of these low-gamma NMR nuclei, due mainly to the low spectral resolution and poor signal-to-noise ratio, the observed global trends compare well with the solution-state NMR data. This would open an avenue for application of solid-state NMR to POMs, especially when liquid-state NMR is not possible, e.g., for poorly soluble or unstable compounds in solution, and for giant molecules with slow tumbling motion. This is the case of Keplerate where we provide here the first NMR characterization of this class of POMs in the solid state. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Crystal Structure and Band Gap Engineering in Polyoxometalate-Based Inorganic-Organic Hybrids.

    PubMed

    Roy, Soumyabrata; Sarkar, Sumanta; Pan, Jaysree; Waghmare, Umesh V; Dhanya, R; Narayana, Chandrabhas; Peter, Sebastian C

    2016-04-04

    We have demonstrated engineering of the electronic band gap of the hybrid materials based on POMs (polyoxometalates), by controlling its structural complexity through variation in the conditions of synthesis. The pH- and temperature-dependent studies give a clear insight into how these experimental factors affect the overall hybrid structure and its properties. Our structural manipulations have been successful in effectively tuning the optical band gap and electronic band structure of this kind of hybrids, which can find many applications in the field of photovoltaic and semiconducting devices. We have also addressed a common crystallographic disorder observed in Keggin-ion (one type of heteropolyoxometalate [POMs])-based hybrid materials. Through a combination of crystallographic, spectroscopic, and theoretical analysis of four new POM-based hybrids synthesized with tactically varied reaction conditions, we trace the origin and nature of the disorder associated with it and the subtle local structural coordination involved in its core picture. While the crystallography yields a centrosymmetric structure with planar coordination of Si, our analysis with XPS, IR, and Raman spectroscopy reveals a tetrahedral coordination with broken inversion symmetry, corroborated by first-principles calculations.

  5. Tungsten polyoxometalate molecules as active nodes for dynamic carrier exchange in hybrid molecular/semiconductor capacitors

    NASA Astrophysics Data System (ADS)

    Balliou, A.; Douvas, A. M.; Normand, P.; Tsikritzis, D.; Kennou, S.; Argitis, P.; Glezos, N.

    2014-10-01

    In this work we study the utilization of molecular transition metal oxides known as polyoxometalates (POMs), in particular the Keggin structure anions of the formula PW12O403-, as active nodes for potential switching and/or fast writing memory applications. The active molecules are being integrated in hybrid Metal-Insulator/POM molecules-Semiconductor capacitors, which serve as prototypes allowing investigation of critical performance characteristics towards the design of more sophisticated devices. The charging ability as well as the electronic structure of the molecular layer is probed by means of electrical characterization, namely, capacitance-voltage and current-voltage measurements, as well as transient capacitance measurements, C (t), under step voltage polarization. It is argued that the transient current peaks observed are manifestations of dynamic carrier exchange between the gate electrode and specific molecular levels, while the transient C (t) curves under conditions of molecular charging can supply information for the rate of change of the charge that is being trapped and de-trapped within the molecular layer. Structural characterization via surface and cross sectional scanning electron microscopy as well as atomic force microscopy, spectroscopic ellipsometry, UV and Fourier-transform IR spectroscopies, UPS, and XPS contribute to the extraction of accurate electronic structure characteristics and open the path for the design of new devices with on-demand tuning of their interfacial properties via the controlled preparation of the POM layer.

  6. Tungsten polyoxometalate molecules as active nodes for dynamic carrier exchange in hybrid molecular/semiconductor capacitors

    SciTech Connect

    Balliou, A.; Douvas, A. M.; Normand, P.; Argitis, P.; Glezos, N.; Tsikritzis, D.; Kennou, S.

    2014-10-14

    In this work we study the utilization of molecular transition metal oxides known as polyoxometalates (POMs), in particular the Keggin structure anions of the formula PW₁₂O₄₀³⁻, as active nodes for potential switching and/or fast writing memory applications. The active molecules are being integrated in hybrid Metal-Insulator/POM molecules-Semiconductor capacitors, which serve as prototypes allowing investigation of critical performance characteristics towards the design of more sophisticated devices. The charging ability as well as the electronic structure of the molecular layer is probed by means of electrical characterization, namely, capacitance-voltage and current-voltage measurements, as well as transient capacitance measurements, C (t), under step voltage polarization. It is argued that the transient current peaks observed are manifestations of dynamic carrier exchange between the gate electrode and specific molecular levels, while the transient C (t) curves under conditions of molecular charging can supply information for the rate of change of the charge that is being trapped and de-trapped within the molecular layer. Structural characterization via surface and cross sectional scanning electron microscopy as well as atomic force microscopy, spectroscopic ellipsometry, UV and Fourier-transform IR spectroscopies, UPS, and XPS contribute to the extraction of accurate electronic structure characteristics and open the path for the design of new devices with on-demand tuning of their interfacial properties via the controlled preparation of the POM layer.

  7. Photochromism and Dual-Color Fluorescence in a Polyoxometalate-Benzospiropyran Molecular Switch.

    PubMed

    Parrot, Arnaud; Bernard, Aurélie; Jacquart, Aurélie; Serapian, Stefano Artin; Bo, Carles; Derat, Etienne; Oms, Olivier; Dolbecq, Anne; Proust, Anna; Métivier, Rémi; Mialane, Pierre; Izzet, Guillaume

    2017-04-18

    The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (λem (closed form)=530 nm, λem (open form)=670 nm) and that the fluorescence of the BSPR unit of the hybrid is considerably enhanced compared to BSPR parent compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), improving the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of the hybrid give an intimate understanding of the conformation adopted by the hybrid and show that the nitroaryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR.

  8. Visible-light-driven hydrogen evolution with polyoxometalate as electron relay

    NASA Astrophysics Data System (ADS)

    Liu, Xing; Li, Yuexiang; Peng, Shaoqin; Lai, Hua; Yi, Zhengji

    2016-10-01

    A visible-light-driven hydrogen evolution system was constructed in one step with xanthene dye as photosensitizer, triethanolamine (TEOA) as electron donor, Pt as cocatalyst, and Keggin-type silicon-tungsten polyoxometalate (POM) as electron relay. The average rate of hydrogen evolution from the eosin Y-POM-TEOA-PtCl62- systems is 51.8 μmol h-1, and the apparent quantum yield is 8.9% during 20 h irradiation (λ>420 nm, a high-pressure Hg lamp was used as the light source). Ultraviolet-visible absorption spectra and fluorescence spectra were used to study the mechanism of charge transfer. A radical anion Dye, which generates from quenching of the triplet-excited state Dye3* by sacrificial electron donor, was considered the main species for transmitting electrons to POM and then to Pt. SiW9O3410-, derived from SiW12O404-, is the main form of POM in our reaction system, which can mediate the electron transfer from Dye to Pt, so an enhanced hydrogen evolution was realized. The present study highlights POM as electron relay in the photocatalytic hydrogen evolution process, which is expected to contribute to the development of functional and efficient artificial photosynthetic systems.

  9. Polyoxometalate-based layered structures for charge transport control in molecular devices.

    PubMed

    Douvas, Antonios M; Makarona, Eleni; Glezos, Nikos; Argitis, Panagiotis; Mielczarski, Jerzy A; Mielczarski, Ela

    2008-04-01

    Hybrid organic-inorganic films consisted of molecular layers of a Keggin-structure polyoxometalate (POM: 12-tungstophosphoric acid, H(3)PW(12)O(40)) and 1,12-diaminododecane (DD) on 3-aminopropyl triethoxysilane (APTES)-modified silicon surface, fabricated via the layer-by-layer (LBL) self-assembly method are evaluated as molecular materials for electronic devices. The effect of the fabrication process parameters, including primarily compositions of deposition solutions, on the structural characteristics of the POM-based multilayers was studied extensively with a combination of spectroscopic methods (UV, FTIR, and XPS). Well-characterized POM-based films (both single-layers and multilayers) in a controlled and reproducible way were obtained. The conduction mechanisms in single-layered and multilayered structures were elucidated by the electrical characterization of the produced films supported by the appropriate theoretical analysis. Fowler-Nordheim (FN) tunneling and percolation mechanisms were encountered in good correlation with the structural characteristics of the films encouraging further investigation on the use of these materials in electronic and, in particular, in memory devices.

  10. Polyoxometalates as antitumor agents: Bioactivity of a new polyoxometalate with copper on a human osteosarcoma model.

    PubMed

    León, I E; Porro, V; Astrada, S; Egusquiza, M G; Cabello, C I; Bollati-Fogolin, M; Etcheverry, S B

    2014-10-05

    Polyoxometalates (POMs) are early transition metal oxygen anion clusters. They display interesting biological effects mainly related to their antiviral and antitumor properties. On the other hand, copper compounds also show different biological and pharmacological effects in cell culture and in animal models. We report herein for the first time, a detailed study of the mechanisms of action of a copper(II) compound of the group of HPOMs with the formula K7Na3[Cu4(H2O)2(PW9034)2]20H2O (PW9Cu), in a model of human osteosarcoma derived cell line, MG-63. The compound inhibited selectively the viability of the osteosarcoma cells in the range of 25-100μM (p<0.01). Besides, we have clearly shown a more deleterious action of PW9Cu on tumor osteoblasts than in normal cells. Cytotoxicity studies also showed deleterious effects for PW9Cu. The increment of reactive oxygen species (ROS) and the decrease of the GSH/GSSG ratio were involved in the antiproliferative effects of PW9Cu. Moreover, the compound caused cell cycle arrest in G2 phase, triggering apoptosis as determined by flow cytometry. As a whole, these results showed the main mechanisms of the deleterious effects of PW9Cu in the osteosarcoma cell line MG-63, demonstrating that this compound is a promissory agent for cancer treatments. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  11. Efficient water oxidation at carbon nanotube-polyoxometalate electrocatalytic interfaces

    NASA Astrophysics Data System (ADS)

    Toma, Francesca M.; Sartorel, Andrea; Iurlo, Matteo; Carraro, Mauro; Parisse, Pietro; Maccato, Chiara; Rapino, Stefania; Gonzalez, Benito Rodriguez; Amenitsch, Heinz; da Ros, Tatiana; Casalis, Loredana; Goldoni, Andrea; Marcaccio, Massimo; Scorrano, Gianfranco; Scoles, Giacinto; Paolucci, Francesco; Prato, Maurizio; Bonchio, Marcella

    2010-10-01

    Water is the renewable, bulk chemical that nature uses to enable carbohydrate production from carbon dioxide. The dream goal of energy research is to transpose this incredibly efficient process and make an artificial device whereby the catalytic splitting of water is finalized to give a continuous production of oxygen and hydrogen. Success in this task would guarantee the generation of hydrogen as a carbon-free fuel to satisfy our energy demands at no environmental cost. Here we show that very efficient and stable nanostructured, oxygen-evolving anodes are obtained by the assembly of an oxygen-evolving polyoxometalate cluster (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes. Our bioinspired electrode addresses the one major challenge of artificial photosynthesis, namely efficient water oxidation, which brings us closer to being able to power the planet with carbon-free fuels.

  12. Immobilization of Polyoxometalate in the Metal-Organic Framework rht-MOF-1: Towards a Highly Effective Heterogeneous Catalyst and Dye Scavenger

    NASA Astrophysics Data System (ADS)

    Sun, Jing-Wen; Yan, Peng-Fei; An, Guang-Hui; Sha, Jing-Quan; Li, Guang-Ming; Yang, Guo-Yu

    2016-05-01

    A series of three remarkable complexes [PMo12O40]@[Cu6O(TZI)3(H2O)9]4·OH·31H2O (H3TZI = 5-tetrazolylisophthalic acid; denoted as HLJU-1, HLJU = Heilongjiang University), [SiMo12O40]@[Cu6O(TZI)3(H2O)9]4·32H2O (denoted as HLJU-2), and [PW12O40]@[Cu6O(TZI)3(H2O)6]4·OH·31H2O (denoted as HLJU-3) have been isolated by using simple one-step solvothermal reaction of copper chloride, 5-tetrazolylisophthalic acid (H3TZI), and various Keggin-type polyoxometalates (POMs), respectively. Crystal analysis of HLJU 1‑3 reveals that Keggin-type polyoxoanions have been fitted snuggly in the cages of rht-MOF-1 (MOF: metal‑organic framework) with large cell volume in a range of 87968‑88800 Å3 and large pore volume of about 68%. HLJU 1–3 exhibit unique catalytic selectivity and reactivity in the oxidation of alkylbenzene with environmental benign oxidant under mild condition in aqueous phase as well as the uptake capacity towards organic pollutants in aqueous solution.

  13. Immobilization of Polyoxometalate in the Metal-Organic Framework rht-MOF-1: Towards a Highly Effective Heterogeneous Catalyst and Dye Scavenger

    PubMed Central

    Sun, Jing-Wen; Yan, Peng-Fei; An, Guang-Hui; Sha, Jing-Quan; Li, Guang-Ming; Yang, Guo-Yu

    2016-01-01

    A series of three remarkable complexes [PMo12O40]@[Cu6O(TZI)3(H2O)9]4·OH·31H2O (H3TZI = 5-tetrazolylisophthalic acid; denoted as HLJU-1, HLJU = Heilongjiang University), [SiMo12O40]@[Cu6O(TZI)3(H2O)9]4·32H2O (denoted as HLJU-2), and [PW12O40]@[Cu6O(TZI)3(H2O)6]4·OH·31H2O (denoted as HLJU-3) have been isolated by using simple one-step solvothermal reaction of copper chloride, 5-tetrazolylisophthalic acid (H3TZI), and various Keggin-type polyoxometalates (POMs), respectively. Crystal analysis of HLJU 1−3 reveals that Keggin-type polyoxoanions have been fitted snuggly in the cages of rht-MOF-1 (MOF: metal−organic framework) with large cell volume in a range of 87968−88800 Å3 and large pore volume of about 68%. HLJU 1–3 exhibit unique catalytic selectivity and reactivity in the oxidation of alkylbenzene with environmental benign oxidant under mild condition in aqueous phase as well as the uptake capacity towards organic pollutants in aqueous solution. PMID:27157290

  14. Macromolecule-to-amphiphile conversion process of a polyoxometalate-polymer hybrid and assembled hybrid vesicles.

    PubMed

    Xiao, Yu; Han, Yao-Kun; Xia, Nan; Hu, Min-Biao; Zheng, Ping; Wang, Wei

    2012-09-03

    We report our findings on the macromolecule-to-amphiphile conversion process of a polyoxometalate-polymer hybrid and the assembled hybrid vesicles formed by aggregation of the hybrid amphiphile. The polyoxometalate-polymer hybrid is composed of a polyoxometalate (POM) cluster, which is covered by five tetrabutylammonium (Bu(4)N(+)) countercations, and a polystyrene (PS) chain. Through a cation-exchange process the Bu(4)N(+) countercations can be replaced by protons to form a hybrid amphiphile composed of a hydrophilic, protonated POM cluster and a hydrophobic PS chain. By implementing a directed one-dimensional diffusion and analyzing the diffusion data, we confirmed that the diffusion of solvated protons rather than macromolecules or aggregates is the key factor controlling the conversion process. Once the giant hybrid amphiphiles were formed, they immediately assembled into kinetically favored vesicular aggregates. During subsequent annealing these vesicular aggregates were transformed into thermodynamically stable vesicular aggregates with a perfect vesicle structure. The success in the preparation of the POM-containing hybrid vesicles provides us with an opportunity of preparing POM-functionalized vesicles. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Recent advances in polyoxometalate based delignification

    Treesearch

    R. H. Atalla; L. A. Weinstock; R. S. Reiner; C. J. Houtman; S. Reichel; C. G. Hill; C. L. Hill

    1999-01-01

    A new delignification technology based on the use of polyoxometalates (POMs) as delignification agents is under development at the USDA Forest Service, Forest Products Labotatory (FPL), in Madison, Wisconsin. These reagents are chlorine free and can be used under conditions wherein they oxidize lignin and chromophores in wood pulp fibers while leaving the cellulose...

  16. Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions.

    PubMed

    Copping, Roy; Jonasson, Leif; Gaunt, Andrew J; Drennan, Dennis; Collison, David; Helliwell, Madeleine; Pirttijarvi, Ross J; Jones, Chris J; Huguet, Anne; Apperley, David C; Kaltsoyannis, Nikolas; May, Iain

    2008-07-07

    We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions

  17. Involvement of heteroatoms in charge transfer of Keggin-type heteropolyanion.

    PubMed

    Nakayama, Masaharu; Ii, Takahiro; Komatsu, Hiroyuki; Ogura, Kotaro

    2004-05-07

    Spectroscopic measurements of an electrochemically deposited film from a Keggin-type heteropolyanion solution indicate that electron transfer takes place not only on polyatoms but also on heteroatoms of silicon.

  18. Photocatalytic bacterial inactivation by polyoxometalates.

    PubMed

    Bae, Eunyoung; Lee, Jae Won; Hwang, Byeong Hee; Yeo, Jiman; Yoon, Jeyong; Cha, Hyung Joon; Choi, Wonyong

    2008-05-01

    The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO2 photocatalyst. Aqueous suspensions of the microorganisms (10(7)-10(8)cfu ml(-1)) and POM (or TiO2) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO2-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H(3)PW(12)O(40), H(3)PMo(12)O(40), and H(4)SiW(12)O(40)) tested in this study, the inactivation of E. coli was fastest with H(4)SiW(12)O(40) while that of B. subtilis was the most efficient with H(3)PW(12)O(40). Although the biocidal action of TiO2 photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO2-PCI. While TiO2 caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO2-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.

  19. Spectroscopic Study of the Interaction between Horse Heart Myoglobin and Zirconium(IV)-Substituted Polyoxometalates as Artificial Proteases.

    PubMed

    Ly, Hong Giang T; Parac-Vogt, Tatjana N

    2017-07-04

    A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and (1) H and (31) P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr(IV) -Keggin, exhibits the strongest interaction with HHM. (31) P NMR spectroscopy studies show that this POM dissociates in solution, resulting in the formation of a monomeric 1:1 Zr(IV) -Keggin structure, which is likely to be a catalytically active species. In the presence of Zr(IV) -POMs, HHM does not undergo complete denaturation, as evidenced by CD, UV/Vis, tryptophan fluorescence, and (1) H NMR spectroscopy. CD spectroscopy shows a gradual decrease in the α-helical content of HHM upon addition of Zr(IV) -POMs. The largest effect is observed in the presence of a large Zr(IV) -Wells-Dawson structure, whereas small Zr(IV) -Lindqvist POM has the least influence on the decrease in the α-helical content of HHM. In all cases, the Soret band at λ=409 nm is maintained in the presence of all examined Zr-POMs, which indicates that no conformational changes in the protein occur near the heme group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Spontaneous growth of self-relief wrinkles in freely floating lipid-based nanomembranes, formed on a reactive bath of polyoxometalate aqueous solution.

    PubMed

    Mougin, Karine; Vonna, Laurent; Vidal, Loic; Haidara, Hamidou

    2010-05-15

    Wetting and capillarity have appeared over the last decadesas potential tools for the guided actuation, self-assembly and nanostructuration, and most recently as powerful "tool-free" techniques of micro-, and nano-fabrication, in the field of nanotechnology. The present work deals with such a use of wetting, achieving for the first time the spontaneous growth of composite (lipid-capped polyoxometalate) nanomembranes, using the reactive spreading film formed by the droplets of a lipid solution, on an aqueous foundation hosting the polyoxometalate ions. Moreover, we show that the internal stress produced by the reactive wetting, and the resulting self-movements of the drop could be accumulated within the drying spreading film, driving the spontaneous occurrence of wrinkles, in the freely floating nanomembranes that are thus formed. Finally, we showed that gravity-driven scaling relations for buckling instabilities apply to these spontaneously occurring wrinkles, allowing the in situ characterization of the physical properties of the nanomembranes. This approach that allowed producing floating nanomembranes of "lipid-capped Keggin ions" that were collectable as freestanding nanosheets may constitute a potential route for the fabrication of a wide range of functional (copolymers/metal nanoparticles) nanocomposite membranes. Copyright © 2010 Elsevier Inc. All rights reserved.

  1. Polyoxometalates active against tumors, viruses, and bacteria.

    PubMed

    Yamase, Toshihiro

    2013-01-01

    Polyoxometalates (PMs) as discrete metal-oxide cluster anions with high solubility in water and photochemically and electrochemically active property have a wide variety of structures not only in molecular size from sub-nano to sub-micrometers with a various combination of metals but also in symmetry and highly negative charge. One of the reasons for such a structural variety originates from their conformation change (due to the condensed aggregation and the structural assembly) which strongly depends on environmental parameters such as solution pH, concentration, and coexistent foreign inorganic and/or organic substances. In the course of the application of the physicochemical properties of such PMs to the medical fields, antitumoral, antiviral, and antibacterial activities have been developed for realization of a novel inorganic medicine which provides a biologically excellent activity never replaced by other approved medicines. Several PMs as a candidate for clinical uses have been licensed toward the chemotherapy of solid tumors (such as human gastric cancer and pancreatic cancer), DNA and RNA viruses (such as HSV, HIV, influenza, and SARS), and drug-resistant bacteria (such as MRSA and VRSA) in recent years: [NH3Pr(i)]6[Mo7O24]∙3H2O (PM-8) and [Me3NH]6[H2Mo(V) 12O28(OH)12(Mo(VI)O3)4]∙2H2O (PM-17) for solid tumors; K7[PTi2W10O40]∙6H2O (PM-19), [Pr(i)NH3]6H[PTi2W10O38(O2)2]∙H2O (PM-523), and K11H[(VO)3(SbW9O33)2]∙27H2O (PM-1002) for viruses; and K6[P2W18O62]∙14H2O (PM-27), K4[SiMo12O40]∙3H2O (SiMo12), and PM-19 for MRSA and VRSA. The results are discussed from a point of view of the chemotherapeutic clarification in this review.

  2. Polyoxometalate/Polyethylene Glycol Interactions in Water: From Nanoassemblies in Water to Crystal Formation by Electrostatic Screening.

    PubMed

    Buchecker, Thomas; Le Goff, Xavier; Naskar, Bappaditya; Pfitzner, Arno; Diat, Olivier; Bauduin, Pierre

    2017-06-22

    In the last decade organic-inorganic hybrid materials have become essential in materials science as they combine properties of both building blocks. Nowadays the main routes for their synthesis involve electrostatic coupling, covalent grafting, and/or solvent effects. In this field, polyoxometalates (POMs) have emerged as interesting inorganic functional building blocks due to their outstanding properties. In the present work the well-known α-Keggin polyoxometalate, α-PW12 O40(3-) (PW), is shown to form hybrid crystalline materials with industrial (neutral) polyethylene glycol oligomers (PEG) under mild conditions, that is, in aqueous medium and at room temperature. The formation of these materials originates from the spontaneous self-assembly of PW with EOx , (EO=ethylene oxide) with at least four EO units (x>4). The PW-PEG nanoassemblies, made of a POM surrounded by about two PEG oligomers, are stabilized by electrostatic repulsions between the negatively charged PW anions. Addition of NaCl, aimed at screening the inter-nanoassembly repulsions, induces aggregation and formation of hybrid crystalline materials. Single-crystal analysis showed a high selectivity of PW towards EO5 -EO6 oligomers from PEG200, which is made of a mixture of EO3-8 . Therefore, a general "soft" route to produce POM-organic composites is proposed here through the control of electrostatic repulsions between spontaneously formed nanoassemblies in water. However, this rational design of new POM hybrid (crystalline) materials with hydrophilic blocks, using such a simple mixing procedure of the components, requires a deep understanding of the molecular interactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Polyoxometalate complexes of anatase-titanium dioxide cores in water.

    PubMed

    Raula, Manoj; Gan Or, Gal; Saganovich, Marina; Zeiri, Offer; Wang, Yifeng; Chierotti, Michele R; Gobetto, Roberto; Weinstock, Ira A

    2015-10-12

    Polyoxometalate (POM) cluster anions are shown to serve as covalently coordinated ligands for anatase-TiO2 nanocrystals, giving isolable assemblies uniquely positioned between molecular macroanions and traditional colloidal nanoparticles. Na(+) salts of the water-soluble polyanionic structures are obtained by reacting amorphous TiO2 with the 1 nm lacunary ion, Na7 [α-XW11 O39 ] (X=P(5+) ), at 170 °C, after which an average of 55 α-PW11 O39 (7-) clusters are found as pentadentate ligands for Ti(IV) ions covalently linked to 6 nm single-crystal anatase cores. The attached POMs are reversible electron acceptors, the reduction potentials of which shift in a predictable fashion by changing the central heteroatom, X, directly influencing a model catalytic reaction. Just as POM cluster anions control the reactivities of metal centers in molecular complexes, directly coordinated POM ligands with tunable redox potentials now provide new options for rationally controlling the reactions of semiconductor nanocrystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Hybrid Materials Based on the Embedding of Organically Modified Transition Metal Oxoclusters or Polyoxometalates into Polymers for Functional Applications: A Review

    PubMed Central

    Carraro, Mauro; Gross, Silvia

    2014-01-01

    The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) nanoparticles, mono- and polynuclear metal complexes and clusters, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates (POM), layered inorganic systems, inorganic fibers, and whiskers. In this paper, we will review the use of two particular kinds of structurally well-defined inorganic building blocks, namely transition metals oxoclusters (TMO) and polyoxometalates (POM), to obtain hybrid materials with enhanced functional (e.g., optical, dielectric, magnetic, catalytic) properties. PMID:28788659

  5. Classical/Non‐classical Polyoxometalate Hybrids

    PubMed Central

    Santiago‐Schübel, Beatrix; Willbold, Sabine; Heß, Volkmar

    2016-01-01

    Abstract Two polyanions [SeI V 2PdII 4WVI 14O56H]11− and [SeI V 4PdII 4WVI 28O108H12]12− are the first hybrid polyoxometalates in which classical (Group 5/6 metal based) and non‐classical (late transition‐metal based) polyoxometalate units are joined. Requiring no supporting groups, this co‐condensation of polyoxotungstate and isopolyoxopalladate constituents also provides a logical link between POM‐PdII coordination complexes and the young subclass of polyoxopalladates. Solid‐state, solution, and gas‐phase studies suggest interesting specific reactivities for these hybrids and point to several potential derivatives and functionalization strategies. PMID:27617918

  6. Delignification of wood and kraft pulp with polyoxometalates

    Treesearch

    Edward L. Springer; Richard S. Reiner; Ira A. Weinstock; Rajai H. Atalla; Michael W. Wemple; Elena M. G. Barbuzzi

    1998-01-01

    Finely divided aspen and spruce woods and a high lignin pine kraft pulp have been selectively delignified to low lignin levels using aqueous solutions of polyoxometalates under anaerobic conditions. The reduced polyoxometalates in the solutions can be reoxidized with oxygen and act as wet oxidation catalysts for the mineralization of the solubilized lignin and...

  7. Interaction between Mo132 nanocluster polyoxometalate and solvents

    NASA Astrophysics Data System (ADS)

    Ostroushko, A. A.; Safronov, A. P.; Tonkushina, M. O.; Korotaev, V. Yu.; Barkov, A. Yu.

    2014-12-01

    The interaction between solid Mo132 nanocluster polyoxometalate with the structure of a keplerate and solvents of different natures (e.g., water, alcohols, hexane, and tetrachloromethane) is studied thermochemically. NMR spectroscopy is used to analyze interactions in solid polyoxometalate-organic compound systems in a gaseous medium. Data are collected on sorption interactions between a Mo132 nanocluster and camphor.

  8. Controlled assembly and solution observation of a 2.6 nm polyoxometalate 'super' tetrahedron cluster: [KFe12(OH)18(alpha-1,2,3-P2W15O56)4]29-.

    PubMed

    Pradeep, Chullikkattil P; Long, De-Liang; Kögerler, Paul; Cronin, Leroy

    2007-11-07

    A nanoscale FeIII-substituted polyoxotungstate [KFe12(OH)18-(alpha-1,2,3-P2W15O56)4]29- is synthesized starting from the trilacunary {P2W15} Dawson cluster and [Fe3(mu3-O)-(CH2=CHCOO)6(H2O)3]1+ to give a 2.6 nm tetrahedral cluster species and the 16 kDa cluster can be directly observed in solution as revealed by mass spectrometry studies.

  9. Orientations of polyoxometalate anions on gold nanoparticles.

    PubMed

    Sharet, Shelly; Sandars, Ella; Wang, Yifeng; Zeiri, Offer; Neyman, Alevtina; Meshi, Louisa; Weinstock, Ira A

    2012-09-07

    Cryogenic transmission electron microscopy of polyoxometalate-protected gold nanoparticles reveals that the Preyssler ion, [NaP(5)W(30)O(110)](14-), lies "face down" with its C(5) axis perpendicular to the gold surface, while the Finke-Droege ion, [P(4)W(30)Zn(4)(H(2)O)(2)O(112)](16-), is "tilted", with its long axis close to 60° from the normal to the surface.

  10. Charge retention of soft-landed phosphotungstate Keggin anions on self-assembled monolayers

    SciTech Connect

    Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Andersen, Amity; Johnson, Grant E.; Laskin, Julia

    2016-01-01

    Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, PW12O403- (WPOM3-) and PW12O402- (WPOM2-), were soft-landed onto different self-assembled monolayer (SAM) surfaces and examined using in situ infrared reflection absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. Partial retention of the 3- charge was observed when WPOM3- was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM3- and WPOM2- were deposited onto a hydrophilic alkylthiol SAM terminated with cationic NH3+ functional groups (NH3+SAM). We found that during the course of the soft landing of WPOM3-, the relative abundance of WPOM3- on FSAM decreased while that of WPOM2- increased. We propose that the higher stability of immobilized WPOM2- in comparison with WPOM3- makes it the preferred charge state of WPOM on both the FSAM and NH3+SAM. We also observe weaker binding of WPOM anions to SAMs in comparison with phosphomolybdate ions (MoPOM) reported previously (J. Phys. Chem. C 2014, 118, 27611–27622). The weaker binding of WPOM to SAMs is attributed to the lower reactivity of WPOM reported in the literature. This study demonstrates that both the charge retention and the reactivity of deposited anionic POM clusters on surfaces are determined by the type of addenda metal atoms in the cluster.

  11. Unprecedented χ isomers of single-side triol-functionalized Anderson polyoxometalates and their proton-controlled isomer transformation.

    PubMed

    Zhang, Jiangwei; Liu, Zhenhua; Huang, Yichao; zhang, Jin; Hao, Jian; Wei, Yongge

    2015-06-04

    The μ2-O atom in Anderson polyoxometalates was regioselectively activated by the introduction of protons, which, upon functionalization with triol ligands, could afford a series of unique χ isomers of the organically-derived Anderson cluster {[RCC(CH2O)3]MMo6O18(OH)3}(3-). Herein proton-controlled isomer transformation between the δ and χ isomer was observed by using the fingerprint region in the IR spectra and (13)C NMR spectra.

  12. Structure-related frustrated magnetism of nanosized polyoxometalates: aesthetics and properties in harmony.

    PubMed

    Kögerler, Paul; Tsukerblat, Boris; Müller, Achim

    2010-01-07

    The structural versatility characterizing polyoxometalate chemistry, in combination with the option to deliberately use well-defined building blocks, serves as the foundation for the generation of a large family of magnetic clusters, frequently comprising highly symmetric spin arrays. If the spin centers are coupled by antiferromagnetic exchange, some of these systems exhibit spin frustration, which can result in novel magnetic properties of purely molecular origins. We discuss here the magnetic properties of selected nanosized polyoxometalate clusters featuring spin triangles as their magnetic 'building blocks' or fragments. This includes unique porous Keplerate clusters of the type {(Mo)Mo(5)}(12)M(30) (M = Fe(III), Cr(III), V(IV)) with the spin centers defining a regular icosidodecahedron and the {V(15)As(6)}-type cluster sphere containing a single equilateral spin triangle; these species are widely discussed and studied in the literature for their role in materials science as molecular representations of Kagomé lattices and in relation to quantum computing, respectively. Exhibiting fascinating and unique structural features, these magnetic molecules allow the study of the implications of frustrated spin ordering. Furthermore, this perspective covers the impact of spin frustration on the degeneracy of the ground state and related problems, namely strong magnetic anisotropy and the interplay of antisymmetric exchange and structural Jahn-Teller effects.

  13. "Bottom-up" meets "top-down" assembly in nanoscale polyoxometalate clusters: self-assembly of [P4W52O178](24-) and disassembly to [P3W39O134](19-).

    PubMed

    Pradeep, Chullikkattil P; Long, De-Liang; Streb, Carsten; Cronin, Leroy

    2008-11-12

    The pH-controlled assembly/disassembly of a nanoscale {P4W52O178}24- cluster at pH 2 to a {P4W44O152}20- cluster at pH 3-5 via a {P3W39O134}19- cluster species at pH 2-3 to finally give {P2W19O69(OH2)}14- at pH 6 is reported. This process can be traced in the solid state crystallographically and in solution using dynamic light scattering studies.

  14. Development of a polyoxometallate-based photocatalyst assembled with cucurbit[6]uril via hydrogen bonds for azo dyes degradation.

    PubMed

    Cao, Minna; Lin, Jingxiang; Lü, Jian; You, Yanglijun; Liu, Tianfu; Cao, Rong

    2011-02-15

    A water insoluble cucurbit[6]uril-polyoxometallates (CB[6]-POMs) composite assembled from α-Keggin type polysilicontungstate anions and macrocycle cucurbit[6]uril (CB[6]) via hydrogen bonding has been synthesized as visible light active photocatalyst. The physical and photocatalytic properties of such photocatalyst have been fully characterized by PXRD, FTIR, TG, XPS, and UV/vis diffuse reflectance spectra. The catalyst shows a good photocatalytic activity towards the degradation of methyl orange (MO) under visible light irradiation and displays good reproducibility of photocatalytic degradation by a simple recycled procedure without obvious loss in catalytic activity, which is of great significance for practical use of the photocatalyst. In the photodegradation process, the {Ni-CB[6]}(n) chain of the photocatalyst acts as sensitizer and can be induced by visible light, meanwhile the POMs chain of the photocatalyst acts as electron acceptor and deposits the electron in its LUMO. The effects of various experimental parameters and the proposed mechanisms are discussed in detail.

  15. Degradation of dye pollutants by immobilized polyoxometalate with H2O2 under visible-light irradiation.

    PubMed

    Lei, Pengxiang; Chen, Chuncheng; Yang, Juan; Wanhong, Ma; Zhao, Jincai; Zang, Ling

    2005-11-01

    A Keggin polyoxometalate (POM, i.e., PW12O40(3-)) and its lacunary derivative are immobilized on an anionic exchange resin through electrostatic interaction at pH 4.6 in an aqueous dispersion. The resin-supported POM thus obtained catalyzes the efficient degradation of cationic dye pollutants in the presence of H2O2 under visible-light irradiation. To evaluate the photocatalytic system, degradation of a rhodamine B (RB) dye was investigated in detail using UV-visible spectroscopy, high performance liquid chromatography, and gas chromatography/mass spectrometry techniques to identify the intermediates and final products. Fluorescence lifetime measurements revealed the electron transfer from the visible-light-excited RB molecules to the POMs. Electron paramagnetic resonance measurements, investigation of the effects of *OH and *OOH scavengers on the photoreaction kinetics, and IR analysis indicated that de-ethylation of RB was due to *OOH radicals, but the decomposition of the conjugated xanthene structure was caused by the peroxo species formed by interaction of H2O2 with the lacunary POM loaded on the resin. A total organic carbon removal of ca. 22% was achieved, and the recycle experiment suggested excellent stability and reusability of the heterogeneous catalyst. On the basis of the experimental results, a photocatalytic mechanism is discussed.

  16. Visible-light photochromic nanocomposite thin films based on polyvinylpyrrolidone and polyoxometalates supported on clay minerals

    NASA Astrophysics Data System (ADS)

    Wang, Xiang-yu; Dong, Qi; Meng, Qing-ling; Yang, Jun-Yan; Feng, Wei; Han, Xiang-kui

    2014-10-01

    A novel reversible photochromic nanocomposite film was prepared by entrapping phosphomolybdic acid supported on the sodium bentonite (PMoA/Na-MMT) into polyvinylpyrrolidone (PVPd). The microstructure, thermal stability, photochromic behavior and mechanism of the hybrid film were investigated. Fourier transform infrared spectroscopy (FT-IR) results illustrated that the Keggin geometry of polyoxometalates (PMoA) and organic groups of PVPd were still preserved inside the composites and non-covalent bond interaction was built between PMoA/Na-MMT and PVPd polymer matrix. Transmission electron microscopy (TEM) image showed that PMoA nanoparticles were finely dispersed in Na-MMT which exhibited fine stratified structure. Atomic force microscopy (AFM) images indicated that the surface topography of polymeric matrix changed after adding PMoA/Na-MMT, and the surface appearance of nanocomposite film was different before and after visible-light irradiation. The stability of the hybrid film and the effect of the perturbation of Na-MMT on the stability were determined by means of the thermogravimetric analysis (TG) and differential thermal analysis (DTA). Irradiated with visible light, the ultraviolet--visible spectra (UV-vis) showed that the hybrid films changed from colorless to blue and could recover the colorless state gradually in air, where oxygen played an important role during the bleaching process. The hybrid films exhibited excellent bleaching ability during the heating. According to the X-ray photoelectron spectroscopy (XPS) analysis, the appearance of Mo5+ species indicated the photo-reduction reaction between PMoA/Na-MMT and PVPd matrix occurred according to the proton transfer mechanism, and the photochromic reactions were found to exhibit first-order kinetics.

  17. Reversible proton-switchable fluorescence controlled by conjugation effect in an organically-functionalized polyoxometalate.

    PubMed

    Lv, Chunlin; Chen, Kun; Hu, Junjie; Zhang, Jin; Khan, Rao Naumaan Nasim; Wei, Yongge

    2016-06-20

    A novel monosubstituted organoimido hexamolybdate containing 6-nitroquinoline moiety has been successfully synthesized. This organically-functionalized polyoxometalate exhibits proton-induced switchable fluorescence property in aqueous acetonitrile solution at room temperature. Experimental and theoretical investigations of this reversible "on" and "off" switching mechanism have been carried out, and it is found that the protonation and deprotonation at the heterocyclic nitrogen atom within quinoline fragment leads to the breaking and reformation of the conjugation through strong d-π interaction between the hexamolybdate anionic cluster and the quinoline moiety, resulting in "on" and "off" luminescence signal.

  18. Reversible proton-switchable fluorescence controlled by conjugation effect in an organically-functionalized polyoxometalate

    PubMed Central

    Lv, Chunlin; Chen, Kun; Hu, Junjie; Zhang, Jin; Khan, Rao Naumaan Nasim; Wei, Yongge

    2016-01-01

    A novel monosubstituted organoimido hexamolybdate containing 6-nitroquinoline moiety has been successfully synthesized. This organically-functionalized polyoxometalate exhibits proton-induced switchable fluorescence property in aqueous acetonitrile solution at room temperature. Experimental and theoretical investigations of this reversible “on” and “off” switching mechanism have been carried out, and it is found that the protonation and deprotonation at the heterocyclic nitrogen atom within quinoline fragment leads to the breaking and reformation of the conjugation through strong d-π interaction between the hexamolybdate anionic cluster and the quinoline moiety, resulting in “on” and “off” luminescence signal. PMID:27321576

  19. Reversible proton-switchable fluorescence controlled by conjugation effect in an organically-functionalized polyoxometalate

    NASA Astrophysics Data System (ADS)

    Lv, Chunlin; Chen, Kun; Hu, Junjie; Zhang, Jin; Khan, Rao Naumaan Nasim; Wei, Yongge

    2016-06-01

    A novel monosubstituted organoimido hexamolybdate containing 6-nitroquinoline moiety has been successfully synthesized. This organically-functionalized polyoxometalate exhibits proton-induced switchable fluorescence property in aqueous acetonitrile solution at room temperature. Experimental and theoretical investigations of this reversible “on” and “off” switching mechanism have been carried out, and it is found that the protonation and deprotonation at the heterocyclic nitrogen atom within quinoline fragment leads to the breaking and reformation of the conjugation through strong d-π interaction between the hexamolybdate anionic cluster and the quinoline moiety, resulting in “on” and “off” luminescence signal.

  20. Preparation and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo 38) n

    NASA Astrophysics Data System (ADS)

    Wang, L.; Jiang, M.; Wang, E. B.; Duan, L. Y.; Hao, N.; Lan, Y.; Xu, L.; Li, Z.

    2003-11-01

    Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo 38) n and poly(allylamine hydrochloride)(PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo 38) n/PAH) m multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo 38) n adsorption. The electrochemistry behavior of the film at room temperature was investigated.

  1. A porphyrin-polyoxometallate bio-inspired mimic for artificial photosynthesis.

    PubMed

    Elliott, Kristopher J; Harriman, Anthony; Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Mayer, Cédric R; Odobel, Fabrice

    2009-10-21

    A multi-porphyrin cluster has been covalently attached to a polyoxometallate (POM) catalyst so as to form an advanced model for the photosynthetic reaction complex. This bio-inspired mimic displays efficient energy transfer from the peripheral zinc porphyrins (ZnP) to the central free-base porphyrin (FbP). The latter species participates in a light-induced electron transfer with the POM. Charge recombination is hindered by hole transfer from the FbP to one of the ZnPs. Charge accumulation occurs at the POM under illumination in the presence of a sacrificial electron donor.

  2. Phase modulation of thermotropic liquid crystals of tetra-n-alkylammonium polyoxometalate ionic complexes.

    PubMed

    Jiang, Yunxia; Liu, Shuxia; Zhang, Jing; Wu, Lixin

    2013-06-07

    A series of composition analogous polyoxometalate-based ionic complexes are synthesized and studied, with a focus on the correlation between their mesomorphic behavior and their chemical structure. Generally, these polarizable rigid polyoxoanion clusters decorated with hydrophobic flexible alkyl chains have demonstrated a propensity to form thermotropic liquid-crystalline (LC) phases. Characterized by differential scanning calorimetry (DSC), polarized optical microscopy (PM), and X-ray diffraction (XRD), two of the four investigated complexes tend to form thermodynamically stable mesophases. Longer alkyl chains have been found to form mesophases, and the alkyl chain length of the quaternary ammonium cations influences both the occurrence and type of mesophase exhibited.

  3. Fragmenting gadolinium: mononuclear polyoxometalate-based magnetic coolers for ultra-low temperatures.

    PubMed

    Martínez-Pérez, María-José; Montero, Oscar; Evangelisti, Marco; Luis, Fernando; Sesé, Javier; Cardona-Serra, Salvador; Coronado, Eugenio

    2012-08-16

    The polyoxometalate clusters with formula [Gd(W(5) O(18) )(2) ](9-) and [Gd(P(5) W(30) O(110) )](12-) each carry a single magnetic ion of gadolinium, which is the most widespread element among magnetic refrigerant materials. In an adiabatic demagnetization, the lowest attainable temperature is limited by the presence of magnetic interactions that bring about magnetic order below a critical temperature. We demonstrate that this limitation can be overcome by chemically engineering the molecules in such a way to effectively screen all magnetic interactions, suggesting their use as ultra-low-temperature coolers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Selective Imaging of Discrete Polyoxometalate Ions on Graphene Oxide under Variable Voltage Conditions.

    PubMed

    Bosch-Navarro, Concha; Perkins, Laura M; Kashtiban, Reza J; Rourke, Jonathan P; Shannon, Ian J; Sloan, Jeremy

    2016-01-26

    Monosubstituted lacunary Keggin [CoSiW11O39](6-) ions on graphene oxide (GO) were used in a comparative imaging study using aberration corrected transmission electron microscopy at two different acceleration voltages, 80 and 200 kV. By performing a set of static and dynamical studies, together with image simulations, we show how the use of lower voltages results in better stability and resolution of the underlying GO support while the use of higher voltages permits better resolution of the individual tungsten atoms and leads to less kinetic motion of the cluster, thus leading to a more accurate identification of cluster orientation and better stability under dynamical imaging conditions. Applying different voltages also influences the visibility of both GO and the lighter Co at lower or higher voltages, respectively.

  5. Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

    NASA Astrophysics Data System (ADS)

    Yan, Bangbo; Hodsdon, Samantha A.; Li, Yan-Fen; Carmichael, Christopher N.; Cao, Yan; Pan, Wei-Ping

    2011-12-01

    Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy) 3] 2[H 2W 12O 40]·8H 2O ( 1), the [Ru(bpy) 3] 2+ (bpy=2,2'-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H 2W 12O 40] 6- linked through {KO 7} and {NaO 6} polyhedra, while in K 6[Ru(pzc) 3] 2[SiW 12O 40]•12H 2O ( 2), the [Ru(pzc) 3] - (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW 12O 40] 4- clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion⋯π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.

  6. Hydrothermal synthesis and crystal structure of the novel mixed Mo/V metal-oxygen cluster compound [Co(C 2N 2H 8) 3] 4[Mo V2Mo VI14V IV16O 80(PO 4) 2]·10H 2O containing the two types of typical heteropoly anions

    NASA Astrophysics Data System (ADS)

    Xu, Yan; zhu, Dunru; Song, You; Zheng, Xuefang; You, Xiaozeng

    2006-01-01

    A novel polyoxometalate [Co(C 2N 2H 8) 3] 4[Mo V2Mo VI14V IV16O 80(PO 4) 2]·10H 2O 1 has been hydrothermal synthersized from the rection mixture of V 2O 5, CoCl 2·2H 2O, Na 2MoO 4·2H 2O, ethylenediamine(en), H 3PO 3 and H 2O in a reasonable yield(48%). The X-ray crystallography shows that 1 containing two types of typical heteropoly anions: tetra-capping Keggin anions and hexadecametal host shell anions. This is the first structurally characterized example of a heteropoly compound containing two types of anions. In compound 1, the Co 2+ cations are coordinated by three ethylendiamine ligands, and [Co(en) 3] 2+ cations link the metal-oxygen cluster anions, to form a extensive three-dimensional supramolecular assembly through the hydrogen bonding. Compound 1 crystallallizes in the tetragonal with space group I4/mcm, a= b=19.6613(19), c=33.738(5) Å, V=13042(3) Å 3.

  7. {l_brace}XW{sub 12}O{sub 40} [Cu(en){sub 2}(H{sub 2}O)]{sub 3}{r_brace} (X=V, Si): Two novel tri-supported Keggin POMs with transition metal complexes

    SciTech Connect

    Lu Yukun; Cui Xiaobing; Chen Yan; Xu Jianing; Zhang Qingbin; Liu Yabing; Xu Jiqing; Wang Tiegang

    2009-08-15

    Two novel polyoxometalate derivatives, {l_brace}X{sup IV}W{sup VI}{sub 10}W{sup V}{sub 2}O{sub 40}[Cu(en){sub 2}(H{sub 2}O)]{sub 3}{r_brace} [X=V (1), Si (2); en=ethylenediamine], have been hydrothermally synthesized and characterized by elemental analyses, IR, UV-Vis, XPS, EPR, TG and single crystal X-ray diffraction analyses. They represent the first classical Keggin polyoxoanion supported by three transition metal complex moieties, which further act as the neutral molecular unit for the construction of the interesting three-dimensional supramolecular frameworks. The magnetic properties of 1 have also been studied in the temperature range of 4-300 K, and its magnetic susceptibility obeys the Curie-Weiss law, showing antiferromagnetic coupling. - Graphical abstract: The first classical Keggin polyoxoanion tri-supported by TMC moieties via bridge oxygen atoms, {l_brace}X{sup IV}W{sup VI}{sub 10}W{sup V}{sub 2}O{sub 40}[Cu(en){sub 2}(H{sub 2}O)]{sub 3}{r_brace}, act as the neutral molecular unit to construct the interesting 3-D supramolecular frameworks.

  8. Hydrothermal combination of trilacunary Dawson phosphotungstates and hexanickel clusters: from an isolated cluster to a 3D framework.

    PubMed

    Li, Xin-Xiong; Fang, Wei-Hui; Zhao, Jun-Wei; Yang, Guo-Yu

    2014-12-22

    Three novel hexa-Ni-substituted Dawson phosphortungstates [Ni6 (en)3 (H2O)6 (μ3-OH)3 (H3 P2 W15 O56 )]⋅14 H2O (1), [Ni(enMe)2 (H2O)][Ni6 (enMe)3 (μ3-OH)3 (H2O)6 (HP2 W15 O56)]⋅ 10 H2O (2), and [Ni(enMe)2 ]3 [Ni(enMe)2 (H2O)][Ni(enMe)(H2O)2][Ni6 (enMe)3 (μ3-OH)3 (Ac)2 (H2O)(P2 W15 O56)]2 ⋅6 H2O (3) (en=ethylenediamine, enMe=1, 2-diaminopropane, Ac=CH3 COO(-)) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1-3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6 (μ3-OH)3](9+) cluster capping on a [P2 W15 O56](12-) fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1-3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3.

  9. Thermal-induced dynamic self-assembly of adenine-grafted polyoxometalate complexes.

    PubMed

    He, Zhenfeng; Yan, Yi; Li, Bao; Ai, Hui; Wang, Huanbing; Li, Haolong; Wu, Lixin

    2012-09-07

    A new kind of organic-inorganic hybrid complexes based on polyoxometalate were synthesized through symmetrically grafting two adeninyl groups onto Anderson-type MnMo(6) clusters and encapsulating the clusters by organic surfactants. The resultant complexes exhibited thermal-induced dynamic self-assembly behaviors which greatly depended on the ambient temperature and the chain length of cationic surfactants. With the encapsulation of a short surfactant tetrabutyl ammonium, the complex assembled into fibrous, rod-like, and tubular architectures respectively upon heating; while for the case of using a long surfactant dimethyldioctadecyl ammonium as counter ions, the assemblies of the complex transformed from fibers to spheres with the increased temperature. Moreover, the two types of transformations were both reversible during a cooling process. The related mechanism was investigated by combining multiple characterization methods including X-ray crystallography, XPS, FT-IR and temperature-dependent (1)H NMR, which indicated that such a thermal-induced morphological transformation resulted from a synergy effect of the variation of the multiple hydrogen bonds among the complexes and the rearrangement of the surfactants surrounding the MnMo(6) clusters. These results demonstrated a new concept that hydrogen bonds can be rationally employed as the driving force for the fabrication of polyoxometalate-based materials with smart responsive properties.

  10. Pharmacokinetics of antiviral polyoxometalates in rats.

    PubMed Central

    Ni, L; Boudinot, F D; Boudinot, S G; Henson, G W; Bossard, G E; Martellucci, S A; Ash, P W; Fricker, S P; Darkes, M C; Theobald, B R

    1994-01-01

    Polyoxometalates are soluble mineral compounds formed principally of oxide anions and early transition metal cations. The polyoxometalates K12H2[P2W12O48].24H2O (JM 1591), K10[P2W18Zn4(H2O)2O68].20H2O (JM 1596), and [(CH3)3NH]8[Si2W18Nb6O77] (JM 2820) demonstrate potent antiviral activity against human immunodeficiency virus types 1 and 2, herpes simplex virus, and cytomegalovirus in vitro. The preclinical pharmacokinetics of these three compounds were characterized after single-dose intravenous administration of 50 mg/kg to rats. Plasma, urine, and feces were collected for 168 h, and polyoxometalate concentrations were determined by atomic emission. Serum protein binding was measured by equilibrium dialysis. All three compounds were highly bound to serum proteins in a concentration-dependent manner. Total and unbound concentrations of the three compounds in plasma declined in a triexponential manner with terminal half-lives of 246.0 +/- 127.0, 438.4 +/- 129.4, and 32.2 +/- 5.37 h (mean +/- standard deviation) for JM 1591, JM 1596, and JM 2820, respectively. Systemic clearances based on total concentrations in plasma were low, averaging 0.016 +/- 0.002, 0.015 +/- 0.002, and 0.018 +/- 0.003 liter/h/kg for JM 1591, JM 1596, and JM 2820, respectively. The clearances of unbound compounds from plasma averaged 0.966 +/- 0.136, 0.050 +/- 0.005, and 0.901 +/- 0.165 liter/h/kg for JM 1591, JM 1596, and JM 2820, respectively. For JM 1596, the clearance of unbound compound from the kidneys was lower than the glomerular filtration rate (0.086 liter/h/kg), suggesting this polyoxometalate underwent renal tubular reabsorption. However, JM 1591 and JM 2820 appeared to undergo tubular secretion. The fraction of the dose recovered in urine was 11.5, 46.8, and 10.6% for JM 1591, JM 1596, and JM 2820, respectively. Approximately 5% of the dose of each polyoxometalate was recovered in feces. The steady-state volume of distribution based on total concentrations averaged 1.44 liters

  11. Structure and magnetism of [n-BuNH3]12[Cu4(GeW9O34)2].14H2O sandwiching a rhomblike Cu4(8+) tetragon through alpha-Keggin linkage.

    PubMed

    Yamase, Toshihiro; Abe, Hiroko; Ishikawa, Eri; Nojiri, Hiroyuki; Ohshima, Yuhgo

    2009-01-05

    A sandwich-type polyoxometalate, [Cu(4)(GeW(9)O(34))(2)](12-) (1a), in which two B-alpha-[GeW(9)O(34)](12-) ligands sandwich a rhomblike Cu(4)(8+) tetragon through alpha-Kappaeggin linkage, is first isolated as a [n-BuNH(3)](+) salt, [n-BuNH(3)](12)[Cu(4)(GeW(9)O(34))(2)].14H(2)O (1). A Cu(4)O(14) cluster for the rhomblike Cu(4)(8+) tetragon in 1a with C(2h) local symmetry consists of two Jahn-Teller (JT) distorted CuO(6) octahedra (at internal sites) with a short diagonal Cu(int)...Cu(int) distance of 3.10-3.11 A and two CuO(5) square pyramids (at external site) with a long diagonal Cu(ext)...Cu(ext) distance of 5.34-5.35 A, the feature of which is different from [Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)](12-) (2a), comprising the four JT-distorted CuO(6) octahedral Cu(4)(8+) tetragons through beta-Keggin linkage: the axial Cu(ext)-O bond distance (2.27-2.29 A) for 1a is shorter than the corresponding JT-axial distance (2.36 A) for 2a. Measurements of magnetic susceptibility, magnetization, and electron spin resonance spectroscopy for 1 are carried out for better understanding of the molecular magnetism of the Cu(4)(8+) tetragon in comparison with 2a. The analysis of the magnetic behavior, based on the isotropic Heisenberg spin Hamiltonian comprising three exchange parameters (J, J', and J''), gives J = -24.1 cm(-1) for the Cu(ext)..Cu(int) sides, J' = -99.1 cm(-1) for the Cu(int)...Cu(int) diagonal, and J'' = +0.04 cm(-1) for the Cu(ext)...Cu(ext) diagonal of the Cu(4)(8+) rhombus. The S = 1 ground state of 1 displays g(||) = 2.42, g( perpendicular)= 2.07, D = -1.44 x 10(-2) cm(-1), and |A(Cu||)| = 46.5 x 10(-4) cm(-1). An observation of the asymmetric magnetization between a positive and a negative pulsed field (up to 10(3) T/s) at 0.5 K on the hysteresis loop indicates the quantum tunneling at zero field. The magnetic exchange interactions of four unpaired d(x(2)-y(2))-electron spins are discussed in terms of the point-dipole approximation, and the primary contribution

  12. An unprecedented 3D POM-MOF based on (7,8)-connected twin Wells-Dawson clusters: synthesis, structure, electrocatalytic and photocatalytic properties.

    PubMed

    Li, Shaobin; Zhang, Li; O'Halloran, Kevin P; Ma, Huiyuan; Pang, Haijun

    2015-02-07

    The first (7,8)-connected polyoxometalate-based metal-organic framework (POM-MOF) has been constructed from seven- and eight-connected twin Wells-Dawson clusters, and possesses the highest connection number of polyoxometalates to any mixed-connected POM-MOF to date and a unique structural motif that contains both organic-inorganic and all-inorganic networks.

  13. Gas-Phase Fragmentation Pathways of Mixed Addenda Keggin Anions: PMo12-nWnO40 3- (n = 0-12)

    NASA Astrophysics Data System (ADS)

    Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo12-nWnO40 3- (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed addenda POMs examined in this study. CID of molybdenum-rich anions, PMo12-nWnO40 3- (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and 22 oxygen atoms (M7O22 2-) and its complementary singly charged PM5O18 - ion. In comparison, the doubly charged Lindqvist anion, (M6O19 2-) and its complementary singly charged PM6O21 - ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo12-nWnO40 3- (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms in the POM may be attributed to the higher barrier of tungsten-rich anions towards isomerization. We present evidence that the observed distribution of Mo and W atoms in the major M6O19 2- and M7O22 2- fragment ions is different from that predicted by a random distribution, indicating substantial segregation of the addenda metal atoms in the POMs. Charge reduction of the triply charged precursor anion resulting in formation of doubly charged anions is also observed. This is a dominant pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and charge loss pathways in CID of POM anions.

  14. Gas-Phase Fragmentation Pathways of Mixed-Addenda Keggin Anions: PMo12-nWnO403- (n = 0-12)

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo12-nWnO403- (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed POMs examined in this study. CID of molybdenum-rich anions, PMo12- nWnO403- (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and twenty-two oxygen atoms (M7O222-) and its complementary singly charged PM5O18- ion, while the Lindqvist anion, (M6O192-) and its complementary PM6O21- ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo12-nWnO403- (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms may be attributed to the higher stability of tungsten-rich anions towards isomerization. We find that the observed distribution of Mo and W atoms in the major M6O192- and M7O222- fragment ions is different from that predicted by a random distribution indicating substantial segregation of the addenda metal atoms in the POMs. Electron detachment from the triply charged precursor anion resulting in formation of doubly charged anions is observed. This is a dominant dissociation pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and electron detachment pathways of POM anions.

  15. Tetraalkylphosphonium polyoxometalates : Electroactive, 'task-specific' ionic liquids.

    SciTech Connect

    Rickert, P. G.; Antonio, M. R.; Firestone, M. A.; Kubatko, K-A.; Szreder, T.; Wishart, J. F.; Dietz, M. L.; BNL; Univ. of Miami

    2007-01-01

    The pairing of selected polyoxometalate (POM) anions with appropriate tetraalkylphosphonium cations is shown to yield an original family of ionic liquids, among them an ambient-temperature 'liquid POM.'

  16. Novel Polyoxometalate Containing Membranes for PEM Fuel Cells

    SciTech Connect

    Mason K. Harrup; Frederick F. Stewart; Thomas A Luther; Tammy Trowbridge

    2009-03-01

    Current proton exchange membrane (PEM) technologies are inadequate to address the projected needs for fuel cell performance above 80 ºC. Continuing research into traditional ion carriers in novel membrane materials offers the promise of marginal improvement, representing only an evolutionary increase in performance. This conclusion is supported by the role of water in conduction. Thus, the key to better PEMs is not to eliminate water, but to change the role of water by developing ion carriers that will bind water more tightly than traditional sulfur or phosphorus based carriers resulting in materials that will conduct at higher temperatures. This change entails having a carrier structure that interacts more intimately with water and by increasing the ion carrier anionic charge to result in more tightly held inner shell protonated waters of hydration. Both of these factors synergistically act to maintain a critical water concentration at the carrier necessary for conduction. In this work, polyoxometalate (POM) clusters were selected to serve as these different proton carriers.

  17. Intermediate Temperature Polymer Electrolyte Incorporated With Polyoxometalates For Fuel Cell Applications

    DTIC Science & Technology

    2004-12-01

    1 INTERMEDIATE TEMPERATURE POLYMER ELECTROLYTE INCORPORATED WITH POLYOXOMETALATES FOR FUEL CELL APPLICATIONS Charles Rong, Rongzhong Jiang...alkoxysilane precursor with polyoxometalates of different structures. Polyoxometalates H3PW12O40, H4SiW12O40, and H6P2W18O62 were chosen for the study...The proton conductivity of the membrane made with the above polyoxometalates increased with the increase of the temperature in the presence of

  18. Synthesis and characterization of two polyoxometalates consisting of different Cu-ligand hydrogen phosphate units

    SciTech Connect

    Yan, Jinshuang; Zhao, Xiaofang; Huang, Jiao; Gong, Kaining; Han, Zhangang Zhai, Xueliang

    2014-03-15

    Two polyoxometalates [(Cu-mbpy){sub 4}(HPO{sub 4}){sub 2}(H{sub 2}O){sub 2}][PMo{sub 12}O{sub 40}]·H{sub 2}O (1) and [(Cu-mbpy){sub 6}(HPO{sub 4}){sub 4}][PW{sub 12}O{sub 40}]·4H{sub 2}O (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl in 1; 5,5″-dimethyl-2,2'-dipyridyl in 2) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. The structural features of 1–2 are in their cationic moieties consisting of different linkages of [Cu-mbpy]{sup 2+} and HPO{sub 4}{sup 2−} groups. In 1 four Cu-mbpy bridged by two HPO{sub 4}{sup 2−} ions form a discrete cluster with an interesting octahedron of (Cu{sub 4}P{sub 2}), while in 2 Cu-mbpy fragments are bridged by HPO{sub 4}{sup 2−} ions into 1D structure consisting of trigonal bipyramidal polyhedra of (Cu{sub 3}P{sub 2}). Photocatalytic experiments indicate that compounds 1 and 2 are actively photocatalytic for degradation of methyl orange in the presence of H{sub 2}O{sub 2} under UV light irradiation. -- Graphical abstract: Two polyoxometalate-based supramolecular compounds consisting of different linkages based on Cu-ligand and HPO{sub 4}{sup 2−} groups have been synthesized and characterized. The photocatalytic activity are studied. Highlights: • Two polyoxometalate-based supramolecular compounds consisting of different linkages based on Cu-ligand and HPO{sub 4}{sup 2−} groups have been synthesized. • Hydrogen bonding and π…π interactions play important roles in constructing crystal supramolecular frameworks. • Two compounds represent a high photocatalytic activity in the degradation of methyl orange.

  19. Self-assembly of polyoxometalate clusters into a 3-D heterometallic framework via covalent bonding: synthesis, structure and characterization of Na 4[Nd 8(dipic) 12(H 2O) 9][Mo 8O 26]·8H 2O

    NASA Astrophysics Data System (ADS)

    Shen, Enhong; Lü, Jian; Li, Yangguang; Wang, Enbo; Hu, Changwen; Xu, Lin

    2004-11-01

    An unprecedented hybrid solid obtained by self-assembly of octamolybdate clusters into a three-dimensional alkali metal modified neodymium-organic heterometallic framework is described. Crystal data: monoclinic, space group P21/n, a=21.868(4) Å, b=13.039(3) Å, c=22.479(5) Å, β=98.90(3)°; V=6332(2) Å3; Z=2, R (final)=0.0474. The data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K using graphite-monochromated Mo Kα radiation ( λ=0.71073 Å) and oscillation scans technique in the range of 1.98°<θ<27.48°.

  20. Hydrothermal Synthesis and Structure of a Mixed Valent Heteropoly-oxometallate Keggin Salt: [PMo 4.27W 7.73O 6-40] [H 3N(CH 2) 6NH 2+3] 3

    NASA Astrophysics Data System (ADS)

    Gabriel, J.-C. P.; Nagarajan, R.; Natarajan, S.; Cheetham, A. K.; Rao, C. N. R.

    1997-03-01

    The polyoxometallate Keggin (αtype) [PMo4.27W7.73O6-40] [H3N(CH2)6NH2+3]3, involving molybdenum and tungsten present in both V and VI oxidation states, has been synthesized under hydrothermal conditions and its structure determined by single crystal X-ray analysis. Black platelet crystals are formed in the monoclinic system, space groupC2/m(No. 12),a=10.336(9),b=20.097(5),c=13.276(6) Å,β=106.41(7)°,Vcell=2645(3) Å3,Z=8,dcalc=3.555 Mg m-3(CuKαradiation, 2θmax=144°,R(F)=6.56 for 1729 reflections). Due to its location at the origin (2/msite), the anion is found to be disordered, its four independent metal sites occupied with molybdenum and tungsten atoms; a significant preferred localization of the molybdenum on two sites is also reported. The structure has a lamellar organization formed from alternating organic-inorganic planes with their normal parallel toc. A study by ESR has proven the presence of paramagnetic Mo/W(V) in the compound with the observation of a strong signal (g=1.983).

  1. Synthesis, morphologies and applications of polyoxometalate-containing diblock copolymers

    NASA Astrophysics Data System (ADS)

    Chakraborty, Sanjiban

    Block copolymers by virtue of their ability to self assemble and microphase-separation due to the contrast in chemical and physical properties of the covalently linked blocks constitute the essential building blocks towards various nano or micro sized architectures. Polyoxometalates (POM), on the other hand, being an interesting class of metal-oxygen nanometer-sized anionic clusters, are regarded highly due to their excellent electron accepting capability. Combining POM clusters with diblock copolymers can lead to a fascinating class of hybrid materials where the POM cluster not only affect the self-assembly process of various diblock copolymers but also brings its unique electronic properties into the hybrid system. Herein we report the detailed synthesis and characterizations of two hybrid coil-coil diblock copolymers along with two hybrid rod-coil diblock copolymers through polymerization-hybridization approach. The coil-coil diblocks were synthesized via atom transfer radial polymerization (ATRP) of styryl-type monomers and 4-vinylpyridine in sequence. For rod-coil diblock copolymers, the coil block was synthesized through ATRP, followed by the conversion of the terminal bromide to an azide. Ethynyl terminated poly (p-phenylenevinylene) (PPV) and poly (3-hexylthiophene) (P3HT) were prepared separately as the rod blocks. The rod block and the coil block were connected through click chemistry to yield rod-coil diblock copolymers. After removing the phthalimide protecting groups to regenerate aryl amines, POM clusters were finally linked to the coil block of all diblock copolymers to yield the targeted hybrid diblock copolymers. The covalent cluster attachment was confirmed by UV-Vis spectroscopy, FTIR and cyclovoltammetry measurements. The structures, solution and film optical properties, self-assembled morphologies and solar cell performances of these hybrids have been studied. It has been found that solar cell devices based on hybrid P3HT exhibited rather poor

  2. Diphosphates and diphosphonates in polyoxometalate chemistry.

    PubMed

    Banerjee, Abhishek; Bassil, Bassem S; Röschenthaler, Gerd-Volker; Kortz, Ulrich

    2012-11-21

    In the wide area of polyoxometalate (POM) chemistry, diphosphate/diphosphonate-based POMs represent a more recent area of study. However, in this short time it has emerged to become very dynamic, as shown by the wide variety of compounds reported. Ever since the discovery of the first polyoxotungstate framework constructed from diphosph(on)ate ligands, a widespread investigation on the preparative chemistry and properties of such compounds has followed. The main focus of such a study is based on factors such as the oxidation state of the metal, the effect of pH and temperature during synthesis, and the presence of different functional groups on the diphosphonate. In this review we discuss in detail all diphosphate/diphosphonate-based POMs, beginning with early developments, subsequent growth in interest, and finally focusing on the very latest developments.

  3. Role of cation size in the energy of electron transfer to 1:1 polyoxometalate ion pairs {(M+)(Xn+VW11O40)}(8–n)–(M=Li, Na, K)

    Treesearch

    Vladimir A. Grigoriev; Craig L. Hill; Ira A. Weinstock

    2000-01-01

    The use of soluble salts of polyoxometalates (d0-early-transition metal oxygen-anion clusters or POMs) as selective oxidation or electron-transfer catalysts, as probes in physical-organic and biological chemistry, and in the study of electron-and energy-transfer phenomena constitutes a substantial and rapidly growing literature. While rarely addressed, however, POM...

  4. Surface induced selective deposition of Dysprosium Polyoxometalate on HOPG surface studied by STM and STS

    NASA Astrophysics Data System (ADS)

    Costa Milan, David; Pinilla Cienfuegos, Elena; Cardona Serra, Salvador; Coronado Miralles, Eugenio; Untiedt Lecuona, Carlos

    2013-03-01

    Scanning Tunneling Microscope (STM) and scanning Tunnelling spectroscopy (STS) techniques have been used to study the Preyssler type Polyoxometalate K12[DyP5W30O110] molecules deposited on Highly Oriented Pyrolytic Graphite surface (HOPG). Chainlike arrangements of clusters containing two or three molecules, as well as different cluster sizes are observed. As many structural artifacts are present on the graphite surface, like Moiré patterns, that could look like the molecular deposits, we have studied their STS and size to ensure the presence of the POM molecules on the surface. This article shows the possibility of addressing POMs on a flat surface to obtain their electronic properties through STS.

  5. Accurately tuning the charge on giant polyoxometalate type Keplerates through stoichiometric interaction with cationic surfactants.

    PubMed

    Kistler, Melissa L; Patel, Komal G; Liu, Tianbo

    2009-07-07

    We report an approach of exploring the interaction between cationic surfactants and a type of structurally well-defined, spherical "Keplerate" polyoxometalate (POM) macroanionic molecular clusters, {Mo72V30}, in aqueous solution. The effectiveness of the interaction can be determined by monitoring the size change of the "blackberry" supramolecular structures formed by the self-assembly of {Mo72V30} macroions, which is determined by the effective charge density on the macroions. Long-chain surfactants (CTAB and CTAT) can interact with {Mo72V30} macroions stoichiometrically and lower their charge density. Consequently, the blackberry size decreases continuously with increasing surfactant concentration in solution. On the other hand, for short-chain surfactants (e.g., OTAB), a larger fraction of surfactants exist as discrete chains in solution and do not strongly interact with the macroions. This approach shows that a controllable amount of suitable surfactants can accurately tune the charge on large molecular clusters.

  6. Layer-by-layer assembly and UV photoreduction of graphene-polyoxometalate composite films for electronics.

    PubMed

    Li, Haolong; Pang, Shuping; Wu, Si; Feng, Xinliang; Müllen, Klaus; Bubeck, Christoph

    2011-06-22

    Graphene oxide (GO) nanosheets and polyoxometalate clusters, H(3)PW(12)O(40) (PW), were co-assembled into multilayer films via electrostatic layer-by-layer assembly. Under UV irradiation, a photoreduction reaction took place in the films which converted GO to reduced GO (rGO) due to the photocatalytic activity of PW clusters. By this means, uniform and large-area composite films based on rGO were fabricated with precisely controlled thickness on various substrates such as quartz, silicon, and plastic supports. We further fabricated field effect transistors based on the composite films, which exhibited typical ambipolar features and good transport properties for both holes and electrons. The on/off ratios and the charge carrier mobilities of the transistors depend on the number of deposited layers and can be controlled easily. Furthermore, we used photomasks to produce conductive patterns of rGO domains on the films, which served as efficient microelectrodes for photodetector devices.

  7. Polyoxometalate-biomolecule conjugates: a new approach to create hybrid drugs for cancer therapeutics.

    PubMed

    Yang, Hai-Kuan; Cheng, Yi-Xing; Su, Ming-Ming; Xiao, Yu; Hu, Min-Biao; Wang, Wei; Wang, Qian

    2013-03-01

    Some polyoxometalate (POM) clusters have demonstrated attractive anticancer properties. Unfortunately, their cytotoxicity upon normal cell is one of fateful side effects obstructing their further clinic application as inorganic drugs. In this communication, we report a new approach to create hybrid drugs potentially for cancer therapeutics. At first, the POM cluster bioconjugates were created by attaching the bioactive ligands on an amine grafted POM via simple amidation reaction. The cytotoxicity study with breast cancer cells (MCF-7 and MDA-MB-231) and non-cancerous breast epithelial cell (MCF-10A) showed that rationally selected ligands with cancer-cell targeting ability on POM-biomolecule conjugates can impart enhanced anti-tumor activity and selectivity, thus representing a new concept to develop novel POM-biomolecule hybrid drugs with the potential synergistic effect: increased bioactivity and lower side effect.

  8. Effects of europium polyoxometalate encapsulated in silica nanoparticles (nanocarriers) in soil invertebrates

    NASA Astrophysics Data System (ADS)

    Bicho, Rita C.; Soares, Amadeu M. V. M.; Nogueira, Helena I. S.; Amorim, Mónica J. B.

    2016-12-01

    Polyoxometalates (POMs) are metal oxo clusters that have been investigated for several applications in material sciences, catalysis, and biomedicine; these gained increasing interest in the field of nanotechnology as nanocarriers for drug delivery. Associated to the increasing applications, there is the need for information regarding the effects on the environment of these compounds, which is completely absent in the literature. In the present study, the effects of europium polyoxometalates encapsulated into silica nanoparticles (Eu-POM/SiO2 NPs) were assessed on the soil representative Enchytraeus crypticus. The individual materials were also assessed (Eu-POMs and SiO2 NPs). Toxicity was evaluated in various test media with increasing complexity: water, soil/water extracts, and soil. Toxicity was only observed for Eu-POM/SiO2 NPs and in the presence of soil components. Despite the fact that effects were observed for concentrations higher than current predicted environmental concentration (PEC), attention should be given to the growing use of these compounds. The present study shows the importance of assessing the effects in soil media, also compared to water. Moreover, results of "no effect" are critically needed and often unpublished. The present study can contribute to the improvement of the OECD guidelines for safety of manufactured nanomaterials on environmental toxicity in the soil compartment providing an improved test alternative.

  9. Polyoxometalate-modified carbon nanotubes: new catalyst support for methanol electro-oxidation.

    PubMed

    Pan, Dawei; Chen, Jinhua; Tao, Wenyan; Nie, Lihua; Yao, Shouzhuo

    2006-06-20

    A new catalyst support, polyoxometalate-modified carbon nanotubes, is presented in this paper through the chemisorption between polyoxometalate and carbon. Pt and Pt-Ru nanoparticles were electrochemically deposited on polyoxometalate-modified carbon nanotubes electrodes, and their electrocatalytic properties for methanol electro-oxidation are investigated in detail. Due to the unique electrical properties of carbon nanotubes and the excellent redox properties and the high protonic conductivity of polyoxometalate, for the similar deposition charge of Pt and Pt-Ru catalysts, 1.4 times larger exchange current density, 1.5 times higher specific activity, and better cycle stabilities can be obtained at polyoxometalate-modified carbon nanotube electrodes as compared to the electrodes without polyoxometalate modification. These results show that polyoxometalate-modified carbon nanotubes as a new catalyst support have good potential application in direct methanol fuel cells.

  10. Hybrid assemblies based on a gadolinium-containing polyoxometalate and a cationic polymer with spermine side chains for enhanced MRI contrast agents.

    PubMed

    Chai, Wenqiang; Wang, Shan; Zhao, Hang; Liu, Guifeng; Fischer, Karl; Li, Haolong; Wu, Lixin; Schmidt, Manfred

    2013-09-27

    Supramolecular assembly: Spherical and stable hybrid assemblies based on a cationic polymer with spermine side chains and an anionic Gd(3+)-containing polyoxometalate cluster (GdW) are prepared by electrostatic interaction. The T1-weighted MRI performance of GdW is enhanced about three times in the assemblies; meanwhile, the assemblies show good biocompatibility, which enables them to be promising candidates for MRI contrast agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Polyoxometalate-based organic-inorganic hybrid compounds containing transition metal mixed-organic-ligand complexes of N-containing and pyridinecarboxylate ligands.

    PubMed

    Zhao, De-Chuan; Hu, Yang-Yang; Ding, Hong; Guo, Hai-Yang; Cui, Xiao-Bing; Zhang, Xiao; Huo, Qi-Sheng; Xu, Ji-Qing

    2015-05-21

    Five new organic–inorganic hybrid compounds based on the Keggin-type polyoxoanion [SiW12O40]4−, namely [Cu3(2,2′-bpy)3(inic)(μ2-OH)(H2O)][SiW12O40]·2H2O (1), [Cu6(phen)6(μ3-Cl)2(μ2-Cl)2Cl2(inic)2][SiW12O40]·6H2O (2), [Cu2(hnic)(2,2′-bpy)2Cl]2[H2SiW12O40] (3), [Cu2(nic)(phen)2Cl2]2[SiW12O40] (4) and [Cu2(pic)(2,2′-bpy)2Cl]2[SiW12O40] (5) (inic = isonicotinic acid, hnic = 2-hydroxy-nicotinic acid, nic = nicotinic acid, pic = picolinic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by IR, UV-Vis, XPS, XRD, cyclic voltammetric measurements, photoluminescence analysis and single crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 exhibits a 2-D double layered framework structure constructed from [SiW12O40]4− and copper-aqua-2,2′-bipy-hydroxyl-isonicotinate complexes. Compound 2 is a 0-D discrete structure formed by [SiW12O40]4− and copper-chloro-isonicotinate-phenanthroline complexes. Compound 3 shows a 1-D single chain structure based on the linkage of copper-2,2-bpy-chloro-2-hydroxy-nicotinate complexes and [SiW12O40]4−. Compounds 4 and 5 both contain polyoxometalate supported transition metal complexes, one is a polyoxometalate supported copper-chloro-nicotinate-phenanthroline complex in 4, and the other is a polyoxometalate supported copper-2,2-bpy-chloro-nicotinate complex in 5. It should be noted that nicotinic, isonicotinic and picolinic acids are structural isomers and 2-hydroxy-nicotinic acid is an in situ hydroxylated product of nicotinic acid. In addition, photocatalytic degradation of Rhodamine B (RhB) by compounds 1–5 has been investigated in aqueous solutions.

  12. Gold nanoparticle-decorated keggin ions/TiO2 photococatalyst for improved solar light photocatalysis.

    PubMed

    Pearson, Andrew; Jani, Harit; Kalantar-zadeh, Kourosh; Bhargava, Suresh K; Bansal, Vipul

    2011-06-07

    We demonstrate a facile localized reduction approach to synthesizing a Au nanoparticle-decorated Keggin ion/TiO(2) photococatalyst for improved solar light photocatalysis application. This has been achieved by exploiting the ability of TiO(2)-bound Keggin ions to act as a UV-switchable, highly localized reducing agent. Notably, the approach proposed here does not lead to contamination of the resultant cocatalyst with free metal nanoparticles during aqueous solution-based synthesis. The study shows that for Keggin ions (phosphotungstic acid, PTA), being photoactive molecules, the presence of both Au nanoparticles and PTA on the TiO(2) surface in a cocatalytic system can have a dramatic effect on increasing the photocatalytic performance of the composite system, as opposed to a TiO(2) surface directly decorated with metal nanoparticles without a sandwiched PTA layer. The remarkable increase in the photocatalytic performance of these materials toward the degradation of a model organic Congo red dye correlates to an increase of 2.7-fold over that of anatase TiO(2) after adding Au to it and 4.3-fold after introducing PTA along with Au to it. The generalized localized reduction approach to preparing TiO(2)-PTA-Au cocatalysts reported here can be further extended to other similar systems, wherein a range of metal nanoparticles in the presence of different Keggin ions can be utilized. The composites reported here may have wide potential implications toward the degradation of organic species and solar cell applications.

  13. Crystal structures and spectral properties of two polyoxometalate-based inorganic-organic compounds from silver-azine building blocks with bis-bidentate and tridentate ligands.

    PubMed

    An, Bing; Zhou, Rui-Min; Sun, Li; Bai, Yan; Dang, Dong-Bin

    2014-07-15

    Two polyoxometalate-based inorganic-organic hybrid compounds constructed from silver(I)-L species and saturated Keggin type polyoxoanion, [Ag2L2(1)]2(SiMo12O40)·1.5DMF·0.5CH3OH⋅H2O 1 and [{Ag4L2(2)(DMF)5}(SiMo12O40)] 2 (L(1) = phenyl 2-pyridyl ketone azine, L(2) = 3-phenyltriazolo[1,5-a]pyridine), have been synthesized and structurally characterized by IR, UV, elemental analysis, XRPD and complete single crystal structure analyses, where the ligands L(1) and L(2) are bis-bidentate and tridentate azines synthesized with the same materials under different conditions. The structure of 1 exhibits a dinuclear double-helicate with [SiMo12O40](4)(-) anions as counter ions, where all of the Ag centers coordinate to bis-bidentate chelating ligands. Compound 2 displays a two-dimensional sheet formed by the Ag-organic infinite chains and the [SiMo12O40](4)(-) alternately arranged in a "rail-like" fashion. The luminescent properties of 1 and 2 in the solid state were investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer.

    PubMed

    Raj, Gijo; Swalus, Colas; Guillet, Alain; Devillers, Michel; Nysten, Bernard; Gaigneaux, Eric M

    2013-04-02

    Hybridization of polyoxometalates (POMs) via the formation of an organic-inorganic association constitutes a new route to develop a heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies to obtain tunable well-defined supramolecular architectures of an organic-inorganic heterogeneous hybrid catalyst formed by the association of a hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property of the initial polyampholyte copolymer matrix is modulated by controlling the pH of the hybridization solution. When deposited on a mica surface, isolated, long and extended polymer chains are formed under basic conditions (pH 7.9), while globular or coiled structures are formed under acidic conditions (pH 2). The supramolecular assembly of the POM-polymer hybrid is found to be directed by the type and quantities of charges present on the polyampholyte copolymer, which themselves depend on the pH conditions. The hypothesis is that the Keggin type [PW12O40](3-) anions, which have a size of ~1 nm, electrostatically bind to the positive charge sites of the polymer backbone. The hybrid material stabilized at pH 5.3 consists of POM-decorated polymer chains. Statistical analysis of distances between pairs of POM entities show narrow density distributions, suggesting that POM entities are attached to the polymer chains with a high level of order. Conversely, under acidic conditions (pH 2), the hybrid shows the formation of a core-shell type of structure. The strategies reported here, to tune the supramolecular assembly of organic-inorganic hybrid materials, are highly valuable for the design and a more rational utilization of POM heterogeneous catalysts in several chemical transformations.

  15. Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass Selected Ions

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Johnson, Grant E.; Andersen, Amity; Du, Dan; Zhang, Weiying; Prabhakaran, Venkateshkumar; Lin, Yuehe; Laskin, Julia

    2014-12-04

    We investigate the controlled deposition of Keggin polyoxometalate (POM) anions, PMo12O403- and PMo12O402-, onto different self-assembled monolayer (SAM) surfaces via soft landing of mass-selected ions. Utilizing in situ infrared reflection absorption spectroscopy (IRRAS), ex situ cyclic voltammetry (CV) and electronic structure calculations, we examine the structure and charge retention of supported multiply-charged POM anions and characterize the redox properties of the modified surfaces. SAMs of alkylthiol (HSAM), perfluorinated alkylthiol (FSAM), and alkylthiol terminated with NH3+ functional groups (NH3+SAM) are chosen as model substrates for soft landing to examine the factors which influence the immobilization and charge retention of multiply charged anionic molecules. The distribution of charge states of POMs on different SAM surfaces are determined by comparing the IRRAS spectra with vibrational spectra calculated using density functional theory (DFT). In contrast to the results obtained previously for multiply charged cations, soft landed anions are found to retain charge on all three SAM surfaces. This charge retention is attributed to the substantial electron binding energy of the POM anions. Investigation of redox properties by CV reveals that, while surfaces prepared by soft landing exhibit similar features to those prepared by adsorption of POM from solution, the soft landed POM2- has a pronounced shift in oxidation potential compared to POM3- for one of the redox couples. These results demonstrate that ion soft landing is uniquely suited for precisely controlled preparation of substrates with specific electronic and chemical properties that cannot be achieved using conventional deposition techniques.

  16. Polyoxometalate-based Catalysts for Toxic Compound Decontamination and Solar Energy Conversion

    NASA Astrophysics Data System (ADS)

    Guo, Weiwei

    Polyoxometalates (POMs) have been attracting interest from researchers in the fields of Inorganic Chemistry, Physical Chemistry, Biomolecular Chemistry, etc. Their unique structures and properties render them versatile and facilitate applications in medicine, magnetism, electrochemistry, photochemistry and catalysis. In particular, toxic compound (chemical warfare agents (CWAs) and toxic industrial compounds (TICs)) decontamination and solar energy conversion by POM-based materials have becoming promising and important research areas that deserve much attention. The focus of this thesis is to explore the structural features of POMs, to develop POM-based materials and to investigate their applications in toxic compound decontamination and solar energy conversion. The first part of this thesis gives a general introduction on the history, structures, properties and applications of POMs. The second part reports the synthesis, structures, and reactivity of different types of POMs in the destruction of TICs and CWAs. Three tetra-n-butylammonium (TBA) salts of polyvanadotungstates, [n-Bu4N]6[ PW9V3], [n-Bu4N] 5H2PW8V4O40 (PW 8V4), [n-Bu4N]4H 5PW6V6O40· 20H2O (PW6V6) are discussed in detail. These vanadium-substituted Keggin type POMs show effective activity for the aerobic oxidation of formaldehyde (a major TIC and human-environment carcingen) to formic acid under ambient conditions. Moreover, two types of POMs have also been developed for the removal of CWAs and/or their simulants. Specifically, a layered manganese(IV)-containing heteropolyvanadate with a 1:14 Stoichiometry, K4Li2[MnV14O40]˙21H2 O has been prepared. Its catalytic activity for oxidative removal of 2-chloroethyl ethyl sulfide (a mustard simulant) is discussed. The second type of POM developed for decontamination of CWAs and their simulants is the new one-dimensional polymeric polyniobate (P-PONb), K12[Ti 2O2][GeNb12O40]˙19H2O (KGeNb). The complex has been applied to the decontamination of a wide range

  17. Incorporating polyoxometalates into a porous MOF greatly improves its selective adsorption of cationic dyes.

    PubMed

    Yan, Ai-Xue; Yao, Shuang; Li, Yang-Guang; Zhang, Zhi-Ming; Lu, Ying; Chen, Wei-Lin; Wang, En-Bo

    2014-06-02

    Various polyoxometalates (POMs) were successfully immobilized to the mesoporous coordination polymer MIL-101 resulting in a series of POM-MOF composite materials POM@MIL-101 (POM = K4PW11VO40, H3PW12O40, K4SiW12O40). These materials were synthesized by a simple one-pot reaction of Keggin POMs, tetramethylammonium hydroxide (TMAH), terephthalic acid (H2bdc), and Cr(3+) ions. XRD, FTIR, thermogravimetric analyses (TG), inductively coupled plasma (ICP) spectrometry, and energy-dispersive X-ray spectroscopy (EDX) collectively confirmed the successful combination of POMs and the porous framework. Further, these composites POM@MIL-101 with different loading of POMs were achieved by variation of the POM dosage. Notably, the uptake capacity of MIL-101 towards organic pollutants in aqueous solution was significantly improved by immobilization of hydrophilic POMs into cages of MIL-101. An uptake capacity of 371 mg g(-1), comparable to that of the graphene oxide sponges, and much higher than that of the commercial activated carbon, was achieved at room temperature in 5 min when dipping 20 mg PW11V@MIL-101 in the methylene blue (MB) solution (100 mL of 100 mg L(-1) MB solution). Further study revealed that the POM@MIL-101 composite materials not only exhibited a fast adsorption rate towards dye molecules, but also possessed of selective adsorption ability of the cationic dyes in wastewater. For example, the adsorption efficiency of PW11V@MIL-101 (10 mg) towards MB (100 mL of 10 mg L(-1)) could reach 98 % in the initial 5 min, and it could capture MB dye molecules from the binary mixture of the MB and MO with similar size. Also, the POM@MIL-101 materials could be readily recycled and reused, and no POM leached in the dye adsorption process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands.

    PubMed

    Zhu, Guibo; Geletii, Yurii V; Zhao, Chongchao; Musaev, Djamaladdin G; Song, Jie; Hill, Craig L

    2012-09-07

    A dodecazinc silicotungstate K(20)Na(2)[Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))](2)·34H(2)O (1) has been synthesized and characterized by X-ray crystallography, elemental analysis, infrared, UV-vis spectroscopy, cyclic voltammetry, acid-base titration, and DFT calculations. The twelve zinc atoms between the two [Si(2)W(18)O(66)](16-) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, [Si(2)W(18)O(66)](16-), themselves. The structurally unique central Zn(12) core is formed by the fusion of two [Zn(6)(OH)(7)(H(2)O)](5+) units through two edge-sharing Zn6 atoms. DFT B3LYP calculations give HOMO-LUMO and (HOMO - 1)-LUMO energy gaps of ∼3.65 and 3.91 eV, respectively, as compared to the band gap in ZnO of 3.35 eV.

  19. Solid-state dynamics of uranyl polyoxometalates.

    PubMed

    Alam, Todd M; Liao, Zuolei; Zakharov, Lev N; Nyman, May

    2014-07-01

    Understanding fundamental uranyl polyoxometalate (POM) chemistry in solution and the solid state is the first step to defining its future role in the development of new actinide materials and separation processes that are vital to every step of the nuclear fuel cycle. Many solid-state geometries of uranyl POMs have been described, but we are only beginning to understand their chemical behavior, which thus far includes the role of templates in their self-assembly, and the dynamics of encapsulated species in solution. This study provides unprecedented detail into the exchange dynamics of the encapsulated species in the solid state through Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although it was previously recognized that capsule-like molybdate and uranyl POMs exchange encapsulated species when dissolved in water, analogous exchange in the solid state has not been documented, or even considered. Here, we observe the extremely high rate of transport of Li(+) and aqua species across the uranyl shell in the solid state, a process that is affected by both temperature and pore blocking by larger species. These results highlight the untapped potential of emergent f-block element materials and vesicle-like POMs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Spin-lattice relaxation via quantum tunneling in an Er3+ -polyoxometalate molecular magnet

    NASA Astrophysics Data System (ADS)

    Luis, F.; Martínez-Pérez, M. J.; Montero, O.; Coronado, E.; Cardona-Serra, S.; Martí-Gastaldo, C.; Clemente-Juan, J. M.; Sesé, J.; Drung, D.; Schurig, T.

    2010-08-01

    We investigate the mechanism of spin-lattice relaxation of Er ions encapsulated in polyoxometalate clusters, which below 4 K can only reverse its spin via quantum tunneling processes. The temperature-independent rate τ-1 is, at zero field, ten orders of magnitude larger than the rates predicted for direct phonon-induced processes. In addition, we observe that τ-1 is suppressed by external magnetic bias and hyperfine interactions but enhanced by increasing the concentration of Er ions. The observed relaxation agrees with predictions for pure quantum tunneling, showing that this phenomenon drives the thermalization of electronic spins. A possible link between these two phenomena is discussed, involving the collective emission of phonons from particular spin configurations attained via quantum tunneling.

  1. A polyoxometalate based 3D framework with helix and multinuclear Ag-pyttz cycles

    NASA Astrophysics Data System (ADS)

    Sha, Jing-Quan; Zhou, Bai-Bin; Wang, Cheng; Sun, Jing-Wen; Yan, Peng-Fei

    2015-02-01

    A new 3D hybrid compound based on polyoxometalates (POMs), [Ag6(Hpyttz) (pyttz) (H2O)][PMo12O40] (pyttz = 3-(pyrid-2-yl)-5-(1H-1,2,4-triazol- 3-yl)-1,2,4-triazolyl), has been hydrothermally synthesized and structurally characterized by routine techniques. X-ray diffraction analysis reveals that the title compound is constructed by the 2D Ag-pyttz coordination polymer with 12-nuclear cycles and Ag-POM inorgnaic architecture. The whole 3D framework contains the helix and cycles double configuration tunnels, which is formed by the right- and left-helical chain linking with TMCs subunit in hand-in-hand mode. Note that such structural feature is rare in POMOF system. Unfortunately, because of the opposite direction of the helical chains spiral inward, the tunnels are occupied by the {PMo12} clusters. Furthermore, the title compound exhibits good photocatalytic activity toward degradation of RhB.

  2. Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells.

    PubMed

    Gao, Junkuo; Miao, Jianwei; Li, Yongxin; Ganguly, Rakesh; Zhao, Yang; Lev, Ovadia; Liu, Bin; Zhang, Qichun

    2015-08-28

    A simple and facile one-step method for the synthesis of an organic dye-functionalized polyoxometalate (POM) hybrid with visible-light photo-response was reported. The POM hybrid was fully characterized via single crystal XRD, powder XRD, FTIR and elemental analysis. The reaction of the organic dye with inorganic salts gave the dye-functionalized POM (MoBB3), in which the POM cluster was formed in situ. The electronic absorption peak of this hybrid was successfully extended beyond 680 nm. Photoelectrochemical measurement indicated that MoBB3 was photoresponsive under visible-light illumination, suggesting that it is an n-type (electron conductive) semiconducting material. This result might offer a method for the design of novel organic dye-functionalized POMs for photoelectric applications.

  3. Polyoxometalate (POM) Nanocluster-Induced Phase Transition and Structural Disruption in Lipid Bilayers.

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Zhu, Y. Elaine; Hutin, Marie; Cronin, Leroy

    2012-02-01

    Polyoxometalate (POM) nanoclusters that are transition metal oxygen clusters with well defined atomic coordination structures have recently emerged as new and functional nanocolloidal materials used as catalysts, anti-cancer medicines, and building blocks for novel functional materials. However, their implications to human health and environment remain poorly investigated. In this work, we examine the interaction of highly charged anionic POM nanocluters with lipid bilayers as a model cell membrane system. It is observed that upon the adsorption of anionic POMs, lipid dynamics is significantly suppressed and lipid bilayers are disrupted with resultant pore and budding-like structural formation. Direct calorimetric experiment of POM interaction with lipid bilayers of varied lipid compositions confirms the POM-induced fluid-to-gel phase transition in lipid bilayers, due to strong electrostatic interaction between POM nanocluster and lipid head groups.

  4. Differentiation of stem cells into insulin-producing cells under the influence of nanostructural polyoxometalates.

    PubMed

    Bâlici, Ştefana; Şuşman, Sergiu; Rusu, Dan; Nicula, Gheorghe Zsolt; Soriţău, Olga; Rusu, Mariana; Biris, Alexandru S; Matei, Horea

    2016-03-01

    Two polyoxometalates (POMs) with W were synthesized by a two-step, self-assembling method. They were used for stimulation of mesenchymal stem cell differentiation into insulin-producing cells. The nanocompounds (tris(vanadyl)-substituted tungsto-antimonate(III) anions [POM1] and tris-butyltin-21-tungsto-9-antimonate(III) anions [POM2]) were characterized by analytical techniques, including ultraviolet-visible, Fourier transform infrared, nuclear magnetic resonance spectroscopy, and transmission electron microscopy. We found that these polyoxotungstates, with 2-4 nm diameters, did not present toxic effects at the tested concentrations. In vitro, POM1 stimulated differentiation of a greater number of dithizone-positive cells (also organized in clusters) than the second nanocompound (POM2). Based on our in vitro studies, we have concluded that both the POMs tested had significant biological activity acting as active stimuli for differentiation of stem cells into insulin-producing cells.

  5. Induced circular dichroism of polyoxometalates via electrostatic encapsulation with chiral organic cations.

    PubMed

    Wang, Yizhan; Shi, Lei; Yang, Yang; Li, Bao; Wu, Lixin

    2014-09-21

    To explore the principle of chiral induction in inorganic clusters, chiral organic cations with two stereocenters, R- and S-BPEA, are used to encapsulate a series of polyoxometalates (POMs) bearing different structures and transition absorption bands in aqueous solution, constructing a series of chiral supramolecular complexes. Due to the induction of chiral organic cations, POMs possessing both chiral and achiral structures show an induced circular dichroism (ICD) effect. ICD signals in the absorption bands corresponding to ligand to metal charge transfer (LMCT) transitions, d-d transitions and intervalence charge transfer (IVCT) transitions are observed for different complexes. Moreover, the ICD of the POMs exhibits a direct correlation with the degree of POM distortion and the distance between the chiral center and the POM surface. The encapsulation of POMs with chiral organic cations via electrostatic interactions provides a facile and effective method for constructing optically pure POM-based materials.

  6. Immobilization of polyoxometalates in crystalline solids for highly efficient heterogeneous catalysis.

    PubMed

    Ye, Ji-Jie; Wu, Chuan-De

    2016-06-21

    Polyoxometalates (POMs) are a unique class of molecular metal-oxygen clusters with attractive architecture and tunable properties. Due to their strong acidity, redox chemistry, photoactivity, charge distribution and multielectron transformation, POMs have been used as efficient catalysts in a variety of chemical reactions. To meet the requirement of sustainable chemistry, great effort has been focused on immobilization of the active POMs on different solid supports to realize heterogeneous catalysis. This short review summarizes the recent progress on immobilization of POM moieties in crystalline solids with defined crystal structures, including organic-inorganic hybrid materials, POM-based inorganic crystalline solids and POM-encapsulated metal-organic frameworks (POM@MOFs), and their catalytic properties in oxidation, hydrolysis, cyanosilylation, photocatalysis and electrocatalysis. As illustrated in the text, these crystalline solids exhibit interesting catalytic properties, such as high activity, stability and selectivity, and simple recovery and easy recycling, which are much superior to those of the corresponding constituent species in most cases.

  7. New type of heterometallic 3d-4f rhomblike core in Weakley-like polyoxometalates.

    PubMed

    Reinoso, Santiago; Galán-Mascarós, José Ramón; Lezama, Luis

    2011-10-03

    The first heterometallic copper-cerium polyoxometalate, [{Ce(IV)(OAc)}Cu(II)(3)(H(2)O)(B-α-GeW(9)O(34))(2)](11-) (1), is composed of an unprecedented copper(II)-trisubstituted Weakley-type tungstogermanate subunit stabilized by coordination of a {Ce(OAc)}(3+) group at the vacant position. The title species contains a central {Ce(IV)Cu(II)(3)O(18)} rhomblike cluster that belongs to a new {(4f(ext))(3d(ext))(3d(int))(2)} type and magnetically behaves as a triangular Cu(3) system with overall antiferromagnetic exchange affected by the structural distortions the vicinity of diamagnetic Ce(IV) induces.

  8. Interaction of Keggin anions of 12-tungstophosphoric acid with Ce(x)Zr(1-x)O2 solid solutions.

    PubMed

    Rao, G Ranga; Rajkumar, T

    2008-08-01

    The interaction of 20 wt% 12-tungstophosphoric acid with Ce(x)Zr(1-x)O(2) solid solutions has been studied by PXRD, FTIR, FT-Raman, H(2)-TPR, NH(3)-TPD, diffuse reflectance UV-vis-NIR, and (31)P MAS NMR techniques. The study indicates that the Keggin anions are attached to Lewis metal ion centres and anion vacancies on Ce(x)Zr(1-x)O(2) supports through WO terminal bonds. The Keggin units at the interface are chemically perturbed as indicated by non-intrinsic IR bands observed at 958 cm(-1) (WO(ter) bond), and 1052, 1102 cm(-1) (PO bond). NH(3)-TPD shows that the Keggin anions fixed to Lewis sites and/or oxygen ion vacancies decrease the ammonia uptake on Ce(x)Zr(1-x)O(2) solid solutions. H(2)-TPR shows modified redox behaviour of Ce(x)Zr(1-x)O(2) solid solutions due to the simultaneous reduction of ceria, decomposition of Keggin anions and the reduction of WO(3). The broadening of (31)P MAS NMR and DR-UV-vis-NIR spectra demonstrate the existence of chemical interactions between the Keggin anions and Ce(x)Zr(1-x)O(2) supports.

  9. Nanoscale characterization of polyoxometalate catalysts by scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Kaba, Mahmoud Samah

    Polyoxometalates (POMs) are dsp0 early transition metal oxide anion clusters that have found applications in acid and oxidation catalysis, electrode functionalization, and anti-retroviral therapy. Scanning tunneling microscopy (STM) is a powerful surface science technique that was used to determine the structural properties of self-assembled monolayers of POMs, and to probe the electronic properties of individual POM molecules. In our studies, POMs were deposited from aqueous solutions onto graphite surfaces, and the STM operated in ambient conditions gave well-resolved images of the POM-derivatized surfaces, showing highly ordered, two-dimensional surface arrays (corrugations). The shape and periodicity of the corrugations were consistent with the molecular dimensions and structures of POMs as determined by X-ray diffraction. Different coadsorbed species were also imaged in air using STM; the species were distinguished based on differences in shapes and on electronic properties. These results are important steps toward real-space STM imaging of chemical reactions. Tunneling spectroscopy (TS) measurements (current-voltage, or I-V spectra) taken atop the corrugations and compared with the I-V spectra of bare graphite, confirmed that the STM imaged individual POM molecules in monolayer arrays on graphite. The characteristics of the POM monolayers, such as the effects of counter-cation substitution and anion-framework substitution on the ordered arrays, were also examined by STM. The ubiquity of the ordered array formation of these metal oxide clusters suggests that they can be utilized to create well-defined surfaces with more complex chemical functions than one typically encounters in studies of metal and oxide single crystal surfaces. The POM corrugations exhibited localized electronic phenomena, referred to as negative differential resistance (NDR), at specific voltages in their I-V spectra. The NDR voltage in the I-V spectrum was dependent on the identity of the

  10. A photochromic naphthalene diimide coordination network sensitized by polyoxometalates.

    PubMed

    Liu, Jian-Jun; Wang, Yao; Hong, Yu-Jian; Lin, Mei-Jin; Huang, Chang-Cang; Dai, Wen-Xin

    2014-12-28

    Metal-ion-directed assembly of naphthalene diimide tectons cooperatively enhanced by anion-π interactions of giant anions, PMo12O40(3-), leads to a novel organic-inorganic hybrid with ultrafast-responsive photochromic properties, which is attributed to the polyoxometalate-sensitized photo-induced radical generation of naphthalene diimide units.

  11. Nucleophilic substitution reaction for post-functionalization of polyoxometalates

    SciTech Connect

    Yin, Panchao; Li, Qiang; Zhang, Jin; Wang, Longsheng; Hao, Jian; Wei, Yongge

    2015-07-06

    In this study, a hexamolybdate-based organic inorganic hybrid molecule containing a chloralkane fragment is synthesized and its Cl atom can be substituted by iodine and nitrate through nucleophilic substitution reactions in high yields, which provide a post-functionalization protocol to bring in various additional functional groups into polyoxometalate-based hybrid materials under mild conditions.

  12. Progress in the development and optimization of polyoxometalate delignification systems

    Treesearch

    R.H. Atalla; I.A. Weinstock; R.S. Reiner; E.L. Springer; C.G. Hill

    2003-01-01

    We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

  13. Progress in the development and optimization of polyoxometalate delignification systems

    Treesearch

    R.H. Atalla; I.A. Weinstock; J.S. Bond; R.S. Reiner; E.L. Springer; C.G. Hill; Yu. Geletii; V.A. Grigoriev; A.J. Bailey; L. Delannoy; C.L. Hill

    2002-01-01

    We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

  14. Nucleophilic substitution reaction for post-functionalization of polyoxometalates

    DOE PAGES

    Yin, Panchao; Li, Qiang; Zhang, Jin; ...

    2015-07-06

    In this study, a hexamolybdate-based organic inorganic hybrid molecule containing a chloralkane fragment is synthesized and its Cl atom can be substituted by iodine and nitrate through nucleophilic substitution reactions in high yields, which provide a post-functionalization protocol to bring in various additional functional groups into polyoxometalate-based hybrid materials under mild conditions.

  15. An all-inorganic polyoxometalate-polyoxocation chemical garden.

    PubMed

    Points, Laurie J; Cooper, Geoffrey J T; Dolbecq, Anne; Mialane, Pierre; Cronin, Leroy

    2016-01-31

    Herein, we show it is possible to produce wholly inorganic chemical gardens from a cationic polyoxometalate (POM) seed in an anionic POM solution, demonstrating a wholly POM-based chemical garden system that produces architectures over a wide concentration range. Six concentration dependent growth regimes have been discovered and characterized: clouds, membranes, slugs, tubes, jetting and budding.

  16. Electrochemical delignification of wood pulp using polyoxometalate mediators

    Treesearch

    R.S. Reiner; E.L. Springer; R.H. Atalla

    2003-01-01

    It has been found that polyoxometalates (POMs) can act as mediators in the electrochemical oxidation of lignin in pulps. An electrochemical cell, with a Nafion® membrane separating the anode and cathode compartments, was used in the delignification experiments. A softwood kraft pulp was placed in the anode compartment with a buffered 0.01M solution of the...

  17. New Iron Polyoxometalate - Based Catalysts for Decontamination of HD and G Agents

    DTIC Science & Technology

    2003-11-19

    New iron polyoxometalate - based catalysts for decontamination of HD and G agents Nelya Okun, Chris Tarr, Lei Zhang and Craig Hill... polyoxometalate - based catalysts for decontamination of HD and G agents 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S...Si/AlO2n+. Catalytic activity of iron POMs bound to Si/AlO2n+. New iron containing POMs Recently developed iron containing polyoxometalates (POMs

  18. Photocatalytic reduction and recovery of copper by polyoxometalates.

    PubMed

    Troupis, A; Hiskia, A; Papaconstantinou, E

    2002-12-15

    A series of polyoxometalates PW12O40(3-), SiW12O40(4-), and P2Mo18O62(6-) have been used as photocatalysts for recovery of copper and production of fine metal particles. The process involves absorption of light by polyoxometalates, oxidation of an organic substrate, for instance, propan-2-ol as sacrificial reducing reagent, and reoxidation of the reduced polyoxometalates by Cu2+ ions, closing the photocatalytic cycle. Copper(II) ions are reduced to copper(I) and finally to zero-state particles in a 2-electron process, as also suggested by the half-order dependence. Increase of catalyst or propan-2-ol concentration, or both, accelerates the photodeposition of copper until a saturation value is reached. The method is operational at a wide range of copper concentrations varying from 3 to 1300 ppm, leading to very low final concentrations (<0.2 ppm). The presence of dioxygen suppresses the initiation of copper recovery, though the process is equally effective after dioxygen is consumed. The process is independent of pH within the range 0.3-5.0. Addition of ClO4-, NO3-, or CH3COO- has no effect on the removal of copper ions. Chloride ions retard the enhancement of copper precipitation through stabilization of copper(I). This homogeneous, polyoxometalate-based process exhibits some benefits in comparison with the semiconductor-based (heterogeneous) recovery of metals: The final zero-state metal particles are obtained in pure form. No separation from the catalyst is needed, and moreover, the process is catalytic as the photodeposited metal particulates do not hinder the photocatalytic action of polyoxometalate anions.

  19. Keggin (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O: Characterization and crystal structure

    SciTech Connect

    Bonfim, Rodrigo de Paiva Floro; Moura, Luiza Cristina de; Eon, Jean-Guillaume; Mentré, Olivier; Vezin, Hervé; Caldarelli, Stefano

    2014-05-01

    Single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O of the vanadium tri-substituted α-Keggin dodecatungstosilicate were prepared and analyzed by vibrational, EPR and {sup 51}V NMR spectroscopy. Varying the synthesis conditions allows crystallization of partially reduced anions. The crystal structure was determined for both oxidized (V{sup 5+}) and partially reduced (V{sup 4+/5+}) potassium salts. Single crystal X-ray diffraction data and solid state {sup 51}V-NMR spectra confirm the occurrence of a single vanadium site in a cubic structure due to rotational disorder of the Keggin ion. Partially reduced compounds crystallize within the same structure as fully oxidized ones. EPR experiments confirm strong interaction of V{sup 4+} with two V{sup 5+} ions, in accordance with insertion of a V{sub 3} subunit into the lacunary Keggin ion as designed in the synthesis method. The 3D-edifice is composed of K{sup +}/H{sub 2}O counter-sublattice with evidence of tunable water occupancy. - Graphical abstract: Relative arrangements of HPA clusters in (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}]·xH{sub 2}O. - Highlights: • We prepared single crystals of the potassium salt (K{sub 5}, H{sub 3}O)[SiV{sub 3}W{sub 9}O{sub 40}H]·xH{sub 2}O. • The synthesis was designed to give the α-1,2,3-[SiV{sub 3}W{sub 9}O{sub 40}] Keggin ion. • Strict pH control was necessary to avoid vanadium partial reduction. • Reduced compounds crystallize within the same structure as fully oxidized ones. • EPR confirms strong interaction of V{sup 4+} with two V{sup 5+} ions in a V{sub 3} subunit.

  20. Nanostructured polyoxometalate arrays with unprecedented properties and functions.

    SciTech Connect

    Dunphy, Darren Robert; Brinker, C. Jeffrey; Singh, Seema; Nyman, May Devan

    2003-11-01

    Polyoxometalates (POMs) are ionic (usually anionic) metal -oxo clusters that are both functional entities for a variety of applications, as well as structural units that can be used as building blocks if reacted under appropriate conditions. This is a powerful combination in that functionality can be built into materials, or doped into matrices. Additionally, by assembling functional POMs in ordered materials, new collective behaviors may be realized. Further, the vast variety of POM geometries, compositions and charges that are achievable gives this system a high degree of tunability. Processing conditions to link together POMs to build materials offer another vector of control, thus providing infinite possibilities of materials that can he nano-engineered through POM building blocks. POM applications that can be built into POM-based materials include catalysis, electro-optic and electro-chromic, anti-viral, metal binding, and protein binding. We have begun to explore three approaches in developing this field of functional, nano-engineered POM-based materials; and this report summarizes the work carried out for these approaches to date. The three strategies are: (1) doping POMs into silica matrices using sol-gel science, (2) forming POM-surfactant arrays and metal-POM-surfactant arrays, (3) using aerosol-spray pyrolysis of the POM-surfactant arrays to superimpose hierarchical architecture by self-assembly during aerosol-processing. Doping POMs into silica matrices was successful, but the POMs were partially degraded upon attempts to remove the structure-directing templates. The POM-surfactant and metal-POM-surfactant arrays approach was highly successful and holds much promise as a novel approach to nano-engineering new materials from structural and functional POM building blocks, as well as forming metastable or unusual POM geometries that may not be obtained by other synthetic methods. The aerosol-assisted self assembly approach is in very preliminary state of

  1. Mechanism of thioether oxidation over di- and tetrameric ti centres: kinetic and DFT studies based on model Ti-containing polyoxometalates.

    PubMed

    Skobelev, Igor Y; Zalomaeva, Olga V; Kholdeeva, Oxana A; Poblet, Josep M; Carbó, Jorge J

    2015-10-05

    The oxidation of thioethers by the green oxidant aqueous H2 O2 catalysed by the tetratitanium-substituted Polyoxometalate (POM) (Bu4 N)8 [{γ-SiTi2 W10 O36 (OH)2 }2 (μ-O)2 ], as a model catalyst comprising tetrameric titanium centres, was investigated by kinetic modelling and DFT calculations. Several mechanisms of sulfoxidation were evaluated by using methyl phenyl sulfide (PhSMe) as a model substrate in the experiments and dimethyl sulfide in the calculations. The first mechanism assumes that the active hydroperoxo species forms directly through interaction of the Ti2 (μ-OH)2 group in [{γ-SiTi2 W10 O36 (OH)2 }2 (μ-O)2 ](8-) (1 D) with H2 O2 . The second mechanism includes hydrolysis of Ti-O-Ti bonds linking two γ-Keggin units in structure 1 D to produce the monomer [(γ-SiW10 Ti2 O38 H2 )(OH)2 ](4-) (1 M), followed by the formation of an active hydroperoxo species upon interaction of the Ti hydroxo group with H2 O2 . Both kinetic modelling and DFT calculations support the mechanism through the monomeric species that involves the hydrolysis step. According to the DFT studies the activation of H2 O2 by compound 1 M is preferred by 6.5 kcal mol(-1) with respect to anion 1 D due to the more flexible Ti environment of the terminal Ti hydroxo group in 1 M. The calculations also indicate that for the "monomeric" mechanism two pathways are operative: the mono- and the multinuclear pathway. In the mononuclear mechanism, the active group is the terminal TiOH group, whereas in the multinuclear path the active group is the bridging Ti2 (μ-OH) moiety. Moreover, unlike previous studies, the sulfoxidation is preferred through a β-oxygen atom transfer from the Ti hydroperoxo group because the α-oxygen atom transfer leads to an unfavourable seven-fold coordinated Ti environment in the transition state. Finally, we have generalised these results to other Ti-containing POMs: the Ti-monosubstituted α-Keggin ion [α-PTi(OH)W11 O39 ](4-) and the dititanium

  2. Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance.

    PubMed

    Tucher, Johannes; Wu, Yanlin; Nye, Leanne C; Ivanovic-Burmazovic, Ivana; Khusniyarov, Marat M; Streb, Carsten

    2012-09-07

    The photochemical properties of homo- and heterometallic molybdate-based Lindqvist polyoxometalate clusters are investigated in a comparative study and it is shown that vanadium substitution can be used as a facile synthetic tool to optimize the visible light absorption and photocatalytic activity of the cluster. The mono-vanadium substituted unit, [VMo(5)O(19)](3-) shows light absorption up to 480 nm whereas the light absorption of the molybdate analogue [Mo(6)O(19)](2-) is mainly in the UV region below 400 nm. The electronic absorption properties of both clusters are further investigated using TD-DFT calculations which show that vanadium incorporation leads to the formation of low-energy O → V LMCT transitions. In comparative photochemical dye decomposition test reactions under UV and Vis irradiation, a higher reactivity is observed for [VMo(5)O(19)](3-) together with turnover numbers of more than 1600. In addition it is shown that under anaerobic conditions, the photoreaction proceeds faster than in the presence of oxygen, suggesting that oxygen acts as a quencher in one of the photoredox steps.

  3. Synthesis, structural characterization, and thermoresponsivity of hybrid supramolecular dendrimers bearing a polyoxometalate core.

    PubMed

    Chen, Hailong; Yang, Yang; Wang, Yizhan; Wu, Lixin

    2013-08-12

    A series of cationic dendrons bearing triethylene glycol monomethyl ether terminal groups of different generations have been synthesized and used to encapsulate an inorganic polyanionic cluster [K(12.5)Na(1.5)(NaP5W30O110)] through electrostatic interactions. The resulting dendritic cation-encapsulated polyoxometalate (POM) complexes, cluster-dendrimers, are soluble in water and exhibit lower critical solution temperatures (LCST). The thermoresponsivities of these complexes in aqueous solutions were studied by turbidimetry and variable-temperature (1)H NMR spectroscopy. The observed cloud points show a remarkable dependence on the generation of the dendrons. Complexes composed of first-generation dendrons exhibit no obvious thermoresponsive properties, but for complexes bearing second-generation dendrons, the LCST decreases as the number of dendritic cations around the POM cluster increases. Complexes composed of third-generation cations underwent reversible aggregation and disaggregation upon heating and cooling, respectively. This thermally induced self-aggregation was characterized by DLS and TEM. In addition, the effects of salt and solvent on the LCST were investigated. This research demonstrates a new type of thermoresponsive dendritic organic-inorganic hybrid complex and provides a general route to the endowment of POMs with temperature-sensitive properties through electrostatic interactions.

  4. Acid-Base-Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane-like Silver Thiolate Shell.

    PubMed

    Liu, Hong; Song, Chao-Yu; Huang, Ren-Wu; Zhang, Yu; Xu, Hong; Li, Mei-Jia; Zang, Shuang-Quan; Gao, Guang-Gang

    2016-03-07

    Self-assembly of metavanadate and organosilver(I) salts leads to a novel dodecahedrane-like [Ag30 ((t) BuS)20 ](10+) silver(I) thiolate nanocage that tightly wraps an unusual C2h polyoxovanadate anion. The polyoxovanadate core undergoes transformation to a D3d configuration upon acidification, and reverts back to its original C2h structure upon addition of base. Chromism was observed for the silver(I) thiolate cluster during the configurational change of the central polyoxovanadate core; the color of the solution changes reversibly from green to dark yellow. This work represents the first reported example of chromic polyoxometalate-templated silver(I) thiolate shells that respond to external acid-base stimuli. It also represents an important advance in providing crystallographic proof that structural transformations occur in a nanoscale core-shell cluster. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Modeling the processes of electrophoretic transfer for spherical nanoclusters of iron-molybdenum polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ostroushko, A. A.; Grzhegorzhevskii, K. V.; Bystrai, G. P.; Okhotnikov, S. A.

    2015-09-01

    Processes of electrophoretic transfer of spherical nanocluster polyoxometalates containing molybdenum and iron through a membrane are modeled on the basis of experimental data. Using the thermodynamic approach, the data allow us to predict the depth of polyoxometalate penetration into the membrane and the probability of its accumulation over time.

  6. Closed-mill delignification by design using polyoxometalates

    Treesearch

    C. J. Houtman; R. S. Reiner; S. E. Reichel; M. J. Birchmeier; C. E. Sullivan; L. A. Weinstock; R. H. Atalla

    1999-01-01

    Polyoxometalates (POMs) are a class of delignification agents that promise to provide the basis for a new closed-mill bleaching technology. The results presented here are based on the use of Na6SiV2W10O40, which is effective in reducing the Kappa number of softwood Kraft pulp from 30 to below 10 with minimal loss in viscosity. A critical part of a viable POM process is...

  7. Tube-graft-Sheet Nano-Objects Created by A Stepwise Self-Assembly of Polymer-Polyoxometalate Hybrids.

    PubMed

    Tang, Jing; Li, Xue-Ying; Wu, Han; Ren, Li-Jun; Zhang, Yu-Qi; Yao, Hai-Xia; Hu, Min-Biao; Wang, Wei

    2016-01-19

    In this work, we report the preparation of complex nano-objects by means of a stepwise self-assembly of two polymer-polyoxometalate hybrids (PPHs) in solution. The PPHs are designed and synthesized by tethering two linear poly(ε-caprolactone)s (PCL) of different molecular weights (MW) on a complex of a Wells-Dawson-type polyoxometalate (POM) cluster and its countraions. The higher MW PCL-POM self-assembled into nanosheets, while the lower MW PCL-POM assembled into nanotubes just by altering the ratio of water in the DMF-water mixed solvent system. The two nano-objects have a similar membrane structure in which a PCL layer is sandwiched by the two POM-based complex layers. The PCL layer in the nanosheets is semicrystalline, while the PCL layer in the nanotubes is amorphous. We further exploited this MW-dependence to self-assemble the nanotubes on the nanosheet edges to create complex tube-graft-sheet nano-objects. We found that the nanotubes nucleate on the four {110} faces of the PCL crystal and then further grow along the crystallographic b-axis of the PCL crystal. Our findings offer hope for the further development of nano-objects with increasing complexity.

  8. Polyoxometalate-based eight-connected self-catenated network and fivefold interpenetrating framework

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiming; Liu, Jia; Li, Yangguang; Yao, Shuang; Wang, Enbo; Wang, Xinlong

    2010-01-01

    Two entangled compounds [(bpy) 6Cu I6Cl 3(Mo VW 5O 19)] ( 1) and [(bpy) 7Cu I7Cl 2(BW 12O 40)]·H 2O ( 2) (bpy=4,4'-bipyridine), have been successfully synthesized under hydrothermal conditions and characterized by element analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction analyses. Compound 1 represents the first eight-connected self-penetrating network constructed from cuprous chloride clusters [Cu 6Cl 3] and Lindquist-type polyoxoanions. Compound 2 exhibits an interesting fivefold interpenetrating network consisting of Keggin polyoxoanions and Cu +-metal-organic framework. Crystal data of the two compounds are following: 1, triclinic, P1¯, a=11.502(2) Å, b=13.069(3) Å, c=13.296(3) Å, α=90.55(3)°, β=113.74(3)°, γ=110.48(3)°, Z=1; 2, triclinic, P1¯, a=12.341(3) Å, b=13.119(3) Å, c=15.367(3) Å, α=99.12(3)°, β=90.53(3)°, γ=104.49(3)°, Z=1.

  9. Can Electron-rich Oxygen (O2-) Withdraw Electrons from Metal Centers? -A DFT Study on Oxoanion-caged Polyoxometalates.

    PubMed

    Takazaki, Aki; Eda, Kazuo; Osakai, Toshiyuki; Nakajima, Takahito

    2017-09-19

    The answer to the question "Can electron-rich oxygen (O2-) withdraw electrons from metal centers?" is seemingly simple, but "how the electron population on the M atom behaves when the O-M distance changes" is a matter of controversy. A case study has been conducted for Keggin-type polyoxometalate (POM) complexes, and the first-principles electronic structure calculations were carried out not only for real POM species but also for "hypothetical" ones whose hetero atom was replaced with a point charge. From the results of natural population analysis, it was proved that even an electron-rich O2-, owing to its larger electronegativity as a neutral atom, withdraws electrons when electron redistribution occurs by the change of the bond length. In the case where O2- coexists with a cation having a large positive charge (e.g., 5+(O2-)4 = [PO4]3-), the gross electron population (GEP) on the M atom seemingly increases as the O atom comes closer, but this increment in GEP is not due to the role of the O atom but due to a coulombic effect of the positive charge located on the cation. Furthermore, it was suggested that not GEP but net electron population (NEP) should be responsible for the redox properties.

  10. A novel iron-containing polyoxometalate heterogeneous photocatalyst for efficient 4-chlorophennol degradation by H2O2 at neutral pH

    NASA Astrophysics Data System (ADS)

    Zhai, Qian; Zhang, Lizhong; Zhao, Xiufeng; Chen, Han; Yin, Dongju; Li, Jianhui

    2016-07-01

    An iron-containing polyoxometalate (FeШLysSiW) was synthesized from ferric chloride (FeIII), lysine (Lys) and silicotungstic acid (SiW), and characterized using ICP-AES, TG, FT-IR, UV-vis DRS, XRD and SEM. The chemical formula of FeШLysSiW was determined as [Fe(H2O)5(C6H14N2O2)]HSiW12O40·8H2O, with Keggin-structured SiW12O404- heteropolyanion and lysine moiety. As a heterogeneous catalyst, the as prepared FeШLysSiW showed good performance in the degradation of 4-chlorophenol by H2O2 in both the dark and irradiated systems. Under the conditions of 4-chlorophenol 100 mg/L, FeШLysSiW 1.0 g/L, H2O2 20 mmol/L and pH 6.5, 4-chlorophenol could be completely degraded in ca. 40 min in the dark and ca. 15 min upon irradiation. Prolonging the reaction time to 3 h, the TOC removal reached to ca. 71.3% in the dark and ca. 98.8% under irradiation. The catalytic activity of FeШLysSiW stems from synergetic effect of ferric iron and SiW12O404- in the catalyst, corresponding to Fenton-like catalysis and photocatalysis, respectively. The enhanced degradation of 4-CP under irradiation is due to the simultaneous oxidation of 4-CP through the Fenton-like and photocatalytic processes. The high catalytic activity of FeШLysSiW is also strongly related to the chemisorption of H2O2 on FeШLysSiW surface by hydrogen bonding, which promotes both the Fenton-like and photocatalytic processes.

  11. Multinuclear diffusion NMR spectroscopy and DFT modeling: a powerful combination for unraveling the mechanism of phosphoester bond hydrolysis catalyzed by metal-substituted polyoxometalates.

    PubMed

    Luong, Thi Kim Nga; Shestakova, Pavletta; Mihaylov, Tzvetan T; Absillis, Gregory; Pierloot, Kristine; Parac-Vogt, Tatjana N

    2015-03-09

    A detailed reaction mechanism is proposed for the hydrolysis of the phosphoester bonds in the DNA model substrate bis(4-nitrophenyl) phosphate (BNPP) in the presence of the Zr(IV)-substituted Keggin type polyoxometalate (Et2NH2)8[{α-PW11O39Zr(μ-OH)(H2O)}2]⋅7 H2O (ZrK 2:2) at pD 6.4. Low-temperature (31)P DOSY spectra at pD 6.4 gave the first experimental evidence for the presence of ZrK 1:1 in fast equilibrium with ZrK 2:2 in purely aqueous solution. Moreover, theoretical calculations identified the ZrK 1:1 form as the potentially active species in solution. The reaction intermediates involved in the hydrolysis were identified by means of (1)H/(31)P NMR studies, including EXSY and DOSY NMR spectroscopy, which were supported by DFT calculations. This experimental/theoretical approach enabled the determination of the structures of four intermediate species in which the starting compound BNPP, nitrophenyl phosphate (NPP), or the end product phosphate (P) is coordinated to ZrK 1:1. In the proposed reaction mechanism, BNPP initially coordinates to ZrK 1:1 in a monodentate fashion, which results in hydrolysis of the first phosphoester bond in BNPP and formation of NPP. EXSY NMR studies showed that the bidentate complex between NPP and ZrK 1:1 is in equilibrium with monobound and free NPP. Subsequently, hydrolysis of NPP results in P, which is in equilibrium with its monobound form.

  12. Bridging the gap between solution and solid state studies in polyoxometalate chemistry: Discovery of a familiy of [V1M17]-based cages encapsulating two {VO4} moieties

    SciTech Connect

    Miras, H.; Long, D. L.; Kogerler, P; Cronin, L.

    2007-11-02

    A family of polyoxometalates with the composition [H2V3M17O62](6-) features a Dawson-like architecture containing two tetrahedral {l_brace}VVO4{r_brace} templates rather than main group hetero-anions ({l_brace}PO4{r_brace} or {l_brace}SO4{r_brace} etc.) typically associated with classical heteropolyacids, situated within a mixed-metal {l_brace}MVI17VIVO54{r_brace} cage and these clusters were first discovered using mass spectrometry.

  13. Thermochromic and solvatochromic properties of Lindqvist polyoxometalates.

    PubMed

    Herrmann, S; Margraf, J T; Clark, T; Streb, C

    2015-09-14

    The thermochromic and solvatochromic properties of Lindqvist metal oxide clusters [V(x)M(6-x)O19](n-) (x = 0, 1, 2, M = Mo, W) are reported. The cluster anions show pronounced changes of their electronic structure depending on their chemical environment (e.g. solvent polarity, temperature). These are rationalized using experimental and theoretical methods. A combined density functional theory and (51)V-NMR study suggests that temperature-dependent changes in the structural dynamics of the metal oxide framework are the underlying cause for the observed thermochromism. The results might open new avenues for the design of molecular optical sensors.

  14. Trilacunary A-beta-Keggin tungstogermanates and -silicates functionalized with phenyltin(IV) electrophiles.

    PubMed

    Reinoso, Santiago; Piedra-Garza, Luis Fernando; Dickman, Michael H; Praetorius, Antonia; Biesemans, Monique; Willem, Rudolph; Kortz, Ulrich

    2010-01-07

    The first organic derivative of a beta-Keggin tungstogermanate, the monomeric Keggin anion [{(C(6)H(5))Sn(OH)}(3)(A-beta-GeW(9)O(34))](4-) (1), was the only species isolated from the reaction of (C(6)H(5))SnCl(3) with Na(10)[A-beta-GeW(9)O(34)] in water, whereas the Si-analogue [{(C(6)H(5))Sn(OH)}(3)(A-beta-SiW(9)O(34))](4-) (2) and two dimeric tungstosilicates, the unprecedented species [{(C(6)H(5))Sn(A-beta-H(3)SiW(9)Sn(2)O(37))}(2)O(2)](8-) (3) and the known sandwich-type polyanion [{(C(6)H(5))Sn(OH)}(3)(A-beta-H(3)SiW(9)O(34))(2)](8-) (4), were isolated starting from [A-beta-SiW(9)O(34)](10-). The novel polyanion 3 can be described as the product of a double Sn-C hydrolysis followed by condensation of two subunits of 2 through double Sn-O-Sn bridge formation. Solid-state characterization has been carried out by infrared spectroscopy, thermogravimetry and single-crystal X-ray diffraction, representing the first structural analysis for 4. A full solution multinuclear NMR ((1)H, (13)C, (117)Sn, and (183)W) and solid-state (117)Sn CP-MAS NMR study enabled full characterization of 1. A weak 1-dimensional polyanion association through (Sn)O-HO(t) hydrogen contacts involving one of the protonated bridging O atoms of the (C(6)H(5))(3)Sn(3)O(12) corner-shared triad is observed for 1 by X-ray diffraction, resulting in a local C(s) pseudosymmetry for the Sn centers detected by solid-state (117)Sn NMR spectroscopy.

  15. Polyoxometalate-based eight-connected self-catenated network and fivefold interpenetrating framework

    SciTech Connect

    Zhang Zhiming; Liu Jia; Li Yangguang; Yao Shuang; Wang Enbo; Wang Xinlong

    2010-01-15

    Two entangled compounds [(bpy){sub 6}Cu{sup I}{sub 6}Cl{sub 3}(Mo{sup V}W{sub 5}O{sub 19})] (1) and [(bpy){sub 7}Cu{sup I}{sub 7}Cl{sub 2}(BW{sub 12}O{sub 40})].H{sub 2}O (2) (bpy=4,4'-bipyridine), have been successfully synthesized under hydrothermal conditions and characterized by element analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction analyses. Compound 1 represents the first eight-connected self-penetrating network constructed from cuprous chloride clusters [Cu{sub 6}Cl{sub 3}] and Lindquist-type polyoxoanions. Compound 2 exhibits an interesting fivefold interpenetrating network consisting of Keggin polyoxoanions and Cu{sup +}-metal-organic framework. Crystal data of the two compounds are following: 1, triclinic, P1-bar, a=11.502(2) A, b=13.069(3) A, c=13.296(3) A, alpha=90.55(3){sup o}, beta=113.74(3){sup o}, gamma=110.48(3){sup o}, Z=1; 2, triclinic, P1-bar, a=12.341(3) A, b=13.119(3) A, c=15.367(3) A, alpha=99.12(3){sup o}, beta=90.53(3){sup o}, gamma=104.49(3){sup o}, Z=1. - Graphical abstract: Compound 1 is the POM-based unprecedented eight-connected self-penetrating organic-inorganic hybrid network constructed from the cuprous chloride clusters [Cu{sub 6}Cl{sub 3}], Lindquist-type polyoxoanions [Mo{sup V}W{sub 5}O{sub 19}], and the 4,4'-bipyridine ligands.

  16. Atom-precise polyoxometalate-ag2 s core-shell nanoparticles.

    PubMed

    Li, Xiao-Yu; Tan, Yuan-Zhi; Yu, Kai; Wang, Xing-Po; Zhao, Ya-Qin; Sun, Di; Zheng, Lan-Sun

    2015-06-01

    Atomically precise polyoxometalate-Ag2 S core-shell nanoparticles were generated in a top-down approach under solvothermal conditions and structurally confirmed by X-ray single-crystal diffraction as an interesting core-shell structure comprising an in situ generated Mo6 O22 (8-) polyoxometalate core and a mango-like Ag58 S38 shell. This result demonstrates the possibility to integrate polyoxometalate and Ag2 S nanoparticles into a core-shell heteronanostructure with precisely controlled atomical compositions of both core and shell. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. In situ fabrication and electrochemical behavior of amino acid polyoxometalate nanoparticles-embedded microcapsules.

    PubMed

    Fan, Dawei; Deng, Yongming; Hao, Jingcheng

    2010-11-01

    Amino acid polyoxometalate nanoparticles-embedded microcapsules were in situ fabricated by layer-by-layer (LbL) self-assembly method [polyoxometalate, H3PMo12O40·nH2O (PMo12); amino acid, glycine (Gly)]. The morphology of the obtained microcapsules was characterized by transmission electron microscopy and scanning electron microscopy. The electrochemical behavior of the amino acid polyoxometalate nanoparticles-embedded microcapsules was studied by cyclic voltammetry. The microcapsules show the pH-dependent properties, indicating that the pH of solution plays an important role in the electrochemical behavior of heteropolyanions.

  18. Synthesis and photochromic property of nanosized amino acid polyoxometalate compounds

    NASA Astrophysics Data System (ADS)

    Sun, Dehui; Zhang, Jilin; Ren, Huijuan; Cui, Zhenfeng

    2009-07-01

    A series of novel nanosized amino acid-polyoxometalate compounds were successfully synthesized using a low temperature solid-state chemical reaction method. Their compositions, structures, morphologies, photochromic properties were characterized by ICP-AES/MS, TG/DTA, FTIR, XRD, SEM and UV-Vis diffuse reflectance spectra (DRS), respectively. The elemental analysis results showed that the compounds ((HThr)7PMo12O42•4H2O, (HTyr)7PMo12O42Â.5H2O, (HSer)7PMo12O42•5H2O and (HGlu)7PMo12O42•4H2O) were obtained. The analyses of the TG/DTA, XRD and FTIR confirmed that the four compounds are new phases different from the corresponding reactants and they are composed of the polyoxometalate anions and the corresponding protonated amino acids, respectively. Observation of the SEM revealed that the particle shape (e.g. (HThr)7PMo12O42Â.4H2O nanoplates, (HTyr)7PMo12O42•5H2O nanorods, (HSer)7PMo12O42•5H2O and (HGlu)7PMo12O42•4H2O nanoparticles) depended strongly on the structures of amino acids. This implied that the amino acids can play a structural template agent role in synthesis of the Silverton-type polyoxometalate compounds. After irradiated with ultraviolet light, these samples all exhibited photochromism. Their photochromic mechanism may be explained based on Yamase's photochromic model. These photochromic compounds could be applied to the field of photosensitive materials.

  19. Surface and bulk aspects of mixed oxide catalytic nanoparticles: oxidation and dehydration of CH(3)OH by polyoxometallates.

    PubMed

    Nakka, Lingaiah; Molinari, Julie E; Wachs, Israel E

    2009-10-28

    The molecular structures and surface chemistry of mixed metal oxide heteropolyoxo vanadium tungstate (H(3+x)PW(12-x)V(x)O(40) with x = 0, 1, 2, and 3) Keggin nanoparticles (NPs), where vanadium is incorporated into the primary Keggin structure, and supported VO(x) on tungstophosphoric acid (TPA, H(3)PW(12)O(40)), where vanadium is present on the surface of the Keggin unit, were investigated with solid-state magic angle spinning (51)V NMR, FT-IR, in situ Raman, in situ UV-vis, CH(3)OH temperature-programmed surface reaction (TPSR), and steady-state methanol oxidation. The incorporated VO(x) unit possesses one terminal V horizontal lineO bond, four bridging V-O-W/V bonds, and one long V-O-P bond in the primary Keggin structure, and the supported VO(x) unit possesses a similar coordination in the secondary structure under ambient conditions. The specific redox reaction rate for VO(x) in the Keggin primary structure is comparable to that of bulk V(2)O(5) and the more active supported vanadium oxide catalysts. The specific acidic reaction rate for the WO(x) in the TPA Keggin, however, is orders of magnitude greater than found for bulk WO(3), supported tungsten oxide catalysts, and even the highly acidic WO(3)-ZrO(2) catalyst synthesized by coprecipitation of ammonium metatungstate and ZrO(OH)(2). From CH(3)OH-TPSR and in situ Raman spectroscopy it was found that incorporation of vanadium oxide into the primary Keggin structure is also accompanied by the formation of surface VO(x) species at secondary sites on the Keggin outer surface. Both CH(3)OH-TPSR and steady-state methanol oxidation studies demonstrated that the surface VO(x) species on the Keggin outer surface are significantly less active than the VO(x) species incorporated into the primary Keggin structure. The presence of the less active surface VO(x) sites in the Keggins, thus, decreases the specific reaction rates for both methanol oxidation and methanol dehydration. During methanol oxidation/dehydration (O(2

  20. Self-assembly of lacunary Dawson type polyoxometalates and poly(allylamine hydrochloride) multilayer films: photoluminescent and electrochemical behavior

    NASA Astrophysics Data System (ADS)

    Jiang, Min; Wang, Enbo; Wang, Xiuli; Wu, Aiguo; Kang, Zhenhui; Lian, Suoyuan; Xu, Lin; Li, Zhuang

    2005-03-01

    Ultrathin multilayer films containing a lacunary Dawson type polyoxometalate (POM) cluster K 17[Ln(P 2Mo 17O 61) 2] (LnPMo, Ln = Eu, Tb) and poly(allylamine hydrochloride) have been prepared by electrostatic layer-by-layer self-assembly (ELSA) method. The multilayer films have been characterized by UV-vis absorption spectroscopy, ellipsometry and atomic force microscopy (AFM). The photoluminescent behavior of films at room temperature was investigated to show the Ln 3+ characteristic emission pattern. The occurrence of photoluminescent activity confirms the potential applications in creating luminescent materials. Additionally, the electrochemical behavior of multilayer films was studied and the growth of multilayer films can be observed.

  1. Biofunctionalization of Polyoxometalates with DNA Primers, Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products.

    PubMed

    Debela, Ahmed M; Ortiz, Mayreli; Beni, Valerio; Thorimbert, Serge; Lesage, Denis; Cole, Richard B; O'Sullivan, Ciara K; Hasenknopf, Bernold

    2015-12-01

    The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11 O39 {Sn(CH2 )2 CO}](8-) and [P2 W17 O61 {Sn(CH2 )2 CO}](6-) have been used to link to a 5'-NH2 terminated 21-mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM-labeled primers was demonstrated through hybridization with a surface-immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry.

    PubMed

    Zheng, Qi; Vilà-Nadal, Laia; Busche, Christoph; Mathieson, Jennifer S; Long, De-Liang; Cronin, Leroy

    2015-06-26

    By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HP(III)O3)2(H2O)2](8-), was isolated, in which the reaction of the two phosphite anions [HPO3](2-) within the {W18O56} cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two P(III) template moieties to form P(V) centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells-Dawson {W18O54} cluster. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry**

    PubMed Central

    Zheng, Qi; Vilà-Nadal, Laia; Busche, Christoph; Mathieson, Jennifer S; Long, De-Liang; Cronin, Leroy

    2015-01-01

    By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HPIIIO3)2(H2O)2]8−, was isolated, in which the reaction of the two phosphite anions [HPO3]2− within the {W18O56} cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two PIII template moieties to form PV centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells–Dawson {W18O54} cluster. PMID:26013548

  4. An unusual mono-substituted Keggin anion-chain based 3D framework with 24-membered macrocycles as linker units

    SciTech Connect

    Pang Haijun; Ma Huiyuan; Yu Yan; Yang Ming; Xun Ye; Liu Bo

    2012-02-15

    A new compound, [Cu{sup I}(H{sub 2}O)(Hbpp){sub 2}] Subset-Of {l_brace}[Cu{sup I}(bpp)]{sub 2}[PW{sub 11}Cu{sup II}O{sub 39}]{r_brace} (1) (bpp=1,3-bis(4-pyridyl)propane), has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. In compound 1, the unusual -A-B-A-B- array mono-substituted Keggin anion-chains and 24-membered (Cubpp){sub 2} cation-macrocycles are linked together to form a (2, 4) connected 3D framework with channels of ca. 9.784 Multiplication-Sign 7.771 A{sup 2} along two directions, in which the [Cu(H{sub 2}O)(Hbpp){sub 2}] coordination fragments as guest components are trapped. The photocatalytic experiments of compound 1 were performed, which show a good catalytic activity of compound 1 for photodegradation of RhB. Furthermore, the IR, TGA and electrochemical properties of compound 1 were investigated. - Graphical abstract: An unusual example of mono-substituted Keggin anion-chain based hybrid compound that possesses a 3D structure has been synthesized, which offers a feasible route for synthesis of such compounds. Highlights: Black-Right-Pointing-Pointer The first example of -A-B-A-B- array mono-substituted Keggin chain is observed. Black-Right-Pointing-Pointer An unusual three dimensional structure based mono-substituted Keggin anion-chains. Black-Right-Pointing-Pointer The photocatalysis and electrochemical properties of the title compound were studied.

  5. Five inorganic–organic hybrids based on Keggin polyanion [SiMo{sub 12}O{sub 40}]{sup 4−}: From 0D to 2D network

    SciTech Connect

    Yu, Xiao-Yang; Cui, Xiao-Bing; Lu, Jing; Luo, Yu-Hui; Zhang, Hong; Gao, Wei-Ping

    2014-01-15

    Five new inorganic–organic hybrids based on 4,4′-bipyridine and Keggin-type polyoxometalate [SiMo{sub 12}O{sub 40}]{sup 4−}, (SiMo{sub 12}O{sub 40})(H{sub 2}bipy){sub 2}·2H{sub 2}O (1), [Cu(Hbipy){sub 4}(HSiMo{sub 12}O{sub 40})(SiMo{sub 12}O{sub 40})](H{sub 2}bipy){sub 0.5}·7H{sub 2}O (2), [Cu{sub 2}(Hbipy){sub 6}(bipy)(SiMo{sub 12}O{sub 40}){sub 3}](Hbipy){sub 2}·6H{sub 2}O (3), [Cu(bipy){sub 2}(SiMo{sub 12}O{sub 40})](H{sub 2}bipy)·2H{sub 2}O (4) and [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}](SiMo{sub 12}O{sub 40})·13H{sub 2}O (5) (bipy=4,4′-bipyridine), have been hydrothermally synthesized. 1 consists of H{sub 2}bipy{sup 2+} and [SiMo{sub 12}O{sub 40}]{sup 4−} units. In 2, two [SiMo{sub 12}O{sub 40}]{sup 4−} are bridged by [Cu(Hbipy){sub 4}]{sup 6+} to form a [Cu(Hbipy){sub 4}(SiMo{sub 12}O{sub 40}){sub 2}]{sup 2−} dimmer. In 3, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as bidentated bridging ligands and monodentated auxiliary ligands connect [Cu{sub 2}(Hbipy){sub 6}(bipy)]{sup 8+} units into a 1D zigzag chain. In 4, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions bridge neighboring 1D [Cu(bipy){sub 2}]{sup 2+} double chains into a 2D extended layer. In 5, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as templates site alternately upon the grids from both sides of the square grid [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}]{sup 4+} layer. In addition, the electrochemical behaviors of 1, 3 and 4 and the photocatalysis property of 1 have been investigated. - Graphical abstract: Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been successfully generated. [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the structures of the five compounds. Display Omitted - Highlights: • Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been generated. • [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the five structures. • The electrochemical behaviors of 1, 3 and 4 have been

  6. A high fatigue resistant, photoswitchable fluorescent spiropyran-polyoxometalate-BODIPY single-molecule.

    PubMed

    Saad, Ali; Oms, Olivier; Dolbecq, Anne; Menet, Clotilde; Dessapt, Rémi; Serier-Brault, Hélène; Allard, Emmanuel; Baczko, Krystyna; Mialane, Pierre

    2015-11-18

    The tuning of the fluorescence through the activation of the photochromic part in an unprecedented covalent spiropyran-polyoxometalate-BODIPY tricomponent points out the high photofatigue resistance of such molecular switches.

  7. Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing.

    PubMed

    Clemente-Juan, Juan M; Coronado, Eugenio; Gaita-Ariño, Alejandro

    2012-11-21

    In this review we discuss the relevance of polyoxometalate (POM) chemistry to provide model objects in molecular magnetism. We present several potential applications in nanomagnetism, in particular, in molecular spintronics and quantum computing.

  8. Synthesis and crystal structure of two supramolecular compounds constructed from amantadine and polyoxometalate

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Huang, Kunlin; Pu, Zhifa; Gong, Yun; Li, Hui; Hu, Changwen

    2006-05-01

    Two organic-inorganic hybrid compounds based on amantadines and polyoxometalates formulated as (C 10H 18N) 4(H 2V 10O 28)·2DMF·2H 2O ( 1) and (C 10H 18N) 3(PMo 12O 40) ( 2), were synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR, UV and TGA. Compounds 1 and 2 consist of protonated amantadines together with different polyoxometalates, [H 2V 10O 28] 4- and [PMo 12O 40] 3-, respectively. There are hydrogen bonding interactions and electrostatic attractions between polyoxometalates and amantadines in 1 and 2. Polyoxometalates are linked through amantadines into a two-dimensional network via hydrogen bonds in the two compounds. The two-dimensional framework is further extended into supramolecular network by hydrophobic interaction of amantadines between adjacent layers. The crystal packing patterns of the two compounds reveal various supramolecular framework.

  9. Multifunctional polyoxometalates-modified upconversion nanoparticles: integration of electrochromic devices and antioxidants detection.

    PubMed

    Zhai, Yanling; Zhu, Chengzhou; Ren, Jiangtao; Wang, Erkang; Dong, Shaojun

    2013-03-25

    We report a novel design, based on a combination of lanthanide-doped upconversion nanoparticles and polyoxometalates, for electrically controlled fluorescence switches and sensitive detection of antioxidants in aqueous solution.

  10. Cationic D4R zinc phosphate-anionic polyoxometalate hybrids: synthesis, spectra, structure and catalytic studies.

    PubMed

    Kalita, Alok Ch; Roch-Marchal, Catherine; Murugavel, Ramaswamy

    2013-07-14

    A facile synthetic strategy for the generation of a new class of inorganic-organic-inorganic hybrids is reported. Replacement of labile DMSO ligands from the preformed Double-Four-Ring (D4R) zinc phosphate cluster [Zn(dipp){(CH3)2SO}]4 by the addition of 4-aminopyridine (4-ampyr) results in the isolation of another discrete D4R cluster [Zn(dipp)(4-ampyr)]4 (1), which forms a hydrogen-bonded framework in solid-state. If 1-methyl-4,4'-bipyridinium salts are employed instead, tetra-cationic D4R cluster [Zn(dipp)(L)]4[PF6]4 (2) and [Zn(dipp)(L)]4[ClO4]4 (3) (L = 1-methyl-4,4'-bipyridinium, dipp = 2,6-di-iso-propylphenylphosphate) are isolated. Compound 2 was reacted with three different polyoxometalates, [TBA]4[Mo8O26] (POM-1), [TBA]4[PMo11VO40] (POM-2), and [TBA]4[SiMo12O40] (POM-3) to obtain amorphous hybrids, [Zn(dipp)(L)]4[Mo8O26] (4), [Zn(dipp)(L)]4[PMo11VO40] (5), and [Zn(dipp)(L)]4[SiMo12O40] (6), respectively. All the hybrid materials have been characterized by analytical and spectroscopic studies. The molecular structure of 1 has also been determined by single-crystal XRD measurements. N2 gas sorption analyses show moderate BET surface area and also establish the mesoporous nature of the hybrids 4-6. The catalytic potential of hybrids 4, 5 and 6 has been explored towards epoxidation of cyclohexene.

  11. Human versus Robots in the Discovery and Crystallization of Gigantic Polyoxometalates

    PubMed Central

    Duros, Vasilios; Grizou, Jonathan; Xuan, Weimin; Hosni, Zied; Long, De‐Liang; Miras, Haralampos N.

    2017-01-01

    Abstract The discovery of new gigantic molecules formed by self‐assembly and crystal growth is challenging as it combines two contingent events; first is the formation of a new molecule, and second its crystallization. Herein, we construct a workflow that can be followed manually or by a robot to probe the envelope of both events and employ it for a new polyoxometalate cluster, Na6[Mo120Ce6O366H12(H2O)78]⋅200 H2O (1) which has a trigonal‐ring type architecture (yield 4.3 % based on Mo). Its synthesis and crystallization was probed using an active machine‐learning algorithm developed by us to explore the crystallization space, the algorithm results were compared with those obtained by human experimenters. The algorithm‐based search is able to cover ca. 9 times more crystallization space than a random search and ca. 6 times more than humans and increases the crystallization prediction accuracy to 82.4±0.7 % over 77.1±0.9 % from human experimenters. PMID:28649740

  12. Synthesis and characterization of two polyoxometalates consisting of different Cu-ligand hydrogen phosphate units

    NASA Astrophysics Data System (ADS)

    Yan, Jinshuang; Zhao, Xiaofang; Huang, Jiao; Gong, Kaining; Han, Zhangang; Zhai, Xueliang

    2014-03-01

    Two polyoxometalates [(Cu-mbpy)4(HPO4)2(H2O)2][PMo12O40]·H2O (1) and [(Cu-mbpy)6(HPO4)4][PW12O40]·4H2O (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl in 1; 5,5″-dimethyl-2,2'-dipyridyl in 2) have been synthesized and characterized by IR, X-ray powder diffraction, TG analysis and electrochemical property. The structural features of 1-2 are in their cationic moieties consisting of different linkages of [Cu-mbpy]2+ and HPO42- groups. In 1 four Cu-mbpy bridged by two HPO42- ions form a discrete cluster with an interesting octahedron of {Cu4P2}, while in 2 Cu-mbpy fragments are bridged by HPO42- ions into 1D structure consisting of trigonal bipyramidal polyhedra of {Cu3P2}. Photocatalytic experiments indicate that compounds 1 and 2 are actively photocatalytic for degradation of methyl orange in the presence of H2O2 under UV light irradiation.

  13. Synthesis of diamondoid lanthanide-polyoxometalate solids as tunable photoluminescent materials.

    PubMed

    Zhao, Wen-Feng; Zou, Chao; Shi, Lian-Xu; Yu, Jian-Can; Qian, Guo-Dong; Wu, Chuan-De

    2012-09-07

    The reaction between polyoxometalate (POM) [TBA](12)[WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] (TBA = tetrabutyl ammonium) and lanthanide (Ln) nitrate (Ln = La, Eu and Tb) in a mixed solvent of CH(3)CN and DMF yielded three noncentrosymmetric diamondoid Ln-POM solid materials, {[Ln(2)(DMF)(8)(H(2)O)(6)][ZnW(12)O(40)]}·4DMF (Ln-POM; Ln = La, Eu and Tb). In these compounds, the {ZnW(12)O(40)} unit, transferred from the metastable [WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] cluster, acts as a tetradentate ligand to connect with four Ln nodes, while the Ln ion links up two {ZnW(12)O(40)} units. These compounds generated interesting luminescence emissions that are dependent on the Ln ions and their ratios. White light emission was obtained by a doped approach with a rational ratio of the Eu(3+) and Tb(3+) ions.

  14. Noncovalent fabrication and tunable fusion of block copolymer-giant polyoxometalate hybrid micelles.

    PubMed

    Zhang, Liying; Li, Haolong; Wu, Lixin

    2014-09-21

    The block copolymers (BCs), as structure-directing agents, co-assembling with nanoscale inorganic additives is an important route to fabricate nanostructured hybrid materials. In this work, we present a facile approach to fabricate hybrid micelles composed of BCs and polyoxometalates (POMs), in which the POM clusters are premodified with the groups that can specifically interact with a certain BC block. A representative POM (NH4)42[Mo(132)O(372)(CH(3)COO)(30)(H2O)72] (Mo(132)) is chosen as the example and encapsulated with cationic molecules containing carboxyphenyl groups through electrostatic interactions, and then the resulting hybrid complex can further co-assemble with poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) through hydrogen bonding with the pyridine groups, which leads to the formation of hybrid micelles and the localization of Mo(132) in the micelle cores. The micelles exhibit a high stability despite time and dilution. Furthermore, the fusion of the micelles can be readily adjusted by varying the length of PS blocks, which is promising to be used in constructing polymer-POM hybrid materials with discrete or continuous hybrid domains. This work is based on the electrostatic premodification of POMs and thus its concept is generally suitable for the whole anionic POM system, which may create a large class of BC-POM nanocomposites with tunable structures.

  15. Functionalization of Krebs-type polyoxometalates with N,O-chelating ligands: a systematic study.

    PubMed

    Artetxe, Beñat; Reinoso, Santiago; San Felices, Leire; Vitoria, Pablo; Pache, Aroa; Martín-Caballero, Jagoba; Gutiérrez-Zorrilla, Juan M

    2015-01-05

    The first organic derivatives of 3d-metal-disubstituted Krebs-type polyoxometalates have been synthesized under mild bench conditions via straightforward replacement of labile aqua ligands with N,O-chelating planar anions on either preformed or in situ-generated precursors. Nine hybrid clusters containing carboxylate derivatives of five- or six-membered aromatic N-heterocycles as antenna ligands have been obtained as pure crystalline phases and characterized by elemental and thermal analyses, infrared spectroscopy, and single-crystal X-ray diffraction. They all show the general formula [{M(II)L(H2O)}2(WO2)2(B-β-XW9O33)2](n-) and can be classified as follows: 1-SbM, where L = 1H-imidazole-4-carboxylate (imc), X = Sb(III), n = 12, and M(II) = Mn, Co, Ni, Zn; 1-TeM, where L = imc, X = Te(IV), n = 10, and M(II) = Mn, Co; 2-SbNi, where L = 1H-pyrazole-3-carboxylate (pzc), X = Sb(III), n = 12, and M(II) = Ni; and 3-SbM, where L = pyrazine-2-carboxylate (pyzc), X =Sb(III), n = 12, and M(II) = Co, Zn. The 3d-metal-disubstituted tungstotellurate(IV) skeleton of compounds 1-TeM is unprecedented in polyoxometalate chemistry. The stability of these hybrid Krebs-type species in aqueous solution has been confirmed by (1)H NMR spectroscopy performed on the diamagnetic 1-SbZn and 3-SbZn derivatives. Our systematic study of the reactivity of disubtituted Krebs-type polyoxotungstates toward diazole-, pyridine-, and diazinecarboxylates demonstrates that organic derivatization is strongly dependent on the nature of the ligand, as follows: imc displays a "universal ligand" character, as functionalization takes place regardless of the external 3d metal and heteroatom; pzc and pyzc show selectivity toward specific 3d metals; pyridazine-3-carboxylate and pyrimidine-4-carboxylate promote partial decomposition of specific precursors, leading to [M(II)L2(H2O)2] complexes; and picolinate is inert under all conditions tested.

  16. Probing Polyoxometalate-Protein Interactions Using Molecular Dynamics Simulations.

    PubMed

    Solé-Daura, Albert; Goovaerts, Vincent; Stroobants, Karen; Absillis, Gregory; Jiménez-Lozano, Pablo; Poblet, Josep M; Hirst, Jonathan D; Parac-Vogt, Tatjana N; Carbó, Jorge J

    2016-10-17

    The molecular interactions between the Ce(IV) -substituted Keggin anion [PW11 O39 Ce(OH2 )4 ](3-) (CeK) and hen egg-white lysozyme (HEWL) were investigated by molecular dynamics simulations. The analysis of CeK was compared with the Ce(IV) -substituted Keggin dimer [(PW11 O39 )2 Ce](10-) (CeK2 ) and the Zr(IV) -substituted Lindqvist anion [W5 O18 Zr(OH2 )(OH)](3-) (ZrL) to understand how POM features such as shape, size, charge, or type of incorporated metal ion influence the POM⋅⋅⋅protein interactions. Simulations revealed two regions of the protein in which the CeK anion interacts strongly: cationic sites formed by Arg21 and by Arg45 and Arg68. The POMs chiefly interact with the side chains of the positively charged (arginines, lysines) and the polar uncharged residues (tyrosines, serines, aspargines) via electrostatic attraction and hydrogen bonding with the oxygen atoms of the POM framework. The CeK anion shows higher protein affinity than the CeK2 and ZrL anions, because it is less hydrophilic and it has the right size and shape for establishing interactions with several residues simultaneously. The larger, more negatively charged CeK2 anion has a high solvent-accessible surface, which is sub-optimal for the interaction, while the smaller ZrL anion is highly hydrophilic and cannot efficiently interact with several residues simultaneously. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Polyoxometalate-Modified Boron-Doped Diamond Electrodes

    NASA Astrophysics Data System (ADS)

    Kondo, Takeshi; Taniguchi, Yuichi; Yuasa, Makoto; Kawai, Takeshi

    2012-09-01

    Polyoxometalates were immobilized on a boron-doped diamond (BDD) surface modified by a photochemical modification method. The BDD surface was first modified with allyltriethylammonium bromide (ATAB) to form surface quaternary ammonium groups. The ATAB-BDD was then immersed in a phosphomolybdic acid (H3PMo12O40, denoted as PMo12) solution to fabricate PMo12-adsorbed ATAB-BDD (PMo12-ATAB-BDD). The electrostatic interaction between PMo12 and the quaternary ammonium group on ATAB-BDD is considered to be critical to the stable immobilization. Polyoxometalate-modified BDD was also fabricated from phosphonic-acid-terminated BDD. BDD was first modified with vinylphosphonic acid (VPA), followed by the reaction of the surface phosphonic acid groups with ammonium molybdate to generate a lacunary phosphomolybdic acid (PMox) group. Although the coverage of the PMox group on PMox-BDD was less than that of PMo12-ATAB-BDD, PMox-BDD was found to be more stable to potential cycling than PMo12-ATAB-BDD, indicating that covalent modification methods are effective for creating stable functional groups on diamond.

  18. Synthesis and crystal structure of 1D polyoxometalate-based composite compound, [{Gd(NMP) 6}(PMo 12O 40)] n (NMP= N-methyl-2-pyrrolidone)

    NASA Astrophysics Data System (ADS)

    Niu, Jing-Yang; Wei, Mei-Lin; Wang, Jing-Ping; Dang, Dong-Bin

    2003-07-01

    A novel compound, [{Gd(NMP) 6}(PMo 12O 40)] n, has been synthesized and characterized by IR, and UV spectroscopy, and single crystal X-ray structural analysis. It forms an unprecedented one-dimensional zigzag chain built from alternating polyanions and cationic units through Mo-O t-Gd-O t-Mo links in the crystal. In the compound, Gd 3+ is eight-coordinated with a bicapped trigonal prism geometry environment of oxygen atoms. The results of the single crystal X-ray diffraction analyses and IR are agreement and both show the metal cation units are coordinately bonded to the Keggin cluster. The UV spectrum of the title compound suggests that the compound is entirely dissociated in dilute solution.

  19. Electronic and relativistic contributions to ion-pairing in polyoxometalate model systems.

    PubMed

    Sures, Dylan J; Serapian, Stefano A; Kozma, Károly; Molina, Pedro I; Bo, Carles; Nyman, May

    2017-03-29

    Ion pairs and solubility related to ion-pairing in water influence many processes in nature and in synthesis including efficient drug delivery, contaminant transport in the environment, and self-assembly of materials in water. Ion pairs are difficult to observe spectroscopically because they generally do not persist unless extreme solution conditions are applied. Here we demonstrate two advanced techniques coupled with computational studies that quantify the persistence of ion pairs in simple solutions and offer explanations for observed solubility trends. The system of study, ([(CH3)4N](+),Cs)8[M6O19] (M = Nb,Ta), is a set of unique polyoxometalate salts whose water solubility increases with increasing ion-pairing, contrary to most ionic salts. The techniques employed to characterize Cs(+) association with [M6O19](8-) and related clusters in simple aqueous media are (133)Cs NMR (nuclear magnetic resonance) quadrupolar relaxation rate and PDF (pair distribution function) from X-ray scattering. The NMR measurements consistently showed more extensive ion-pairing of Cs(+) with the Ta-analogue than the Nb-analogue, although the electrostatics of the ions should be identical. Computational studies also ascertained more persistent Cs(+)-[Ta6O19] ion pairs than Cs(+)-[Nb6O19] ion pairs, and bond energy decomposition analyses determined relativistic effects to be the differentiating factor between the two. These distinctions are likely responsible for many of the unexplained differences between aqueous Nb and Ta chemistry, while they are so similar in the solid state. The X-ray scattering studies show atomic level detail of this ion association that has not been prior observed, enabling confidence in our structures for calculations of Cs-cluster association energies. Moreover, detailed NMR studies allow quantification of the number of Cs(+) associated with a single [Nb6O19](8-) or [Ta6O19](8-) anion which agrees with the PDF analyses.

  20. Polyoxometalate water oxidation catalysts and methods of use thereof

    DOEpatents

    Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

    2014-09-02

    Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

  1. Heterogeneous Catalysis of Polyoxometalate Based Organic-Inorganic Hybrids.

    PubMed

    Ren, Yuanhang; Wang, Meiyin; Chen, Xueying; Yue, Bin; He, Heyong

    2015-03-31

    Organic-inorganic hybrid polyoxometalate (POM) compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic-inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis.

  2. Polyoxometalates in Oxidative Delignification of Chemical Pulps: Effect on Lignin

    PubMed Central

    Bujanovic, Biljana; Ralph, Sally; Reiner, Richard; Hirth, Kolby; Atalla, Rajai

    2010-01-01

    Chemical pulps are produced by chemical delignification of lignocelluloses such as wood or annual non-woody plants. After pulping (e.g., kraft pulping), the remaining lignin is removed by bleaching to produce a high quality, bright paper. The goal of bleaching is to remove lignin from the pulp without a negative effect on the cellulose; for this reason, delignification should be performed in a highly selective manner. New environmentally-friendly alternatives to conventional chlorine-based bleaching technologies (e.g., oxygen, ozone, or peroxide bleaching) have been suggested or implemented. In an attempt to find inorganic agents that mimic the action of highly selective lignin-degrading enzymes and that can be applicable in industrial conditions, the researchers have focused on polyoxometalates (POMs), used either as regenerable redox reagents (in anaerobic conditions) or as catalysts (in aerobic conditions) of oxidative delignification. The aim of this paper is to review the basic concepts of POM delignification in these two processes.

  3. Resonance tunneling electron-vibrational spectroscopy of polyoxometalates.

    PubMed

    Dalidchik, F I; Kovalevskii, S A; Balashov, E M

    2017-05-21

    The tunneling spectra of the ordered monolayer films of decamolybdodicobaltate (DMDC) compounds deposited from aqueous solutions on HOPG were measured by scanning tunnel microscopy in air. The DMDC spectra, as well as the tunneling spectra of other polyoxometalates (POMs), exhibit well-defined negative differential resistances (NDRs). The mechanism of formation of these spectral features was established from the collection of revealed NDR dependences on the external varying parameters and found to be common to all systems exhibiting Wannier-Stark localization. A model of biresonance tunneling was developed to provide an explanation for the totality of experimental data, both the literature and original, on the tunneling POM probing. A variant of the tunneling electron-vibrational POM spectroscopy was proposed allowing the determination of the three basic energy parameters-energy gaps between the occupied and unoccupied states, frequencies of the vibrational transitions accompanying biresonance electron-tunneling processes, and electron-vibrational interaction constants on the monomolecular level.

  4. Cationic cure kinetics of a polyoxometalate loaded epoxy nanocomposite

    SciTech Connect

    Anderson, Benjamin J.

    2012-08-06

    The reaction cure kinetics of a novel polyoxometalate (POM) loaded epoxy nanocomposite is described. The POM is dispersed in the epoxy resin up to volume fractions of 0.1. Differential scanning calorimetry measurements show the cure of the epoxy resin to be sensitive to the POM loading. A kinetics study of the cure exotherm confirms that POM acts as a catalyst promoting cationic homopolymerization of the epoxy resin. The cure reaction is shown to propagate through two cure regimes. A fast cure at short time is shown to be propagation by the activated chain end (ACE) mechanism. A slow cure at long time is shown to be propagation by the activated monomer (AM) mechanism. The activation energies for the fast and slow cure regimes agree well with other epoxy based systems that have been confirmed to propagate by the ACE and AM mechanisms.

  5. Formation of gold nanoparticles via a thiol functionalized polyoxometalate.

    PubMed

    Hegde, Shweta; Joshi, Satyawati; Mukherjee, Tulsi; Kapoor, Sudhir

    2013-05-01

    A useful method for the synthesis of Au nanoparticles is presented. The synthesis of Au nanoparticles with various morphologies was carried out at room temperature using gamma radiolysis and NaBH4 reduction of HAuCl4 in N,N'-dimethylformamide:water solutions containing polyoxometalate (POM). The results demonstrated that by controlling the rate of reduction and ratio of DMF and water, metal particle size and shape can be further tailored. It is shown that gold nanoparticles with controllable size can be synthesized. In principle, the general finding of this work can be extended to other transition/noble metal nanoparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids

    PubMed Central

    Ren, Yuanhang; Wang, Meiyin; Chen, Xueying; Yue, Bin; He, Heyong

    2015-01-01

    Organic–inorganic hybrid polyoxometalate (POM) compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic–inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis. PMID:28788017

  7. Pharmacokinetics of Anti-HBV Polyoxometalate in Rats

    PubMed Central

    Qi, Yanfei; Li, Jinhua; Song, Xiuling; Li, Li; Yin, Dehui; Xu, Kun; Li, Juan

    2014-01-01

    Polyoxometalates are non-nucleoside analogs that have been proven to exhibit broad-spectrum antiviral activity. In particular, Cs2K4Na[SiW9Nb3O40].H2O 1 shows low toxicity and high activity against HBV. The preclinical pharmacokinetics of Compound 1 in rats were characterized by establishing and applying inductively coupled plasma-mass spectrometry method to determine the concentration of W in plasma, urine, feces, bile and organ samples. The quantitative ICP-MS method demonstrated good sensitivity and application in the pharmacokinetics study of polyoxometalates. The pharmacokinetic behavior of Compound 1 after intravenous or oral administration fit a two-compartment model. Tmax ranges from 0.1 h to 3 h and the T1/2 of Compound 1 is between 20 h and 30 h. The absolute bioavailability of Compound 1 at 45, 180 and 720 mg/kg groups were 23.68%, 14.67% and 11.93%, respectively. The rates of plasma protein binding of Compound 1 at 9, 18 and 36 mg/ml of Compound 1 are 62.13±9.41%, 71.20±24.98% and 49.00±25.59%, respectively. Compound 1 was widely distributed throughout the body, and high levels of compound 1 were found in the kidney and liver. The level of Compound 1 in excretion was lower: 30% for urine, 0.28% for feces and 0.42% for bile, respectively. For elaborate pharmacokinetic characteristics to be fully understood, the metabolism of Compound 1 needs to be studied further. PMID:24921932

  8. Pharmacokinetics of anti-HBV polyoxometalate in rats.

    PubMed

    Wang, Juan; Qu, Xiaofeng; Qi, Yanfei; Li, Jinhua; Song, Xiuling; Li, Li; Yin, Dehui; Xu, Kun; Li, Juan

    2014-01-01

    Polyoxometalates are non-nucleoside analogs that have been proven to exhibit broad-spectrum antiviral activity. In particular, Cs2K4Na[SiW9Nb3O40].H2O 1 shows low toxicity and high activity against HBV. The preclinical pharmacokinetics of Compound 1 in rats were characterized by establishing and applying inductively coupled plasma-mass spectrometry method to determine the concentration of W in plasma, urine, feces, bile and organ samples. The quantitative ICP-MS method demonstrated good sensitivity and application in the pharmacokinetics study of polyoxometalates. The pharmacokinetic behavior of Compound 1 after intravenous or oral administration fit a two-compartment model. Tmax ranges from 0.1 h to 3 h and the T1/2 of Compound 1 is between 20 h and 30 h. The absolute bioavailability of Compound 1 at 45, 180 and 720 mg/kg groups were 23.68%, 14.67% and 11.93%, respectively. The rates of plasma protein binding of Compound 1 at 9, 18 and 36 mg/ml of Compound 1 are 62.13±9.41%, 71.20±24.98% and 49.00±25.59%, respectively. Compound 1 was widely distributed throughout the body, and high levels of compound 1 were found in the kidney and liver. The level of Compound 1 in excretion was lower: 30% for urine, 0.28% for feces and 0.42% for bile, respectively. For elaborate pharmacokinetic characteristics to be fully understood, the metabolism of Compound 1 needs to be studied further.

  9. A highly stable polyoxometalate-based metal-organic framework with an ABW zeolite-like structure.

    PubMed

    Li, Xiao-Xin; Shen, Feng-Cui; Liu, Jiang; Li, Shun-Li; Dong, Long-Zhang; Fu, Qiang; Su, Zhong-Min; Lan, Ya-Qian

    2017-09-05

    A novel polyoxometalate-based metal-organic framework (POMOF) with an ABW network, NENU-601, was synthesized in situ. To the best of our knowledge, this is the first POMOF with a zeolite-like structure, which was designed by regulating the length and angle of mixed ligands and rationally choosing suitable Polyoxometalates (POMs) as nodes.

  10. Two proton-conductive hybrids based on 2-(3-pyridyl)benzimidazole molecules and Keggin-type heteropolyacids

    SciTech Connect

    Wei, Mei-Lin Wang, Yu-Xia; Wang, Xin-Jun

    2014-01-15

    Two proton-conductive organic/inorganic complexes were constructed by Keggin-type heteropolyacids and 2-(3-pyridyl)benzimidazole molecules. Single-crystal X-ray diffraction analyses revealed that two complexes crystallized in the monoclinic space group P2{sub 1}/c, exhibited different unit cell parameters, and presented different hydrogen-bonded networks constructed by 2-(3-pyridyl)benzimidazole molecules, [PMo{sub 12}O{sub 40}]{sup 3−} anions and solvent molecules. The results of thermogravimetric analyses suggest that two supramolecular complexes have different thermal stability based on the different hydrogen-bonded networks. Two complexes at 100 °C under 35–98% relative humidity showed a good proton conductivity of about 10{sup −3} S cm{sup −1}. The proton conductivities of two complexes under 98% relative humidity both increase on a logarithmic scale with temperature range from 25 to 100 °C. At 100 °C, both complexes showed poor proton conductivities of 10{sup −8}–10{sup −9} S cm{sup −1} under acetonitrile or methanol vapor. - Graphical abstract: Two molecular hybrids constructed by Keggin-type heteropolyacids and 2-(3-pyridyl)benzimidazole molecules showed good proton conductivities of 10{sup −3} S cm{sup −1} at 100 °C under 35–98% relative humidity. Display Omitted - Highlights: • 2-(3-Pyridyl)benzimidazole could form hydrogen bonds via the N–H groups. • Heteropolyacids have suitable characteristics to be used excellent proton conductors. • Two proton-conductive hybrids based on Keggin HPAs and 3-PyBim were constructed. • The structures were determined by using single-crystal X-ray diffraction data. • They showed good proton conductivities of 10{sup −3} S cm{sup −1} at 100 °C under 35–98% RH.

  11. Template-free polyoxometalate-assisted synthesis for ZnO hollow spheres

    SciTech Connect

    Li Qiuyu; Wang Enbo; Li Siheng; Wang Chunlei; Tian Chungui; Sun Guoying; Gu Jianmin; Xu Rui

    2009-05-15

    ZnO hollow spheres with diameters ranging from 400 to 600 nm and the thickness of shell approximate 80 nm were synthesized by a simple polyoxometalate-assisted solvothermal route without using any templates. The effect of polyoxometalate concentration, reaction time and temperature on the formation of the hollow spheres was investigated. The results indicated that the hollow spheres were composed of porous shells with nanoparticles and polyoxometalate play a key role in controlling morphology of ZnO. A possible growth mechanism based on polyoxometalate-assisted assembly and slow Ostwald ripening dissolution in ethanol solution is tentatively proposed. In addition, the room temperature photoluminescence spectrum showed that the ZnO hollow spheres exhibit exciting emission features with wide band covering nearly all the visible region. - Graphical abstract: ZnO hollow spheres with porous shell were synthesized by a one-step polyoxometalate-assisted solvothermal route at low temperature. Room temperature photoluminescence spectrum of the ZnO hollow spheres exhibits exciting emission features with a broad band covering nearly all the visible region.

  12. Delignification of eucalypt kraft pulp with manganese-substituted polyoxometalate assisted by fungal versatile peroxidase.

    PubMed

    Marques, Gisela; Gamelas, José A F; Ruiz-Dueñas, Francisco J; del Rio, José C; Evtuguin, Dmitry V; Martínez, Angel T; Gutiérrez, Ana

    2010-08-01

    Oxidation of the manganese-substituted polyoxometalate [SiW(11)Mn(II)(H(2)O)O(39)](6-) (SiW(11)Mn(II)) to [SiW(11)Mn(III)(H(2)O)O(39)](5-) (SiW(11)Mn(III)), one of the most selective polyoxometalates for the kraft pulp delignification, by versatile peroxidase (VP) was studied. First, SiW(11)Mn(II) was demonstrated to be quickly oxidized by VP at room temperature in the presence of H(2)O(2) (K(m)=6.4+/-0.7 mM and k(cat)=47+/-2s(-1)). Second, the filtrate from eucalypt pulp delignification containing reduced polyoxometalate was treated with VP/H(2)O(2), and 95-100% reoxidation was attained. In this way, it was possible to reuse the liquor from a first SiW(11)Mn(III) stage for further delignification, in a sequence constituted by two polyoxometalate stages, and a short intermediate step consisting of the addition of VP/H(2)O(2) to the filtrate for SiW(11)Mn(II) reoxidation. When the first ClO(2) stage of a conventional bleaching sequence was substituted by the two-stage delignification with polyoxometalate (assisted by VP) a 50% saving in ClO(2) was obtained for similar mechanical strength of the final pulp. (c) 2010 Elsevier Ltd. All rights reserved.

  13. Adjacency of molybdenum redox sites and the oxidation of butene

    SciTech Connect

    Racine, B.N.; Sorensen, C.M.; Weber, R.S. )

    1993-08-01

    The authors have attempted to determine the structure sensitivity of C-H activation and oxygen insertion during the oxidation of 1-butene by measuring how the rates of the reactions depend on variations in the sizes of very small ensembles of redox centers in a catalyst. The authors have employed polyoxometalate cluster compounds in which 3 or 12 of the tungsten ions initially present in a Keggin framework were replaced with molybdenum ions. As in previous work with methanol oxidation, the catalyst derived from the parent Keggin anion, [PW[sub 12]O[sub 40

  14. Polyoxometalate-mediated electron transfer-oxygen transfer oxidation of cellulose and hemicellulose to synthesis gas.

    PubMed

    Sarma, Bidyut Bikash; Neumann, Ronny

    2014-08-01

    Terrestrial plants contain ~70% hemicellulose and cellulose that are a significant renewable bioresource with potential as an alternative to petroleum feedstock for carbon-based fuels. The efficient and selective deconstruction of carbohydrates to their basic components, carbon monoxide and hydrogen, so called synthesis gas, is an important key step towards the realization of this potential, because the formation of liquid hydrocarbon fuels from synthesis gas are known technologies. Here we show that by using a polyoxometalate as an electron transfer-oxygen transfer catalyst, carbon monoxide is formed by cleavage of all the carbon-carbon bonds through dehydration of initially formed formic acid. In this oxidation-reduction reaction, the hydrogen atoms are stored on the polyoxometalate as protons and electrons, and can be electrochemically released from the polyoxometalate as hydrogen. Together, synthesis gas is formed. In a hydrogen economy scenario, this method can also be used to convert carbon monoxide to hydrogen.

  15. Capillary electrophoretic determination of phosphate based on the formation of a Keggin-type [PMo12O40]3- complex.

    PubMed

    Nakashima, Y; Goto, T; Kitazumi, I; Himeno, S

    2001-10-01

    Based on the formation of a Keggin-type [PMo12O40]3- complex, a sensitive capillary electrophoresis (CE) method was developed for the determination of P(V) with direct UV detection at 220 nm. A mixture of alpha- and beta-Keggin-type [PMo12O40]3- complexes was readily formed in a sample solution consisting of a trace amount of P(V), 2.5 mM Mo(VI), 0.050 M p-C6H3(CH3)-2-SO3H (XSA), and 60% v/v CH3CN. When a 0.05 M HCl and 60% v/v CH3CN solution was used as a migration electrolyte, the Keggin complexes exhibited a sharp and well-defined peak in the electropherogram. The peak area was linearly dependent on the P(V) concentration in the range of 5 x 10(-7)-5 x 10(-5) M; a detection limit of 1 x 10(-7) M was achieved. In comparison with indirect UV detection, the direct UV detection is about ten times more sensitive, because the Keggin complexes possess high molar absorptivities. The developed CE method was applied to the determination of P(V) in river water, and the results were in good agreement with those obtained by ion chromatography (IC) and colorimetry (COL) based on the formation of mixed-valence heteropoly blue species.

  16. A novel detection of hydrogen peroxide based on a luminescent polyoxometalate.

    PubMed

    Wang, Bin; Meng, Rui-Qi; Bi, Li-Hua; Wu, Li-Xin

    2011-05-21

    In this paper, we attempt to construct a simple and sensitive detection method for hydrogen peroxide based on reversible colour change and luminescence switching modulated by the electrochemical stimulation and redox reaction of H(2)O(2) with electroreduced polyoxometalate. This method successfully combines the electrochromic and luminescent properties of the polyoxometalate to develop a novel detection method for H(2)O(2) with good reversibility, which displays high sensitivity, a wide linear range and a low detection limit to H(2)O(2).

  17. Polyoxometalate-Based Organic-Inorganic Hybrids as Antitumor Drugs.

    PubMed

    Fu, Lei; Gao, Hanqin; Yan, Mei; Li, Shouzhu; Li, Xinyu; Dai, Zhifei; Liu, Shaoqin

    2015-06-24

    Polyoxometalates (POMs) have shown encouraging antitumor activity. However, their cytotoxicity in normal cells and unspecific interactions with biomolecules are two major obstacles that impede the practical applications of POMs in clinical cancer treatment. Derivatization of POMs with more biocompatible organic ligands is expected to cause a synergetic effect and achieve improved bioactivity and biospecificity. Herein, the synthesis of an amphiphilic organic-inorganic hybrid is reported by grafting a long-chain organoalkoxysilane lipid onto a POM. The amphiphilic POM hybrid could spontaneously assemble into the vesicles and exhibits enhanced antitumor activity for human colorectal cancer cell lines (HT29) compared to that of parent POMs. This detailed study reveals that the amphiphilic nature of POM hybrids enables the as-formed vesicles to easily bind to the cell membranes and then be uptaken by the cells, thus leading to a substantial increase in antitumor activity. Such prominent antitumor action is mostly accomplished via cell apoptosis, which ultimately results in cell death. Our finding demonstrates that novel POM hybrids-based drugs with increased bioactivity could be obtained by decorating POMs with selective organic ligands. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Polyoxometalate oxidation of chemical warfare agent simulants in fluorinated media.

    PubMed

    Johnson, R P; Hill, C L

    1999-12-01

    The aim of this research is to determine if appropriate polyoxometalates (POMs) could be added to perfluoropolyether topical skin protectants (TSPs) currently available or under development to give these TSPs the additional capability of detecting and in some cases catalytically decontaminating sulfur mustard (HD) and perhaps other chemical warfare agents (CWAs) at ambient temperatures. Detection would be based on significant color changes in the POM upon reduction by the CWA whereas catalytic decontamination would be based on the ability of some families of POMs to catalyze O(2)-based oxidations by more than one mechanism. Five POMs (10-25% by weight) were each suspended in ca. 5 g of the perfluoropolyether (PFPE, CF(3)O[-CF(CF(3))CF(2)O-](x)(-CF(2)O-)(y)CF(3)) 'barrier' cream. A stoichiometric amount of HD sulfide simulant was layered on top of each POM-cream mixture. The short reaction times were recorded for each system. Mechanistic studies were conducted using an PFPE oil analog of the barrier cream in a microemulsion with the sulfide simulant, POM, PFPE surfactant and 2,2,2-trifluoroethanol co-surfactant. Copyright 1999 John Wiley & Sons, Ltd.

  19. Polyoxometalates Macroanions: From Self-Recognition to Functional Materials

    NASA Astrophysics Data System (ADS)

    Yin, Panchao

    Large, hydrophilic polyoxoanions with high solubility in water and/or other polar solvents demonstrate unique solution behavior by self-assembling into single layer, hollow, spherical "blackberry"-like structures, which are obviously different from small, simple ions. These macroions cannot be treated as insoluble colloidal suspensions either because they form stable "real solutions". These inorganic macroions demonstrate some features usually Pobelieved to belong only to complex biological molecules, such as the self-recognition, chiral recognition, and chiral selection in dilute solutions. Highly negatively-charged molecular rods with almost identical structures were observed to self-assemble into their individual 'blackberry' structures, demonstrating tiny differences (e.g. charge, charge distribution, and organic ligands) could lead to self-recognition behavior. Chiral recognition behavior was understood by studying the self-assembly process in the racemic mixture solutions. Moreover, chiral organic molecules (lactic acid and tartaric acid) can be used to selectively inhibit the self-assembly process of one of the enantiomers. Meanwhile, polyoxometalate-based organic-inorganic hybrid materials demonstrate amphiphilic properties by self-assembling into vesicles and reverse vesicles in polar and non-polar solvents, respectively, and form catalytic emulsions in biphasic environments. Designed hybrid molecules can be programed to different devices with applications in fluorescence, photo-electronic conversion, molecular switch, and catalyst.

  20. Hybrid Thin Films Based Upon Polyoxometalates-Polymer Assembly

    NASA Astrophysics Data System (ADS)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2014-03-01

    Block copolymers (BCPs) and polyoxometalates (POMs) have been used individually as building blocks for design and synthesis of novel functional materials. POM nanoclusters, the assemblies of transition metal oxides with well-defined atomic coordination structure, have been recently explored as novel nanomaterials... for catalysis, semiconductors, and even anti-cancer treatment due to their unique chemical, optical and electrical characteristics. We have explored the blending of inorganic POM nanocluster with BCPs into hierarchaically structured inorganic-organic hybrid nanocomposites. Using polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin films as the template, we have observed that the spatial organization of BCP thin films is modified by molybdenum based POM nanocluster to form 2D in-plane hexagonal ordered or 3D ordered network of POM-BCP assemblies, depending on the concentration ratio of POM to PS-b-PEO. The dielectric properties of such hybrid thin films can be enhanced by embedded POMs but show a strong dependence on the supramolecular structures of POM-polymer complexes. The assembly of nanoclusters in BCP-templated thin films could pave a new path to design new hybrid nanocomposites with uniquely combined functionality and material properties.

  1. Polyoxometalate delignification of birch kraft pulp and effect on residual lignin

    Treesearch

    Biljana Bujanovic; Richard S. Reiner; Sally A. Ralph; Rajai H. Atalla

    2011-01-01

    To advance the understanding of delignification with polyoxometalates (POMs) that have been explored for use in bleaching of chemical pulps, the transformation of lignin during anaerobic treatment of birch kraft pulp with an equilibrated POM mixture composed of Na5(+2)[SiV1(-0.1)MoW10(+0.1)O

  2. Polyoxometalates for radioactive waste treatment. Annual progress report, June 15, 1996--September 30, 1997

    SciTech Connect

    Pope, M.T.

    1997-01-01

    'Four areas of research have been investigated during the first year of this project: (1) Selective separations of Ln{sup 3+} and An{sup 4+}; (2) Very large tungstate complexes of Ln{sup 3+}; (3) U{sup 4+} and UO{sub 2}{sup 2+} polytungstate complexes; (4) Rhenium (technetium) polyoxometalates. Progress in each of these areas is summarized.'

  3. Studies of lignin transformation in polyoxometalate (POM) bleaching of kraft pulp

    Treesearch

    Biljana Bujanovic; Richard S. Reiner; Kolby C. Hirth; Sally A. Ralph; Rajai H. Atalla

    2005-01-01

    In order to elucidate changes occurring in lignin during polyoxometalate delignification of kraft pulp, residual lignins of a series of POM- delignified kraft pulps of decreasing kappa number were isolated and characterized. Oxidative treatment of commercial unbleached kraft pulp was performed using complex POM solutions containing the active [SiVW11O40]anion. For...

  4. NiO-polyoxometalate nanocomposites as efficient catalysts for the oxidative dehydrogenation of propane and isobutane.

    PubMed

    Zhang, Qinghong; Cao, Chuanjing; Xu, Ting; Sun, Miao; Zhang, Jizhe; Wang, Ye; Wan, Huilin

    2009-05-07

    Novel nanocomposites of NiO and polyoxometalate (Cs(2.5)H(0.5)PMo(12)O(40)) with particle sizes in the range of 5-10 nm showed exceptional oxygen and ammonia adsorption capabilities, and the nanocomposites catalyzed the oxidative dehydrogenation of propane and isobutane efficiently under mild conditions.

  5. Structural changes of residual lignin of softwood and hardwood kraft pulp upon oxidative treatment with polyoxometalates

    Treesearch

    Biljana Bujanovic; Richard S. Reiner; Sally A. Ralph; Umesh P. Agarwal; Rajai H. Atalla

    2005-01-01

    Structural transformation of lignin in pulps bleached with polyoxometalates (POMs) should be explored in order to gain insight into the lignin reactions leading to its solubilization during POM treatment of kraft pulp. Our studies include characterization of residual lignin isolated from softwood commercial and birch laboratory kraft pulps delignified with POMs....

  6. Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors.

    PubMed

    Chen, Yuyun; Han, Min; Tang, Yujia; Bao, Jianchun; Li, Shunli; Lan, Yaqian; Dai, Zhihui

    2015-08-11

    Novel polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm(-2)), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.

  7. Synthesis and Characterization of Metal Nanoparticle Embedded Conducting Polymer–Polyoxometalate Composites

    PubMed Central

    2008-01-01

    Phosphomolybdate has been employed simultaneously as the oxidizing agent for the monomer polymerization and the reduced polyoxometalate is used as reducing agent for the reduction of metal ions. The composites thus obtained have been characterized and may have many potential applications.

  8. Photoisomerisation and light-induced morphological switching of a polyoxometalate-azobenzene hybrid.

    PubMed

    Markiewicz, Grzegorz; Pakulski, Dawid; Galanti, Agostino; Patroniak, Violetta; Ciesielski, Artur; Stefankiewicz, Artur R; Samorì, Paolo

    2017-06-29

    The functionalization of a spherical Keplerate-type polyoxometalate {Mo72V30} with a cationic azobenzene surfactant has been achieved through ionic self-assembly. The photoisomerisation reaction of this complex, which emerges in a light-triggered aggregation-disaggregation process, has been followed by (1)H NMR spectroscopy, dynamic light scattering, absorption spectroscopy and scanning electron microscopy analyses.

  9. Synthesis, structure and magnetism of a S-shaped multi-iron substituted arsenotungstate containing a trivacant Keggin [B-{alpha}-As{sup V}W{sub 9}O{sub 34}]{sup 9-} and a hexavacant Keggin [{alpha}-As{sup V}W{sub 6}O{sub 26}]{sup 11-} fragments

    SciTech Connect

    Zhao Junwei; Han Qiuxia; Shi Dongying; Chen Lijuan; Ma Pengtao; Wang Jingping; Niu Jingyang

    2011-10-15

    A S-shaped multi-iron substituted arsenotungstate [enH{sub 2}]{sub 2}[({alpha}-H{sub 2}As{sup V}W{sub 6}O{sub 26})Fe{sub 3}(H{sub 2}O)(B-{alpha}-H{sub 4}As{sup V}W{sub 9}O{sub 34})]{sub 2}[Fe]{sub 2}.8H{sub 2}O (1) (en=ethylenediamine) has been prepared by reaction of K{sub 14}[As{sub 2}{sup III}W{sub 19}O{sub 67}(H{sub 2}O)].nH{sub 2}O with Fe{sub 2}(SO{sub 4}){sub 3}.xH{sub 2}O under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The skeleton of 1 consists of two asymmetric sandwich-type subunits [({alpha}-H{sub 2}As{sup V}W{sub 6}O{sub 26})Fe{sub 3}(H{sub 2}O)(B-{alpha}-H{sub 4}As{sup V}W{sub 9}O{sub 34})]{sup 5-} linked by a di-Fe{sup III} cluster. Moreover, magnetic susceptibility measurements demonstrate that 1 indicates the antiferromagnetic coupling interactions within Fe{sup III} centers with the best-fitting set of parameters of J{sub 1}=-7.07 cm{sup -1}, J{sub 2}=-0.45 cm{sup -1} and g=2.05, which are generated by the addition of the expressions of the molar susceptibilities of two tri-Fe{sup III} clusters and one di-Fe{sup III} cluster derived from for spin pairs coupled through the isotropic exchange interactions. - Graphical abstract: S-shaped multi-iron substituted arsenotungstate consisting of two asymmetric sandwich-type subunits has been hydrothermally synthesized and structurally characterized. Its magnetic properties have been investigated. Highlights: > Multi-iron substituted arsenotungstate. > Symmetric sandwich-type subunits. > Antiferromagnetic coupling interactions within Fe{sup III} centers. > Hexavacant Keggin POM fragments.

  10. Two novel mono-organoimido functionalized polyoxometalate clusters: Convenient synthesis, crystal structure and bioactivity of [( n-C 4H 9) 4N] 2[Mo 6O 18(NAr)] (Ar = o-CF 3C 6H 4, p-OCF 3C 6H 4)

    NASA Astrophysics Data System (ADS)

    Xue, Sijia; Chai, An; Wei, Yongge; Xiang, Changsheng; Bian, Wangdong; Shen, Jian

    2008-10-01

    The hexamolybdate cluster has been functionalized with fluorine-containing aromatic amine by the DCC ( N, N'-dicyclohexylcarbodiimide) dehydrating protocol and two novel mono-functionalized arylimido derivatives of hexamolybdates bearing the electron-withdrawing trifluoromethyl group and trifluoromethoxy group, (Bu 4N) 2[Mo 6O 18(≡NAr)] (Ar = o-CF 3C 6H 4) 1 and (Bu 4N) 2[Mo 6O 18(≡NAr)] (Ar = p-OCF 3C 6H 4) 2 have been synthesized by improved method. Complete assignments were achieved for the title compounds by elemental analysis, IR, 1H NMR, UV/visible and single-crystal X-ray diffraction analyses. The preliminary herbicidal activity test indicated that they have some herbicidal activities.

  11. Self-assembly of polyoxometalate clusters into a 3-D heterometallic framework via covalent bonding: synthesis, structure and characterization of Na{sub 4}[Nd{sub 8}(dipic){sub 12}(H{sub 2}O){sub 9}][Mo{sub 8}O{sub 26}].8H{sub 2}O

    SciTech Connect

    Shen Enhong; Lue Jian; Li Yangguang; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Hu Changwen; Xu Lin

    2004-11-01

    An unprecedented hybrid solid obtained by self-assembly of octamolybdate clusters into a three-dimensional alkali metal modified neodymium-organic heterometallic framework is described. Crystal data: monoclinic, space group P21/n, a=21.868(4)A, b=13.039(3)A, c=22.479(5)A, {beta}=98.90(3){sup o}; V=6332(2)A3; Z=2, R (final)=0.0474. The data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293K using graphite-monochromated MoK{alpha} radiation ({lambda}=0.71073A) and oscillation scans technique in the range of 1.98 deg. {theta}27.48 deg.

  12. The supramolecular design of low-dimensional carbon nano-hybrids encoding a polyoxometalate-bis-pyrene tweezer.

    PubMed

    Modugno, Gloria; Syrgiannis, Zois; Bonasera, Aurelio; Carraro, Mauro; Giancane, Gabriele; Valli, Ludovico; Bonchio, Marcella; Prato, Maurizio

    2014-05-18

    A novel bis-pyrene tweezer anchored on a rigid polyoxometalate scaffold fosters a unique interplay of hydrophobic and electrostatic supramolecular interactions, to shape carbon nanostructures (CNSs)-based extended architectures.

  13. In situ fabrication of amino acid-polyoxometalate nanoparticle functionalized ultrathin films and relevant electrochemical property study

    SciTech Connect

    Li Siheng; Wang Enbo Tian Chungui; Mao Baodong; Song Yanli; Wang Chunlei; Xu Lin

    2008-11-03

    In this paper, amino acid-polyoxometalate (polyoxometalate H{sub 3}PMo{sub 12}O{sub 40}, H{sub 4}SiW{sub 12}O{sub 40}, and H{sub 3}PW{sub 12}O{sub 40}) nanoparticles functionalized ultrathin polyelectrolyte films were successfully fabricated via Layer-by-Layer (LbL) assembly technique. UV-vis absorption spectrometry was used to investigate the incorporation and reproducible growth process of the amino acid-polyoxometalate nanoparticles in the films. Fourier transform infrared spectroscopy was used to measure the composition of the ultrathin polyelectrolyte films. Transmission electron microscopy was employed to study the morphology and size of the nanoparticles in the films. Electrochemical study of the films shows that the excellent electrochemical property of the polyoxometalate remained.

  14. Self-assembled arrays of polyoxometalate-based metal-organic nanotubes for proton conduction and magnetism.

    PubMed

    Jiao, Yan-Qing; Zang, Hong-Ying; Wang, Xin-Long; Zhou, En-Long; Song, Bai-Qiao; Wang, Chun-Gang; Shao, Kui-Zhan; Su, Zhong-Min

    2015-06-30

    The first polyoxometalate-based metal-organic nanotube constructed via covalent bonds has been synthesized. POM anions stick the metal-organic nanotubes to build 3D nanotubular arrays. The stability, magnetic and proton conducting properties are investigated.

  15. A molecular photovoltaic system based on Dawson type polyoxometalate and porphyrin formed by layer-by-layer self assembly.

    PubMed

    Ahmed, Iftikhar; Farha, Rana; Goldmann, Michel; Ruhlmann, Laurent

    2013-01-18

    Films based on electrostatic interactions between tetracationic porphyrin and Dawson type polyoxometalate are formed by the so called layer-by-layer method. Their photovoltaic performances are investigated by photocurrent transient measurements which showed significant photocurrent response.

  16. The two-step assemblies of basic-amino-Acid-rich Peptide with a highly charged polyoxometalate.

    PubMed

    Zhang, Teng; Li, Hong-Wei; Wu, Yuqing; Wang, Yizhan; Wu, Lixin

    2015-06-15

    Two-step assembly of a peptide from HPV16 L1 with a highly charged europium-substituted polyoxometalate (POM) cluster, accompanying a great luminescence enhancement of the inorganic polyanions, is reported. The mechanism is discussed in detail by analyzing the thermodynamic parameters from isothermal titration calorimetry (ITC), time-resolved fluorescent and NMR spectra. By comparing the actions of the peptide analogues, a binding process and model are proposed accordingly. The driving forces in each binding step are clarified, and the initial POM aggregation, basic-sequence and hydrophobic C termini of peptide are revealed to contribute essentially to the two-step assembly. The present study demonstrates both a meaningful preparation for bioinorganic materials and a strategy using POMs to modulate the assembly of peptides and even proteins, which could be extended to other proteins and/or viruses by using peptides and POMs with similar properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A ternary nanocomposite electrode of polyoxometalate/carbon nanotubes/gold nanoparticles for electrochemical detection of hydrogen peroxide.

    PubMed

    Guo, Shuyue; Xu, Lin; Xu, Bingbing; Sun, Zhixia; Wang, Lihao

    2015-02-07

    In this work, a nanocomposite film electrode containing polyoxometalate (POM) clusters K6P2W18O62 (P2W18), carbon nanotubes (CNTs) and Au nanoparticles (AuNPs) was fabricated by a smart combination of layer-by-layer (LbL) with the self-assembly technique. The synergistic effect of POM, CNTs and AuNPs on the electrocatalysis of H2O2 was investigated to improve the sensitivity of H2O2 detection. The response of (P2W18/CNTs/P2W18/AuNPs)4 electrodes to H2O2 was remarkably enhanced due to large active sites and good electron conducting ability. The sensor exhibited a quick response (less than 1 second) to H2O2 with a high sensitivity (596.1 μAm M(-1) cm(-2)), and a low detection limit (52 nM). Based on the respective advantages of POMs, CNTs and AuNPs, the nanocomposite multilayer POMs/CNTs/POMs/AuNPs will have special properties and high potential for application.

  18. Synthesis and structural characterization of inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates.

    PubMed

    Hirano, Tomohisa; Uehara, Kazuhiro; Uchida, Sayaka; Hibino, Mitsuhiro; Kamata, Keigo; Mizuno, Noritaka

    2013-03-04

    Three inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates with organic linkers of different lengths, TBA8[{(γ-H2SiW10O36Pd2)(O2C(CH2)nCO2)}2] (n = 1 (II), 3 (III), and 5 (IV), TBA = [(n-C4H9)4N](+)), were synthesized by exchange of the acetate ligands in TBA4[γ-H2SiW10O36Pd2(OAc)2] (ITBA) with malonic, glutaric, and pimelic acids, respectively. The X-ray crystallographic analysis of II, IIIA (IIIA: III with DCE, DCE = 1,2-dichloroethane), and IVA (IVA: IV with 10DCE) revealed that the anion parts of II, IIIA, and IVA were inorganic-organic-inorganic hybrids composed of two dipalladium-substituted γ-Keggin silicodecatungstates connected by two dicarboxylate ligands. In the crystal structure of IVA, 10 DCE molecules per polyanion were present in the vicinity of polyanions. Compound IVB (IVB: IV with 0.2DCE) was obtained by the evacuation of IVA. The DCE sorption-desorption isotherms of IVB showed that the amount of DCE sorbed was saturated at 10.5 mol mol(-1), of which the amount was close to that (10 mol mol(-1)) of crystallographically assigned DCE molecules. In the DCE sorption-desorption isotherms, a low-pressure hysteresis was observed probably because of hydrogen-bonding interaction between DCE molecules and polyanions. The powder X-ray diffraction (XRD) pattern of IVA changed with decrease in the relative DCE vapor pressure to form IVC (IVC: IV with 0.7DCE) at P/P0 = 0.0. The in situ powder XRD study showed reversible structure transformation between IVA and IVC driven by the sorption-desorption of DCE.

  19. A series of pure inorganic eight-connected self-catenated network based on Silverton-type polyoxometalate

    SciTech Connect

    Tan Huaqiao; Chen Weilin; Li Yangguang Liu Ding; Chen Limin; Wang Enbo

    2009-03-15

    In this paper, three pure inorganic eight-connected self-catenated networks based on the Silverton-type polyoxometalate [CeMo{sub 12}O{sub 42}]{sup 8-} with lanthanide, transition metal and alkali metal cations as linkers: [Li(H{sub 2}O){sub 4}]{sub 2}Co(H{sub 2}O){sub 4}Ce(H{sub 2}O){sub 3}[CeMo{sub 12}O{sub 42}].3H{sub 2}O (1), H{sub 0.5}[Li(H{sub 2}O){sub 4}]{sub 2.5}[Ni(H{sub 2}O){sub 4}]{sub 0.5}Ce(H{sub 2}O){sub 3}[CeMo{sub 12}O{sub 42}].3H{sub 2}O (2) and H[Li(H{sub 2}O){sub 4}]{sub 3}Ce(H{sub 2}O){sub 3}[CeMo{sub 12}O{sub 42}].3H{sub 2}O (3) have been successfully synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, electrochemical analyses and single crystal X-ray diffraction. The single crystal X-ray diffraction analyses reveal that compounds 1-3 are isostructural. The [Ce{sup IV}Mo{sub 12}O{sub 42}]{sup 8-} polyoxoanions are connected by Ce{sup 4+} to form the infinite 1D chains. And then the parallel stacking chains linked by transition metal cations and lithium ions construct to an eight-connected self-catenated 4{sup 24}56{sup 3} topology framework. - Graphical Abstract: Three extended frameworks based on Silverton-type polyoxometalate have been successfully synthesized. In these compounds, [Ce{sup IV}Mo{sub 12}O{sub 42}]{sup 8-} clusters are connected by lanthanide, transition metal and Li{sup +} to form a 4{sup 24}56{sup 3} network.

  20. Star-like supramolecular polymers fabricated by a Keplerate cluster with cationic terminated polymers and their self-assembly into vesicles.

    PubMed

    Zhang, Qian; He, Lipeng; Wang, Hui; Zhang, Cheng; Liu, Weisheng; Bu, Weifeng

    2012-07-18

    The electrostatic combination of a Keplerate cluster, [Mo(132)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-) with cationic terminated poly(styrene) yields polyoxometalate-based supramolecular star polymers, which can further self-assemble into vesicular aggregates in CHCl(3)-MeOH mixed solvent.

  1. Three new extended Preyssler-type polyoxometalates modified by transition metal-2,2 Prime -biimidazole complexes

    SciTech Connect

    Yang, Chun-Yue; Zhang, Lan-Cui; Wang, Zan-Jiao; Wang, Lin; Li, Xiao-Hui; Zhu, Zai-Ming

    2012-10-15

    Three extended Preyssler-type ({l_brace}P{sub 5}W{sub 30}{r_brace}) polyoxometalates modified by transition metal (TM)-2,2 Prime -biimidazole (abbreviated as H{sub 2}biim) complexes, namely [Mn(H{sub 2}biim){sub 3}]{sub 5}H{sub 2}[{l_brace}Mn(H{sub 2}biim){sub 2}(H{sub 2}O){r_brace} (NaP{sub 5}W{sub 30}O{sub 110})]{center_dot}39H{sub 2}O (1), [{l_brace}(H{sub 2}biim){sub 2}Zn({mu}-OH)Zn(H{sub 2}biim)({mu}-H{sub 2}biim)Zn(H{sub 2}biim)(H{sub 2}O){r_brace}{sub 2}H{sub 4}(NaP{sub 5}W{sub 30}O{sub 110})]{center_dot}22 H{sub 2}O (2), and {l_brace}(H{sub 4}biim){sub 18}NaH{sub 5}[({mu}-Fe(H{sub 3}biim)(H{sub 2}O){sub 3})({mu}-Fe(H{sub 2}O){sub 4})(NaP{sub 5}W{sub 30}O{sub 110}){sub 2}]{sub 2}{center_dot}78H{sub 2}O{r_brace}{sub n} (3) have been hydrothermally synthesized, and characterized by physicochemical and spectroscopic methods. Their catalytic activities have been investigated. 1 contains mono-supporting {l_brace}P{sub 5}W{sub 30}{r_brace} anions. In compound 2, a {l_brace}P{sub 5}W{sub 30}{r_brace} anion is bi-supported by two symmetrical chains constructed by trinuclear zinc complexes. Compound 3 is composed of infinite 1-D zigzag chains built up of {l_brace}P{sub 5}W{sub 30}{r_brace} polyoxoanions linked via [Fe(H{sub 2}O){sub 4}]{sup 3+} and [Fe(H{sub 3}biim)(H{sub 2}O){sub 3}]{sup 4+} fragments. H{sub 2}biim ligands adopt three coordination modes in the structure. All these compounds have 3-D supramolecular frameworks via extensive hydrogen-bonding interactions. - Graphical abstract: Three new extended Preyssler-type polyoxometalates modified by TM-2,2 Prime -biimidazole complexes are obtained, they display high thermal stabilities. Highlights: Black-Right-Pointing-Pointer Three new extended Preyssler-type polyoxometalates were hydrothermally synthesized. Black-Right-Pointing-Pointer An interesting trinuclear zinc-2,2 Prime -biimidazole-polyanion complex was obtained. Black-Right-Pointing-Pointer The huge {l_brace}P{sub 5}W{sub 30}{r_brace} clusters were

  2. Polyoxometalate-anatase TiO2 composites are introduced into the photoanode of dye-sensitized solar cells to retard the recombination and increase the electron lifetime.

    PubMed

    Wang, Shi-Ming; Liu, Lin; Chen, Wei-Lin; Wang, En-Bo; Su, Zhong-Min

    2013-02-28

    Polyoxometalate-TiO(2) composites have been successfully introduced into the photoanode of dye-sensitized solar cells to reduce the recombination of the electrons, which results in a longer electron lifetime. The performance of the cells with the polyoxometalate-modified photoanode is better than the cell with a pure P25 photoanode. The effect of the polyoxometalate was studied by electrochemical impedance spectroscopy and open-circuit voltage decay measurement. The results show that the electron lifetime becomes longer following an increase in the amount of the polyoxometalate.

  3. A new nanohybrid material constructed from Keggin-type polyoxometalate and Cd(II) semicarbazone Schiff base complex with excellent adsorption properties for the removal of cationic dye pollutants

    NASA Astrophysics Data System (ADS)

    Farhadi, Saeed; Amini, Mostafa M.; Dusek, Michal; Kucerakova, Monika; Mahmoudi, Farzaneh

    2017-02-01

    A novel nanohybrid material containing a Cd(II) semicarbazone Schiff base complex and phosphomolybdic acid, [Cd(H2L+)6][H2L]+4[PMo12O40]4·18CH3OH·4H2O (1), [HL = pyridine-2-carbaldehyde semicarbazone] was prepared by a simple sonochemical route and characterized by 1HNMR, 13CNMR, FT-IR, UV-vis, PXRD, FESEM, TG-DTA and BET-BJH surface area analysis. Also the single crystal 1, was characterized by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P-1 and is assembled into 3D supramolecular structure via hydrogen intermolecular interactions. The nanohybrid 1 was tested for the adsorption and removal of organic dyes such as methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) from aqueous solutions. The effects of parameters such as the dosage of adsorbent, the initial concentration and pH of dye solution were investigated on the removal efficiency of methylene blue. The nanohybrid 1 exhibited excellent adsorption ability towards cationic dyes. Moreover, it could be easily separated from the reaction solution and recycled up to three times without significant loss of adsorption activity.

  4. Stabilization of plutonium(III) in the Preyssler polyoxometalate.

    PubMed

    Antonio, Mark R; Chiang, Ming-Hsi

    2008-09-15

    The Na(+) ion encapsulated within the Preyssler heteropolyoxoanion, [NaP5W30O110](14-), was exchanged with Pu(III) under hydrothermal conditions to obtain [Pu(III)P5W30O110](12-) (abbreviated [PuPA](12-)) with hybrid electrochemical properties resulting from the combination of the key redox behaviors of the Pu cation and the P-W-O anion. The electroanalytical chemistry of this two-center, multielectron redox system in a 1 M HCl electrolyte shows that Pu(III) is oxidized to Pu(IV) at the half-wave potential, E(1/2), of +0.960 V versus Ag/AgCl, which is 0.197 V more positive than the corresponding electrode potential for the Pu(III) aqua ion also in 1 M HCl, indicating the stabilization of the trivalent Pu cation by its encapsulation in the Preyssler polyoxometalate (POM). This effect is uncommon in actinide-POM chemistry, wherein electrode potential shifts of the opposite nature (to more negative values), leading to the stabilization of the tetravalent ions by complexation, are renowned. Moreover, in cyclic voltammetry measurements of the Pu(III) aqua ion and [PuPA](12-), the peak currents, i(p), for the one-electron Pu(III)/Pu(IV) processes show different dependencies with the scan rate, nu. The former shows proportionality with nu(1/2), indicating freely diffusing species, whereas the latter shows proportionality with nu, indicating a surface-confined one. The first of the five successive two-electron, W-centered reduction processes in [PuPA](12-) occurs at E(1/2) = -0.117 V versus Ag/AgCl, which is 1.077 V less than the E(1/2) for the Pu(III)/Pu(IV) oxidation, thereby providing an experimental, electrochemical measure of the highest occupied molecular orbital/lowest unoccupied molecular orbital energy gap, which compares well with values previously obtained by density-functional theory, complete active space-self consistent field, and post-Hartree-Fock calculations for a series of M(n+)-exchanged systems, [MPA](n-15) for 1 < or = n < or = 4 (Fernandez, J. A

  5. Removal of Multiple Contaminants from Water by Polyoxometalate Supported Ionic Liquid Phases (POM-SILPs).

    PubMed

    Herrmann, Sven; De Matteis, Laura; de la Fuente, Jesús M; Mitchell, Scott G; Streb, Carsten

    2017-02-01

    The simultaneous removal of organic, inorganic, and microbial contaminants from water by one material offers significant advantages when fast, facile, and robust water purification is required. Herein, we present a supported ionic liquid phase (SILP) composite where each component targets a specific type of water contaminant: a polyoxometalate-ionic liquid (POM-IL) is immobilized on porous silica, giving the heterogeneous SILP. The water-insoluble POM-IL is composed of antimicrobial alkylammonium cations and lacunary polyoxometalate anions with heavy-metal binding sites. The lipophilicity of the POM-IL enables adsorption of organic contaminants. The silica support can bind radionuclides. Using the POM-SILP in filtration columns enables one-step multi-contaminant water purification. The results show how multi-functional POM-SILPs can be designed for advanced purification applications.

  6. Crystallization of a Keplerate-type polyoxometalate into a superposed kagome-lattice with huge channels.

    PubMed

    Saito, Masaki; Ozeki, Tomoji

    2012-09-07

    Crystal structures of two Sr(2+) salts of the Keplerate-type polyoxometalate, [Mo(VI)(72)Mo(V)(60)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-), have been determined by single crystal X-ray diffraction. One compound exhibits a superposed kagome-lattice with huge channels whose diameters measure approximately 3.0 nm, while the arrangement of the Keplerate anions in the other compound approximates to a distorted cubic close packing.

  7. Kinetic analysis of polyoxometalate (POM) oxidation of non-phenolic lignin model compound

    Treesearch

    Tomoya Yokoyama; Hou-min Chang; Ira A. Weinstock; Richard S. Reiner; John F. Kadla

    2003-01-01

    Kinetic and reaction mechanism of non-phenolic lignin model compounds under anaerobic polyoxometalate (POM), Na5(+1.9)[SiV1(-0.1)MoW10(+0.1) 40], bleaching conditions were examined. Analyses using a syringyl type model, 1-(3,4,5-trimethoxyphenyl)ethanol (1), a guaiacyl type, 1-(3,4- imethoxyphenyl)ethanol (2), and 1- (4-ethoxy-3,5-dimethoxyphenyl)ethanol (3) suggest...

  8. Synthesis and characterization of conjugated Dawson-type polyoxometalate-porphyrin copolymers.

    PubMed

    Azcarate, Iban; Ahmed, Iftikhar; Farha, Rana; Goldmann, Michel; Wang, Xiaoxia; Xu, Hualong; Hasenknopf, Bernold; Lacôte, Emmanuel; Ruhlmann, Laurent

    2013-09-21

    Hybrid polyoxometalate-porphyrin copolymeric films were obtained by the electro-oxidation of zinc octaethylporphyrin (ZnOEP) in the presence of a Dawson type polyoxophosphovanadotungstate bearing two pyridyl groups (POM(py)2). The synthesis of a series of POM(py)2 consisting of [P2W15V3O62](9-) functionalized with diol-amide or triol moieties, as well as the characterization of the copolymers are presented.

  9. A general strategy to fabricate simple polyoxometalate nanostructures: electrochemistry-assisted laser ablation in liquid.

    PubMed

    Liu, Pu; Liang, Ying; Lin, Xianzhong; Wang, Chengxin; Yang, Guowei

    2011-06-28

    Polyoxometalate nanostructures have attracted much attention because of significant technical demands in applications such as catalysts, sensors, and smart windows. Therefore, researchers have recently developed many methods for the synthesis of these nanomaterials. However, these techniques have many visible flaws such as high temperatures or high pressure environments, various templates or additives, demanding and complicated synthesis procedures as well as the presence of impurities in the final products. We therefore propose a general strategy for the fabrication of particular polyoxometalate nanostructures by electrochemically assisted laser ablation in liquid (ECLAL). These polyoxometalates are usually simple as they typically contain two metals and are not soluble in water. This approach is a green, simple, and catalyst-free approach under an ambient environment. Apart from these merits, this novel technique allows researchers to choose and design interesting solid targets and to use an electrochemical approach toward the fabrication of polyoxometalate nanostructures for the purpose of fundamental research and for potential applications. Using the synthesis of Cu(3)Mo(2)O(9) nanorods as an example, we substantiate the validity of the proposed strategy. For the fabrication of Cu(3)Mo(2)O(9) nanostructures, we chose molybdenum as a solid target for laser ablation in liquid copper electrodes for the electrochemical reaction and water as a solvent for the ECLAL synthesis. We successfully fabricated Cu(3)(OH)(2)(MoO(4))(2) nanorods with magnetic properties. Interestingly, we obtained well-defined Cu(3)Mo(2)O(9) nanorods by annealing the Cu(3)(OH)(2)(MoO(4))(2) nanostructures at 500 °C. Additionally, the basic physics and chemistry involved in the ECLAL fabrication of nanostructures are discussed.

  10. Donor-acceptor organo-imido polyoxometalates: high transparency, high activity redox-active NLO chromophores.

    PubMed

    Al-Yasari, Ahmed; Van Steerteghem, Nick; El Moll, Hani; Clays, Koen; Fielden, John

    2016-02-21

    We show that polyoxometalates (POMs) are an excellent redox-active acceptor on which to base high performance 2(nd) order non-linear optical (NLO) chromophores. This is demonstrated through three new organoimido-Lindqvist derivatives with HRS β0-values exceeding those of any dipolar organic system with comparable donor, π-system and absorption profile. Thus, organoimido POMs may provide a new generation of high performance, high transparency, and potentially redox-switchable NLO materials.

  11. Lignin modification in the initial phase of softwood kraft pulp delignification with polyoxometalates (POMs)

    Treesearch

    Biljana Bujanovic; Sally A. Ralph; Richard S. Reiner; Rajai H. Atalla

    2007-01-01

    Commercial softwood kraft pulp with kappa number 30.5 (KP30.5) was delignified with polyoxometalates (POM, Na5(+2)[SiV1(-0.1)MoW10(+0.1)O40]), and POM-treated kraft pulp of kappa number 23.6 was obtained (KPPOM,23.6). Residual lignin from pulps was isolated by mild acid hydrolysis and characterized by analytical and spectral methods to gain insight into lignin...

  12. Polyoxometalates for Radioactive Waste Treatment - Final Report - 06/15/1996 - 09/14/2000

    SciTech Connect

    Pope, Michael T.

    2000-09-14

    The research was directed primarily towards the use of polyoxometalate complexes for separation of lanthanide, actinide, and technetium species from aqueous waste solutions, such as the Hanford Tank Wastes. Selective binding of these species responsible for much of the high level waste (HWL) activity, can reduce the volume of material to be subsequently vitrified or otherwise converted for long-term storage. A secondary objective was to explore the direct conversion of the polyoxometalate complexes into possible waste forms, oxide bronzes, thereby avoiding additional handling and energy-intensive vitrification procedures. Although the advantages of polyoxometalate anions (POMs) lie in their high thermal and radiolytical stabilities, that has been no attempt to exploit the remarkable variety of these complexes beyond the use of the two anions mentioned above. Our broad knowledge of POM chemistry has allowed us to address and rectify this omission. The innovative aspects of the project are: (a) the selective sequestration of lanthanide and actinide cations by a POM system in the presence of excess alkali and transition metal cations; (b) the formation of the first examples of POM complexes of UO2-2+ and their extraction into nonaqueous solvents; (c) the thermal conversion of ammonium salts of lanthanide and actinide POM complexes into inert oxide bronzes at relatively low temperatures; and (d) the direct formation of highly thermally-robust niobate and tantalate complexes of Re (surrogate for Tc) in highly basic solutions.

  13. Keggin-type heteropoly compounds supported on montmorillonite clays offering strong option for efficient solid-phase microextraction coating.

    PubMed

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Rafiee, Ezzat

    2014-01-31

    Keggin-type heteropoly compounds supported on montmorillonite clays were prepared and used as a highly porous fiber coating material for solid-phase microextraction (SPME). The prepared nanomaterial was immobilized onto a stainless steel wire for fabrication of the SPME fiber. The fiber was evaluated for the extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions in combination with gas chromatography-mass spectrometry (GC-MS). A one at-the-time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, stirring rate, and desorption temperature and time. In optimum conditions, the repeatability for one fiber (n=3), expressed as relative standard deviation (R.S.D.%), was between 5.1% and 8.4% for the test compounds. The detection limits for the studied compounds were between 0.02 and 0.05pgmL(-1). The developed method offers the advantage of being simple to use, with shorter analysis time, lower cost of equipment, thermal stability of fiber, and high relative recovery in comparison to conventional methods of analysis.

  14. 31P Magic Angle Spinning NMR Spectroscopy of Paramagnetic Rare Earth-Substituted Keggin and Wells-Dawson Solids

    PubMed Central

    Huang, Wenlin; Schopfer, Mark; Zhang, Cheng; Howell, Robertha C.; Todaro, Louis; Gee, Becky A.; Francesconi, Lynn C.; Polenova, Tatyana

    2008-01-01

    Paramagnetic rare-earth elements have been examined as NMR structural probes in polyoxoanionic solids, which have a variety of applications as luminescent materials that are usually disordered and therefore intractable by traditional structural methods. Thirteen Keggin and Wells-Dawson polyoxotungstates containing substitutions with lanthanides of different effective magnetic moments have been examined by 31P magic angle spinning NMR spectroscopy. The electron-nuclear dipolar interaction dominating the spinning sideband envelopes is determined by the lanthanide’s magnetic moment and was found to be a sensitive probe of the nature of the polyoxoanion, of the positional isomerism, and of the ion stoichiometry. Electron-nuclear dipolar anisotropies computed based on the point-dipole approximation are generally in good agreement with the experimental results. The choice of a specific lanthanide as a structural probe can be tailored to the desired distance range between the phosphorus atoms and the paramagnetic centers to be probed. This approach is expected to be particularly useful in the paramagnetic polyoxoanionic materials lacking long-range order. PMID:18095677

  15. Guest-directed supramolecular architectures of {W36} polyoxometalate crowns.

    PubMed

    McGlone, Thomas; Streb, Carsten; Long, De-Liang; Cronin, Leroy

    2009-10-05

    The {W36} isopolyoxotungstate cluster provides a stable inorganic molecular platform for the binding of inorganic and organic guest molecules. This is achieved by a binding pocket formed by six terminal oxo ligands located in the central cavity of the all-inorganic cation binding host. Previously it was shown that the cluster can specifically bind primary amines and importantly, functionalized diamines through a combination of electrostatic and hydrogen bonding interactions. Here we transform this assembly strategy to utilize the binding of long-chain alkyldiammonium guest cations to physically define the supramolecular structure of the clusters with respect to each other and demonstrate the structure direction as a function of alkyl chain length. The systematic variation of the chain length gives access to five supramolecular assemblies which were all fully characterized using single crystal XRD, TGA, 1H NMR, and elemental analysis. In compound 1, diprotonated 1,8-diaminooctane molecules link the {W36} clusters into infinite 1D zigzag chains, whereas compounds 2 and 3 feature trimeric {W36} assemblies directly connected through protonated 1,9-diaminononane (2) or 1,10-diaminodecane (3) linkers. Compound 4 contains dumb-bell shaped dimeric units as a result of direct center-to-center linkages between the {W36} clusters formed by protonated 1,12-diaminododecane. In compound 5, triply protonated bis(hexamethylene)triamine was employed to obtain linear 1D chains of directly connected {W36} cluster units.

  16. An electroswitchable fluorescence thin-film based on a luminescent polyoxometalate cluster.

    PubMed

    Wang, Bin; Yin, Zhen-Dong; Bi, Li-Hua; Wu, Li-Xin

    2010-10-14

    We selected a Eu(3+)-containing tungstogermanate [(CH(3))(4)N](2.5)H(7.5)[Eu(GeW(11)O(39))(H(2)O)(2)](2)·4.5H(2)O (EuGeW) as a molecular dyad combining fluorescence and electroactivity components within the same framework and studied its electroswitchable fluorescence in solution and in the thin-film, which can be reversibly switched by electrochemical stimulation.

  17. Enhanced Visible Photovoltaic Response of TiO₂ Thin Film with an All-Inorganic Donor-Acceptor Type Polyoxometalate.

    PubMed

    Li, Jian-Sheng; Sang, Xiao-Jing; Chen, Wei-Lin; Zhang, Lan-Cui; Zhu, Zai-Ming; Ma, Teng-Ying; Su, Zhong-Min; Wang, En-Bo

    2015-06-24

    In the field of material chemistry, it is of great significance to develop abundant and sustainable materials for solar energy harvesting and management. Herein, after evaluating the energy band characteristics of 13 kinds of polyoxometalates (POMs), the trisubstituted POM compound K6H4[α-SiW9O37Co3(H2O)3]·17H2O (SiW9Co3) was first studied due to its relatively smaller band gap (2.23 eV) and higher lowest unoccupied molecular orbital (LUMO) level (-0.63 V vs NHE). Additionally, the preliminary computational modeling indicated that SiW9Co3 exhibited the donor-acceptor (D-A) structure, in which the cobalt oxygen clusters and tungsten skeletons act as the electron donor and electron acceptor, respectively. By employing SiW9Co3 to modify the TiO2 film, the visible photovoltaic and photocurrent response were both enhanced, and the light-induced photocurrent at 420 nm was improved by 7.1 times. Moreover, the highly dispersive and small sized SiW9Co3 nanoclusters loading on TiO2 were successfully achieved by fabricating the nanocomposite film of {TiO2/SiW9Co3}3 with the layer-by-layer method, which can result in the photovoltaic performance enhancement of dye-sensitized solar cells (DSSCs), of which the overall power conversion efficiency was improved by 25.6% from 6.79% to 8.53% through the synergistic effect of POMs and Ru-complex.

  18. The atomic level journey from aqueous polyoxometalate to metal oxide

    SciTech Connect

    Hou, Yu; Fast, Dylan B.; Ruther, Rose E.; Amador, Jenn M.; Fullmer, Lauren B.; Decker, Shawn R.; Zakharov, Lev N.; Dolgos, Michelle R. Nyman, May

    2015-01-15

    Aqueous precursors tailored for the deposition of thin film materials are desirable for sustainable, simple, low energy production of advanced materials. Yet the simple practice of using aqueous precursors is complicated by the multitude of interactions that occur between ions and water during dehydration. Here we use lithium polyoxoniobate salts to investigate the fundamental interactions in the transition from precursor cluster to oxide film. Small-angle X-ray scattering of solutions, total X-ray scattering of intermediate gels, and morphological and structural characterization of the lithium niobate thin films reveal the atomic level transitions between these states. The studies show that (1) lithium–[H{sub 2}Nb{sub 6}O{sub 19}]{sup 6−} has drastically different solution behaviour than lithium–[Nb{sub 6}O{sub 19}]{sup 8−}, linked to the precursor salt structure (2) in both compositions, the intermediate gel preserves the polyoxoniobate clusters and show similar local order and (3) the morphology and phases of deposited films reflect the ions behaviour throughout the journey from cluster solution to metal oxide. - Graphical abstract: Aqueous lithium polyoxoniobate salts were used to prepare lithium niobate (LiNbO{sub 3}) thin films. Fundamental studies were performed to investigate the interactions in the transition from precursor cluster to the oxide film. It was found that acid–base and ion-association chemistries of the aqueous and gel systems significantly affect the key processes in this atom-level journey. - Highlights: • Lithium polyoxoniobate clusters were synthesized with control over Li:Nb ratio as precursors for LiNbO{sub 3} films. • X-ray scattering studies in solution and the solid-state revealed differences controlled by Li:Nb ratio. • Film deposition studies revealed phase, composition and morphology is controlled by Li:Nb ratio. • Cluster to film transformation was revealed using total X-ray scattering and TGA.

  19. Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength.

    PubMed

    Veen, Sandra J; Kegel, Willem K

    2009-11-19

    We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like assemblies. This instability occurs at significantly lower ionic strength than the colloidal stability limit and only becomes evident after a relatively long time. For the polyoxometalate, abbreviated as {Mo(72)Fe(30)}, it is shown that the structural stability limit of POM-shells lies between a NaCl concentration of 1.00 and 5.00 mM in aqueous solution.

  20. A co-crystal of polyoxometalates exhibiting single-molecule magnet behavior: the structural origin of a large magnetic anisotropy

    SciTech Connect

    Fang, Xikui; McCallum, Kendall; Pratt III, Harry D.; Anderson, Travis M.; Dennis, Kevin; Luban, Marshall

    2012-03-29

    A polyoxometalate-based {MnIII3MnIV} single-molecule magnet exhibits a large axial anisotropy (D = −0.86 cm−1) resulting from a near-parallel alignment of Jahn–Teller axes. Its rigorous three-fold symmetry (i.e. rhombicity E → 0) and increased intercluster separation via co-crystallization effectively hamper quantum tunnelling of the magnetization. Graphical abstract: A co-crystal of polyoxometalates exhibiting single-molecule magnet behavior: the structural origin of a large magnetic anisotropy

  1. A sodalite-type porous metal-organic framework with polyoxometalate templates: adsorption and decomposition of dimethyl methylphosphonate.

    PubMed

    Ma, Feng-Ji; Liu, Shu-Xia; Sun, Chun-Yan; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-03-30

    A sodalite-type porous metal-organic framework with polyoxometalate templates, H(3)[(Cu(4)Cl)(3)(BTC)(8)](2)[PW(12)O(40)]·(C(4)H(12)N)(6)·3H(2)O (NENU-11; BTC = 1,3,5-benzenetricarboxylate), was obtained by a hydrothermal reaction. As a reasonable candidate for eliminating nerve gas, NENU-11 displays good adsorption behavior for dimethyl methylphosphonate (15.5 molecules per formula unit). In virtue of the catalytic activity of polyoxometalate guests, this nerve gas mimic could be facilely decomposed by a hydrolysis reaction.

  2. Synthesis, structure and luminescent property of a new hybrid solid based on Keggin anions and silver-organonitrogen fragments

    SciTech Connect

    Lue Jian; Xiao Fuxian; Shi Linxi; Cao Rong

    2008-02-15

    A new hybrid solid, {l_brace}Ag(phen){sub 2}{r_brace}{sub 2}{l_brace}[Ag(phen)]{sub 2}[PMo{sub 12}O{sub 40}]{r_brace} (phen=1,10-phenanthroline) 1, constructed from one-electron-reduced mono-supported {alpha}-Keggin polyanions and silver-phenanthroline fragments via either covalent bonds or supramolecular interactions, is described. In the structure of 1, mono-supported {l_brace}Ag(phen)[PMo{sub 12}O{sub 40}]{r_brace}{sup 3-} polyanions are connected by {l_brace}Ag(phen){r_brace}{sup +} linking fragments to form a hybrid chain structure with engrafted phen ligands. {l_brace}Ag(phen){sub 2}{r_brace}{sup +} counter-cations occur in pairs trapping in strong inter-chain {pi}-{pi} stacking to form a three-dimensional supramolecular framework. Luminescent investigation of the compound indicates that 1 displays fascinating orange luminescent property at ambient temperature. - Graphical abstract: A novel hybrid solid, {l_brace}Ag(phen){sub 2}{r_brace}{sub 2}{l_brace}[Ag(phen)]{sub 2}[PMo{sub 12}O{sub 40}]{r_brace} (phen=1,10-phenanthroline) 1, is reported. In the structure of 1, {l_brace}Ag(phen)[PMo{sub 12}O{sub 40}]{r_brace}{sup 3-} polyanions are connected by {l_brace}Ag(phen){r_brace}{sup +} fragments to form a hybrid chain structure. {l_brace}Ag(phen){sub 2}{r_brace}{sup +} counter-cations are involved in inter-chain {pi}-{pi} stacking to form a three-dimensional supramolecular framework. Luminescent investigation of 1 indicates that 1 displays fascinating orange luminescent property at ambient temperature.

  3. Targeted synthesis of silicomolybdic acid (Keggin acid) inside mesoporous silica hollow spheres for Friedel-Crafts alkylation.

    PubMed

    Dou, Jian; Zeng, Hua Chun

    2012-10-03

    Herein we report an inside-out preinstallation-infusion-hydration method for targeted synthesis of Keggin heteropoly acids (silicomolybdic acid, H(4)SiMo(12)O(40)) within mesoporous silica (SiO(2)) hollow spheres. In this process, discrete molybdenum dioxide (MoO(2)) nanoparticles with diameter size ranging from 25 to 60 nm were first prepared by a one-pot hydrothermal route in water/ethanol mixed solvents at 180 °C, which were then used as cores to grow the shell of supramolecular templated silica with tetraethyl orthosilicate (TEOS) and hexadecyltrimethyl- ammonium chloride (CTACl) in alkaline solution. By thermal treatment of as-synthesized MoO(2)@SiO(2) core-shell spheres, the organic template was burned off and mesoporous shell was formed (BET specific surface area was as high as 872 m(2)/g). Meanwhile, the encapsulated MoO(2) was oxidized to Mo(6+) and infused to the mesoporous silica shells, forming heptamolybdate species (Mo(7)O(24)(6-)) uniformly dispersed on the mesopore surfaces of silica, while generating void space at the center of spheres. After hydration with water, H(4)SiMo(12)O(40) was formed by reaction between the surface Mo(7)O(24)(6-) and silica species in the presence of water. The prepared H(4)SiMo(12)O(40) @mSiO(2) hollow spheres were tested for Friedel-Crafts alkylation of toluene by benzyl alcohol. The H(4)SiMo(12)O(40)@mSiO(2) catalysts fabricated via this novel route exhibited excellent catalytic activity toward benzylation of toluene, which was approximately 2.6 times as high as that of commercial Amberlyst-15 catalyst. In addition, the H(4)SiMo(12)O(40)@mSiO(2) catalyst was very robust and could be reused after regeneration.

  4. Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure

    SciTech Connect

    Quesada Cabrera, Raul; Firth, Steven; Blackman, Christopher S.; Long, De-Liang; Cronin, Leroy; McMillan, Paul F.

    2012-02-15

    Structural changes occurring within non-conventional Dawson-type [{alpha}/{beta}-Mo{sub 18}O{sub 54}(SO{sub 3}){sub 2}]{sup 4-} polyanions in the form of tetrapentylammonium salts were studied by a combination of IR, Raman and visible spectroscopy at high temperature and high pressure. Evidence of the formation of bronze-type materials above 400 K and also upon pressurization to 8 GPa is presented. This conclusion is suggested to be a general result for polyoxometalate compounds subjected to extreme conditions and it opens opportunities for the design of new materials with interesting optical and electronic properties. - Graphical abstract: Structural changes occurring within non-conventional Dawson-type [{alpha}/{beta}-Mo{sub 18}O{sub 54}(SO{sub 3}){sub 2}]{sup 4-} polyanions in the form of tetrapentylammonium salts were studied by a combination of IR, Raman and visible spectroscopy at high temperature and high pressure. Evidence of the formation of bronze-type materials above 400 K and also upon pressurization to 8 GPa is presented. This conclusion is suggested to be a general result for polyoxometalate compounds subjected to extreme conditions and it opens opportunities for the design of new materials with interesting optical and electronic properties. Highlights: Black-Right-Pointing-Pointer Spectroscopy studies of non-conventional Wells-Dawson polyoxometalates (POMs) at high temperature and high pressure. Black-Right-Pointing-Pointer Discussion on the stability of two POM isomers. Black-Right-Pointing-Pointer Local formation of bronze-like materials: possibilities for a new synthetic method at high pressure from POM precursors.

  5. On the possibility of controlling the hydrophilic/hydrophobic characteristics of toroid Mo138 nanocluster polyoxometalates

    NASA Astrophysics Data System (ADS)

    Grzhegorzhevskii, K. V.; Adamova, L. V.; Eremina, E. V.; Ostroushko, A. A.

    2017-03-01

    The possibility of changing the hydrophilic (polar) surfaces of toroid nanocluster polyoxomolibdates to hydrophobic (nonpolar) surfaces via the modification of Mo138 nanoclusters by surfactant molecules (dodecylpyridinium chloride) as a result of the interaction between these compounds in solutions is demonstrated. Benzene and methanol are used as molecular probes (indicators of the condition of nanocluster surfaces). Comparative characteristics of the equilibrium sorption of benzene and methanol vapors on the initial and modified surfaces of the solid polyoxometalate, and data on the sorption of organic molecules on the surfaces of Rhodamine B-modified nanoclusters of the toroid (Mo138) and keplerate (Mo132) types are obtained.

  6. Covalent Photosensitizer-Polyoxometalate-Catalyst Dyads for Visible-Light-Driven Hydrogen Evolution.

    PubMed

    Schönweiz, Stefanie; Rommel, Sebastian A; Kübel, Joachim; Micheel, Mathias; Dietzek, Benjamin; Rau, Sven; Streb, Carsten

    2016-08-16

    A general concept for the covalent linkage of coordination compounds to bipyridine-functionalized polyoxometalates is presented. The new route is used to link an iridium photosensitizer to an Anderson-type hydrogen-evolution catalyst. This covalent dyad catalyzes the visible-light-driven hydrogen evolution reaction (HER) and shows superior HER activity compared with the non-covalent reference. Hydrogen evolution is observed over periods >1 week. Spectroscopic, photophysical, and electrochemical analyses give initial insight into the stability, electronic structure, and reactivity of the dyad. The results demonstrate that the proposed linkage concept allows synergistic covalent interactions between functional coordination compounds and reactive molecular metal oxides.

  7. Catalytic self-propulsion of supramolecular capsules powered by polyoxometalate cargos.

    PubMed

    del Mercato, Loretta L; Carraro, Mauro; Zizzari, Alessandra; Bianco, Monica; Miglietta, Ruggero; Arima, Valentina; Viola, Ilenia; Nobile, Concetta; Sorarù, Antonio; Vilona, Debora; Gigli, Giuseppe; Bonchio, Marcella; Rinaldi, Rosaria

    2014-08-25

    Multicompartment, spherical microcontainers were engineered through a layer-by-layer polyelectrolyte deposition around a fluorescent core while integrating a ruthenium polyoxometalate (Ru4POM), as molecular motor, vis-à-vis its oxygenic, propeller effect, fuelled upon H2O2 decomposition. The resulting chemomechanical system, with average speeds of up to 25 μm s(-1), is amenable for integration into a microfluidic set-up for mixing and displacement of liquids, whereby the propulsion force and the resulting velocity regime can be modulated upon H2O2-controlled addition. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Recent advances in porous polyoxometalate-based metal-organic framework materials.

    PubMed

    Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2014-07-07

    Polyoxometalate (POM)-based metal-organic framework (MOF) materials contain POM units and generally generate MOF materials with open networks. POM-based MOF materials, which utilize the advantages of both POMs and MOFs, have received increasing attention, and much effort has been devoted to their preparation and relevant applications over the past few decades. They have good prospects in catalysis owing to the electronic and physical properties of POMs that are tunable by varying constituent elements. In this review, we present recent developments in porous POM-based MOF materials, including their classification, synthesis strategies, and applications, especially in the field of catalysis.

  9. Smart high-κ nanodielectrics using solid supported polyoxometalate-rich nanostructures.

    PubMed

    Musumeci, Chiara; Rosnes, Mali H; Giannazzo, Filippo; Symes, Mark D; Cronin, Leroy; Pignataro, Bruno

    2011-12-27

    Utilizing Langmuir-Blodgett deposition and scanning probe microscopy, we have investigated the extent to which cations alter the self-assembly processes of hybrid polyoxometalates (POMs) on surfaces. The well-defined 2D hexagonal nanostructures obtained were extensively characterized and their properties were studied, and this has revealed fascinating dielectric behavior and reversible capacitive properties. The nanostructures are extremely stable under ambient conditions, and yet exhibit fascinating self-patterning upon heating. These findings present POMs as effective smart nanodielectrics and open up a new field for future POM applications.

  10. Polyoxometalate-Driven Self-Assembly of Short Peptides into Multivalent Nanofibers with Enhanced Antibacterial Activity.

    PubMed

    Li, Jingfang; Chen, Zhijun; Zhou, Mengcheng; Jing, Jiangbo; Li, Wen; Wang, Yang; Wu, Lixin; Wang, Liyan; Wang, Yanqiu; Lee, Myongsoo

    2016-02-12

    Multivalent peptide nanofibers have attracted intense attention as promising platforms, but the fabrication of those nanofibers is mainly dependent on the spontaneous assembly of β-sheet peptides. Herein we report an alternative approach to the creation of nanofibers: the polyoxometalate-driven self-assembly of short peptides. The resultant nanofibers with concentrated positive charges are excellent multivalent ligands for binding with bacterial cells and thus lead to a salient improvement in bioactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The atomic level journey from aqueous polyoxometalate to metal oxide

    NASA Astrophysics Data System (ADS)

    Hou, Yu; Fast, Dylan B.; Ruther, Rose E.; Amador, Jenn M.; Fullmer, Lauren B.; Decker, Shawn R.; Zakharov, Lev N.; Dolgos, Michelle R.; Nyman, May

    2015-01-01

    Aqueous precursors tailored for the deposition of thin film materials are desirable for sustainable, simple, low energy production of advanced materials. Yet the simple practice of using aqueous precursors is complicated by the multitude of interactions that occur between ions and water during dehydration. Here we use lithium polyoxoniobate salts to investigate the fundamental interactions in the transition from precursor cluster to oxide film. Small-angle X-ray scattering of solutions, total X-ray scattering of intermediate gels, and morphological and structural characterization of the lithium niobate thin films reveal the atomic level transitions between these states. The studies show that (1) lithium-[H2Nb6O19]6- has drastically different solution behaviour than lithium-[Nb6O19]8-, linked to the precursor salt structure (2) in both compositions, the intermediate gel preserves the polyoxoniobate clusters and show similar local order and (3) the morphology and phases of deposited films reflect the ions behaviour throughout the journey from cluster solution to metal oxide.

  12. Etherification of n-butanol to di-n-butyl ether over Keggin-, Wells-Dawson-, and Preyssler-type heteropolyacid catalysts.

    PubMed

    Kim, Jeong Kwon; Choi, Jung Ho; Park, Dong Ryul; Song, In Kyu

    2013-12-01

    Etherification of n-butanol to di-n-butyl ether was carried out over various structural classes of heteropolyacid (HPA) catalysts, including Keggin- (H3PW12O40), Wells-Dawson- (H6P2W18O62), and Preyssler-type (H14[NaP5W30O110]) HPA catalysts. Successful formation of HPA catalysts was well confirmed by FT-IR, 31P NMR, and ICP-AES analyses. Acid properties of HPA catalysts were determined by NH3-TPD (temperature-programmed desorption) measurements. Acid strength of the catalysts increased in the order of H14[NaP5W30O110] < H6P2W18O62 < H3PW12O40. The catalytic performance of HPA catalysts was closely related to the acid strength of the catalysts. In the etherification of n-butanol to di-n-butyl ether over various structural classes of HPA catalysts, Conversion of n-butanol and yield for di-n-butyl ether increased with increasing acid strength of HPA catalysts. Among the catalysts tested, Keggin-type (H3PW12O40) HPA catalyst with the strongest acid strength showed the best catalytic performance. Acid strength of HPAs served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-butyl ether.

  13. Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration.

    PubMed

    Marcì, G; García-López, E; Bellardita, M; Parisi, F; Colbeau-Justin, C; Sorgues, S; Liotta, L F; Palmisano, L

    2013-08-28

    Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas-solid regime at atmospheric pressure and 85 °C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM species played a key role both for the catalytic and the photo-assisted catalytic reactions, due to their strong acidity and ability to form strong oxidant species under UV irradiation, respectively. The contemporary presence of heat and UV light improved the activity of almost all POM supported materials. All materials were characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM), diffuse reflectance spectroscopy (DRS), determination of the conduction and valence band energy by photovoltage measurements, Fourier transform infrared spectroscopy (FTIR), NH3-TPD experiments and time resolved microwave conductivity (TRMC).

  14. di Synthesis and Characterization of the Platinum-Substituted Keggin Anion alpha-H2SiPtW11O404-

    SciTech Connect

    Klonowski, P; Goloboy, JC; Uribe-Romo, FJ; Sun, FR; Zhu, LY; Gandara, F; Wills, C; Errington, RJ; Yaghi, OM; Klemperer, WG

    2014-12-15

    Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anion salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.

  15. DMAP-catalyzed esterification of pentaerythritol-derivatized POMs: a new route for the functionalization of polyoxometalates.

    PubMed

    Wu, Pingfan; Xiao, Zicheng; Zhang, Jin; Hao, Jian; Chen, Jiake; Yin, Panchao; Wei, Yongge

    2011-05-21

    We have demonstrated that a pentaerythritol-derivatized hexavanadate can be easily esterified with acid anhydrides using 4-(N,N-dimethylamino)pyridine (DMAP) as a catalyst, which provides a convenient method for the functionalization of polyoxometalates. © The Royal Society of Chemistry 2011

  16. Manganese-Substituted Polyoxometalate as an Effective Shuttle Redox Mediator in Z-Scheme Water Splitting under Visible Light.

    PubMed

    Tsuji, Kohei; Tomita, Osamu; Higashi, Masanobu; Abe, Ryu

    2016-08-23

    In the present study, a polyoxometalate is for the first time applied as a shuttle redox in two-step (Z-Scheme) photocatalytic water splitting. Photocatalytic H2 evolution using a Mn-substituted polyoxometalate [SiW11 O39 Mn(II) (H2 O)](6-) as an electron donor proceeded over a Ru-loaded SrTiO3 :Rh photocatalyst under visible light with relatively high selectivity, accompanied by the stoichiometric production of its oxidized form [SiW11 O39 Mn(III) (H2 O)](5-) . Photocatalytic O2 evolution using the oxidized [SiW11 O39 Mn(III) (H2 O)](5-) as an electron acceptor proceeded over PtOx -loaded WO3 photocatalyst under visible light with relatively high quantum efficiency and selectivity, whereas the loading of effective PtOx cocatalyst was necessary to facilitate the reduction of polyoxometalate. Finally, a two-step water splitting into H2 and O2 was demonstrated under visible light using the couple of Mn-substituted polyoxometalate as shuttle redox between Ru/SrTiO3 :Rh and PtOx /WO3 photocatalysts, under mildly acidic conditions with pH≈4.5. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Structural link between giant molybdenum oxide based ions and derived Keggin structure: modular assemblies based on the [BW11O39]9- ion and pentagonal {M'M5} units (M' = W; M = Mo,W).

    PubMed

    Leclerc-Laronze, Nathalie; Marrot, Jérôme; Thouvenot, René; Cadot, Emmanuel

    2009-01-01

    Linked to the Pentagon: The addition of molybdate to [HBW(11)O(39)](8-) ions leads to the formation of mixed pentagonal units {W(Mo(5))} and {W(WMo(4))} trapped as linkers in the resulting modular assemblies, thus establishing the first link between the conventional Keggin ion derivatives and the giant molybdenum oxide and keplerate ions.

  18. Location of protons in anhydrous Keggin heteropolyacids H(3)PMo(12)O(40) and H(3)PW(12)O(40) by (1)H[(31)P]/(31)P[(1)H] REDOR NMR and DFT quantum chemical calculations.

    PubMed

    Ganapathy, S; Fournier, M; Paul, J F; Delevoye, L; Guelton, M; Amoureux, J P

    2002-07-03

    HeteroPolyAcids (HPA's) are a class of solid acids that have broad applications in many fields of science and technology, including catalysis and chemical engineering. The proton locations within the thermally stable and commonly known Keggin unit, which is the primary structure building unit/block, has remained undetermined in anhydrous HPAs, despite numerous theoretical and experimental efforts. However, Rotational Echo DOuble Resonance (REDOR) NMR and Density Functional Theory (DFT) quantum chemical calculations offer a new opportunity to determine the exact locations of protons within the Keggin unit. The crucial experimental evidence is provided for the basic and very extensively studied acidic form of H(8-n)X(n+)M(12)O(40), X = Si, P and M = Mo, W, belonging to the Keggin structure. While showing that the acidic protons are located in the bridging oxygen positions (R(P-H) = 520 +/- 20 pm) in H(3)PMo(12)O(40) and in the terminal oxygen positions (R(P-H) = 570 +/- 20 pm) in H(3)PW(12)O(40), REDOR measurements also provide for the first time the structural basis to consistently rank the acid strength for the important class of Keggin solid catalysts.

  19. Passing Current through Electrically Conducting Lyotropic Liquid Crystals and Micelles Assembled from Hybrid Surfactants with π-Conjugated Tail and Polyoxometalate Head

    PubMed Central

    2016-01-01

    The solvent-mediated ability for molecularly encoded self-assembly into states of higher order (micelles, lyotropic liquid crystals) embodies the basis for many applications of surfactants in science and society. Surfactants are used frequently in recipes for nanoparticle synthesis. Because ordinary surfactants comprise insulating constituents (alkyl groups as side-chains and charged organic heads), such nanostructures are wrapped in an electrically inactive barrier, and this is a large disadvantage for future developments in nanotechnology. Implications of micelles with electrically conducting walls made from either “metallic” or “semiconducting” surfactants are huge, also in other areas such as nanoelectrocatalysis or micellar energy storage. We cross this frontier by replacing not only the hydrophilic chain but also the hydrophilic head by electronically conducting entities. We report the synthesis of surfactants with oligo para-phenylene-ethynylene as a π-conjugated side-chain attached to a redox-active, inorganic polyoxometalate cluster as charged head. It is proven that electronic communication between head and tail takes place. Hybridization on the molecular level leads to the emergence of advanced surfactant features such as semiconductor properties (Egap = 2.6 eV) in soft lyotropic systems (micelles, liquid crystals). PMID:27809472

  20. Passing Current through Electrically Conducting Lyotropic Liquid Crystals and Micelles Assembled from Hybrid Surfactants with π-Conjugated Tail and Polyoxometalate Head.

    PubMed

    Klaiber, Alexander; Polarz, Sebastian

    2016-11-22

    The solvent-mediated ability for molecularly encoded self-assembly into states of higher order (micelles, lyotropic liquid crystals) embodies the basis for many applications of surfactants in science and society. Surfactants are used frequently in recipes for nanoparticle synthesis. Because ordinary surfactants comprise insulating constituents (alkyl groups as side-chains and charged organic heads), such nanostructures are wrapped in an electrically inactive barrier, and this is a large disadvantage for future developments in nanotechnology. Implications of micelles with electrically conducting walls made from either "metallic" or "semiconducting" surfactants are huge, also in other areas such as nanoelectrocatalysis or micellar energy storage. We cross this frontier by replacing not only the hydrophilic chain but also the hydrophilic head by electronically conducting entities. We report the synthesis of surfactants with oligo para-phenylene-ethynylene as a π-conjugated side-chain attached to a redox-active, inorganic polyoxometalate cluster as charged head. It is proven that electronic communication between head and tail takes place. Hybridization on the molecular level leads to the emergence of advanced surfactant features such as semiconductor properties (Egap = 2.6 eV) in soft lyotropic systems (micelles, liquid crystals).

  1. Synthesis and structural characterization of polyoxometalates incorporating with anilinium cations and facile preparation of hybrid film

    NASA Astrophysics Data System (ADS)

    Fukaya, Keisuke; Srifa, Atthapon; Isikawa, Eri; Naruke, Haruo

    2010-08-01

    The self-assembly reaction of tungstate and copper(II) in the presence of aniline (ANI) and phosphoric acid led to the formation of an anilinium (ANIH +) salt of mono-substituted Keggin-type polyoxotungstophosphate (ANIH) 5[PCu(H 2O)W 11O 39](ANI)·8H 2O ( 1), while the reaction of heptamolybdate in the coexistence of copper(II), phosphoric acid and ANI yielded an ANIH + salt of Strandberg-type pentamolybdodiphosphate, (ANIH) 2[(PO 4) 2Mo 5O 15{Cu(ANI) 2(H 2O)} 2](ANI)·2H 2O ( 2). These compounds were characterized by elemental analysis, infrared spectroscopy and X-ray single-crystal analysis. The compound 1, crystallizing in trigonal, P3¯,a = 13.883(4), c = 10.187(3) Å, Z = 1, consists of copper mono-substituted Keggin-typed [PCu(H 2O)W 11O 39] 5- anion surrounded by six ANI molecules, of which five are protonated (ANIH +). The compound 2, crystallizing in triclinic, P1¯,a = 13.98(2), b = 14.73(1), c = 16.24(1) Å, α = 111.27(3), β = 97.42(3), γ = 99.54(4)°, Z = 2, consists of Strandberg-type pentamolybdodiphospate [(PO 4) 2Mo 5O 15] 6- anions interconnected by two Cu(ANI) 2(H 2O) linkers to form a 1D-chain structure. A potentiostatic electrolysis of 1 in aqueous solution gave rise to electropolymerization of the ANIH + cations (and ANI) and deposition with the [PCu(H 2O)W 11O 39] 5- anion on an ITO electrode, forming a nano-structured polyaniline/[PCu(H 2O)W 11O 39] 5- hybrid thin film.

  2. Direct synthesis of inverse hexagonally ordered diblock copolymer/polyoxometalate nanocomposite films.

    PubMed

    Lunkenbein, Thomas; Kamperman, Marleen; Li, Zihui; Bojer, Carina; Drechsler, Markus; Förster, Stephan; Wiesner, Ulrich; Müller, Axel H E; Breu, Josef

    2012-08-01

    Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.

  3. Manual assembly of a rare-earth polyoxometalate microcrystal film showing highly polarized luminescence.

    PubMed

    Zhang, Rui; Qin, Libo; Iqbal, Arshad; Zhou, Yunshan; Zhang, Lijuan; Ren, Haizhou; Lv, Xiaofei; Li, Minglei

    2017-07-18

    Currently, the realization of rationally designed architectures based on polyoxometalates (POMs) with designed functions has mostly been achieved through the preparation of functional films. However, the traditional approaches suffer from the drawbacks such as time-consuming processes, ill-defined structure and quality, random orientation of the POM molecules, and unsatisfactory performance. In this study, microcrystals of Ag9[EuW10O36]·36H2O (denoted as Ag9[EuW10O36]) were synthesized via a titration method by treating Na9[EuW10O36]·32H2O (denoted as Na9[EuW10O36]), selected as a prototype, with Ag(+), leading to the formation of a water-insoluble crystalline powder with a uniform hexagonal platelet morphology. After this, a simple yet efficient manual assembly method was used to rapidly manufacture Ag9EuW10O36 microcrystal thin films on a glass substrate with high coverage, high crystallinity, and highly preferential orientation. Note that the as-prepared films emit orange polarized fluorescence with an anisotropy value of about 0.21, which places them among the materials of largest anisotropy. It is expected that the manual assembly approach can be generally adopted for the fabrication of many other kinds of polyoxometalate-based materials on various substrates for practical applications.

  4. Controllable fabrication of platinum nanospheres with a polyoxometalate-assisted process

    SciTech Connect

    Sun Guoying; Li Qiuyu; Xu Rui; Gu Jianmin; Ju Mingliang; Wang Enbo

    2010-11-15

    Pt nanospheres with an average diameter of 60{+-}10 nm have been successfully synthesized at room temperature through a facile polyoxometalate(POM)-assisted process. Characterization by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) clearly showed that these Pt nanospheres consisted of 2-7 nm Pt nanodots. During the formation of such unique nanostructures, POMs were found to serve as both catalyst and stabilizer. The size of the as-synthesized Pt nanospheres could be controlled solely by adjusting the molar ratio of POMs to H{sub 2}PtCl{sub 6}. A possible formation mechanism based on POMs-mediated electron transfer from ascorbic acid (AA) to PtCl{sub 6}{sup 2-} and AA-assisted aggregation was tentatively proposed to rationalize the formation of such nanostructures. Importantly, these specific Pt nanospheres exhibited good electrocatalytic activity towards the oxidation of methanol, making them promising for applications in direct methanol fuel cells. - Graphical abstract: Large-scale Pt nanospheres were synthesized through a polyoxometalate-assisted process, and exhibited good electrocatalytic activity towards the oxidation of methanol, making them promising for applications in fuel cells. Display Omitted

  5. Identification of a polyoxometalate inhibitor of the DNA binding activity of Sox2.

    PubMed

    Narasimhan, Kamesh; Pillay, Shubhadra; Bin Ahmad, Nor Rizal; Bikadi, Zsolt; Hazai, Eszter; Yan, Li; Kolatkar, Prasanna R; Pervushin, Konstantin; Jauch, Ralf

    2011-06-17

    Aberrant expression of transcription factors is a frequent cause of disease, yet drugs that modulate transcription factor protein-DNA interactions are presently unavailable. To this end, the chemical tractability of the DNA binding domain of the stem cell inducer and oncogene Sox2 was explored in a high-throughput fluorescence anisotropy screen. The screening revealed a Dawson polyoxometalate (K(6)[P(2)Mo(18)O(62)]) as a direct and nanomolar inhibitor of the DNA binding activity of Sox2. The Dawson polyoxometalate (Dawson-POM) was found to be selective for Sox2 and related Sox-HMG family members when compared to unrelated paired and zinc finger DNA binding domains. [(15)N,(1)H]-Transverse relaxation optimized spectroscopy (TROSY) experiments coupled with docking studies suggest an interaction site of the POM on the Sox2 surface that enabled the rationalization of its inhibitory activity. The unconventional molecular scaffold of the Dawson-POM and its inhibitory mode provides strategies for the development of drugs that modulate transcription factors.

  6. Spontaneous structuration in coacervate-based protocells by polyoxometalate-mediated membrane assembly.

    PubMed

    Williams, David S; Patil, Avinash J; Mann, Stephen

    2014-05-14

    Molecularly crowded, polyelectrolyte/ribonucleotide-enriched membrane-free coacervate droplets are transformed into membrane-bounded sub-divided vesicles by using a polyoxometalate-mediated surface-templating procedure. The coacervate to vesicle transition results in reconstruction of the coacervate micro-droplets into novel three-tiered micro-compartments comprising a semi-permeable negatively charged polyoxometalate/polyelectrolyte outer membrane, a sub-membrane coacervate shell, and an internal aqueous lumen. We demonstrate that organic dyes, ssDNA, magnetic nanoparticles and enzymes can be concentrated into the interior of the micro-compartments by sequestration into the coacervate micro-droplets prior to vesicle formation. The vesicle-encapsulated proteins are inaccessible to proteases in the external medium, and can be exploited for the spatial localization and coupling of two-enzyme cascade reactions within single or between multiple populations of hybrid vesicles dispersed in aqueous media. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Oxidative Polyoxometalates Modified Graphitic Carbon Nitride for Visible-Light CO2 Reduction.

    PubMed

    Zhou, Jie; Chen, Weichao; Sun, Chunyi; Han, Lu; Qin, Chao; Chen, Mengmeng; Wang, Xinlong; Wang, Enbo; Su, Zhongmin

    2017-03-24

    Developing a photocatalysis system for converting CO2 to valuable fuels or chemicals is a promising strategy to address global warming and fossil fuel consumption. Exploring photocatalysts with high-performance and low-cost has been two ultimate goals toward photoreduction of CO2. Herein, noble-metal-free polyoxometalates (Co4) with oxidative ability was first introduced into g-C3N4 resulted in inexpensive hybrid materials (Co4@g-C3N4) with staggered band alignment. The staggered composited materials show a higher activity of CO2 reduction than bare g-C3N4. An optimized Co4@g-C3N4 hybrid sample exhibited a high yield (107 μmol g(-1) h(-1)) under visible-light irradiation (λ ≥ 420 nm), meanwhile maintaining high selectivity for CO production (94%). After 10 h of irradiation, the production of CO reached 896 μmol g(-1). Mechanistic studies revealed the introduction of Co4 not only facilitate the charge transfer of g-C3N4 but greatly increased the surface catalytic oxidative ability. This work creatively combined g-C3N4 with oxidative polyoxometalates which provide novel insights into the design of low-cost photocatalytic materials for CO2 reduction.

  8. Hydrothermal syntheses, crystal structures and properties of 0-D, 1-D and 2-D organic-inorganic hybrid borotungstates constructed from Keggin-type heteropolyanion [α-BW 12O 40] 5- and transition-metal complexes

    NASA Astrophysics Data System (ADS)

    Zhao, Junwei; Song, Yiping; Ma, Pengtao; Wang, Jingping; Niu, Jingyang

    2009-07-01

    Three novel organic-inorganic hybrid borotungstates {[Ni(phen) 2(H 2O)] 2H(α-BW 12O 40)}·4H 2O ( 1), [Cu I(2,2'-bipy)(4,4'-bipy) 0.5] 2{[Cu I(2,2'-bipy)] 2Cu I(4,4'-bipy) 2(α-BW 12O 40)} ( 2) and {[Cu I(4,4'-bipy)] 3H 2(α-BW 12O 40)}·3.5H 2O ( 3) (phen=1,10-phenanthroline, 2,2'-bipy=2,2'-bipyridine, 4,4'-bipy=4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and photoluminescence. The structural analysis reveals that 1 consists of a 0-D bisupporting polyoxometalate cluster where two [Ni(phen) 2(H 2O)] 2+ cations are grafted on the polyoxoanion [α-BW 12O 40] 5- through two terminal oxygen atoms, 2 shows a 1-D infinite chain constructed from [α-BW 12O 40] 5- polyoxoanions and {[Cu I(2,2'-bipy)] 2Cu I(4,4'-bipy) 2} 3+ cations by means of alternating fashion, and 3 displays an unprecedented 2D extended structure built by [α-BW 12O 40] 5- polyoxoanions and -Cu I-4,4'-bipy- linear chains, in which each [α-BW 12O 40] 5- polyoxoanion acts as a tetradentate inorganic ligand and provides three terminal oxygen atom and one two-bridging oxygen atom. The presence of Ni II and W VI in 1, Cu I ions and W VI in 2 and 3 are identified by XPS spectra. The photoluminescence of 2 and 3 are also investigated.

  9. Photo-catalytic H 2 evolution over a series of Keggin-structure heteropoly blue sensitized Pt/TiO 2 under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Fu, Ning; Lu, Gongxuan

    2009-02-01

    We report the visible light-induced hydrogen generation over a series of Keggin-structure heteropoly blue (HPB) anions (PW 12O 403-, phosphotungstic blue (PTB), GeW 12O 404- (GTB), SiW 12O 404- (STB), BW 12O 405- (BTB)) sensitized Pt/TiO 2 photo-catalysts. The sensitization of TiO 2 by HPB was certified using photo-electrochemical measurements and UV-vis absorption spectra. PTB showed the most pronounced sensitization effect for TiO 2 in those HPB anions and Pt/TiO 2-PTB showed the highest hydrogen generation activity. The sensitization of TiO 2 was significantly dependent on the reduction potential of HPA, which was determined by the kind of central atom in HPA.

  10. Molecular growth from a Mo176 to a Mo248 cluster

    NASA Astrophysics Data System (ADS)

    Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

    1999-01-01

    In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

  11. A DFT study on NLO response of push-pull hybrid porphyrin-polyoxometalate complexes

    NASA Astrophysics Data System (ADS)

    Yao, Chan; Hu, Bo; Wang, Qingwei; Song, Ping; Su, Zhongmin

    2014-06-01

    Density functional theory (DFT) calculations were carried out to investigate the second-order nonlinear optical (NLO) properties of a series of proposed porphyrin-polyoxometalate-based complexes related to [5-(3,5-dimethyl-4-hexamolybdate amino-phenyl-ethynyl)-15-(4-nitrophenyl-ethynyl)porphinato]zinc(II) which have donor-π conjugated bridge-acceptor (D-π-A) configurations. Our calculations show that these species possess considerably large molecular total second-order polarizability (β0), ˜2000 × 10-30 esu. Furthermore, it can be seen that {W6O18} exhibits stronger electron-donating ability than {Mo6O18}. And two-dimensional (2D) system with A-π-D-π-A structure might be a promising candidate for NLO materials based on the large β0 (4583.5 × 10-30 esu) and in-plane nonlinear anisotropy.

  12. Degradable Organically-Derivatized Polyoxometalate with Enhanced Activity against Glioblastoma Cell Line

    NASA Astrophysics Data System (ADS)

    She, Shan; Bian, Shengtai; Huo, Ruichao; Chen, Kun; Huang, Zehuan; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-09-01

    High efficacy and low toxicity are critical for cancer treatment. Polyoxometalates (POMs) have been reported as potential candidates for cancer therapy. On accounts of the slow clearance of POMs, leading to long-term toxicity, the clinical application of POMs in cancer treatment is restricted. To address this problem, a degradable organoimido derivative of hexamolybdate is developed by modifying it with a cleavable organic group, leading to its degradation. Of note, this derivative exhibits favourable pharmacodynamics towards human malignant glioma cell (U251), the ability to penetrate across blood brain barrier and low toxicity towards rat pheochromocytoma cell (PC12). This line of research develops an effective POM-based agent for glioblastoma inhibition and will pave a new way to construct degradable anticancer agents for clinical cancer therapy.

  13. Degradable Organically-Derivatized Polyoxometalate with Enhanced Activity against Glioblastoma Cell Line

    PubMed Central

    She, Shan; Bian, Shengtai; Huo, Ruichao; Chen, Kun; Huang, Zehuan; Zhang, Jiangwei; Hao, Jian; Wei, Yongge

    2016-01-01

    High efficacy and low toxicity are critical for cancer treatment. Polyoxometalates (POMs) have been reported as potential candidates for cancer therapy. On accounts of the slow clearance of POMs, leading to long-term toxicity, the clinical application of POMs in cancer treatment is restricted. To address this problem, a degradable organoimido derivative of hexamolybdate is developed by modifying it with a cleavable organic group, leading to its degradation. Of note, this derivative exhibits favourable pharmacodynamics towards human malignant glioma cell (U251), the ability to penetrate across blood brain barrier and low toxicity towards rat pheochromocytoma cell (PC12). This line of research develops an effective POM-based agent for glioblastoma inhibition and will pave a new way to construct degradable anticancer agents for clinical cancer therapy. PMID:27658479

  14. Pd0@Polyoxometalate Nanostructures as Green Electrocatalysts: Illustrative Example of Hydrogen Production

    PubMed Central

    Biboum, Rosa N.; Keita, Bineta; Franger, Sylvain; Njiki, Charles P. Nanseu; Zhang, Guangjin; Zhang, Jie; Liu, Tianbo; Mbomekalle, Israel-Martyr; Nadjo, Louis

    2010-01-01

    Green-chemistry type procedures were used to synthesize Pd0 nanostructures encapsulated by a vanadium-substituted Wells-Dawson-type polyoxometalate (Pd0@POM). The cyclic voltammogram run with the Pd0@POM-modified glassy carbon electrode shows well-defined waves, associated with Pd0 nanostructures and the VV/VIV redox couple. The Pd0@POM-modified electrode displayed remarkably reproducible cyclic voltammetry patterns. The hydrogen evolution reaction (HER) was selected as an illustrative example to test the electrocatalytic behavior of the electrode. The kinetic parameters of the HER show the high efficiency of the Pd0@POM-modified electrode. This is the first example of electrochemical characterization of a modified electrode based on a vanado-tungstic POM and Pd0 nanostructures.

  15. Spin dynamics of the giant polyoxometalate molecule {Mn₄₀W₂₂₄} studied by NMR.

    PubMed

    Furukawa, Y; Fang, X; Kögerler, P

    2014-05-14

    (7)Li nuclear magnetic resonance (NMR) studies have been performed to investigate magnetic properties and spin dynamics of Mn(3+) (S = 2) spins in the giant polyoxometalate molecule {Mn₄₀W₂₂₄}. The (7)Li-NMR line width is proportional to the external magnetic field H as expected in a paramagnetic state above 3 K. Below this temperature the line width shows a sudden increase and is almost independent of H, which indicates freezing of the local Mn(3+) spins. The temperature dependence of T₁ for both (1)H and (7)Li reveals slow spin dynamics at low temperatures, consistent with spin freezing. The slow spin dynamics is also evidenced by the observation of a peak of 1/T₂ around 3 K, where the fluctuation frequency of spins is of the order of ∼200 kHz. An explicit form of the temperature dependence of the fluctuation frequency of Mn(3+) spins is derived from the nuclear relaxation data.

  16. Designing artificial photosynthetic devices using hybrid organic-inorganic modules based on polyoxometalates.

    PubMed

    Symes, Mark D; Cogdell, Richard J; Cronin, Leroy

    2013-08-13

    Artificial photosynthesis aims at capturing solar energy and using it to produce storable fuels. However, while there is reason to be optimistic that such approaches can deliver higher energy conversion efficiencies than natural photosynthetic systems, many serious challenges remain to be addressed. Perhaps chief among these is the issue of device stability. Almost all approaches to artificial photosynthesis employ easily oxidized organic molecules as light harvesters or in catalytic centres, frequently in solution with highly oxidizing species. The 'elephant in the room' in this regard is that oxidation of these organic moieties is likely to occur at least as rapidly as oxidation of water, meaning that current device performance is severely curtailed. Herein, we discuss one possible solution to this problem: using self-assembling organic-polyoxometalate hybrid structures to produce compartments inside which the individual component reactions of photosynthesis can occur without such a high incidence of deleterious side reactions.

  17. Supramolecular Assembly of Organic-Inorganic Hybrid Polyoxometalate Nanoclusters at Solid-liquid Interface

    NASA Astrophysics Data System (ADS)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2013-03-01

    Polyoxometalate (POM) inorganic nanoclusters have recently emerged as building blocks for the design and synthesis of novel functional materials for broad applications ranging from catalysis to nanomedicines. Rather than taking the slow self-assembly of POMs in aqueous solutions, we have investigated the assembly of hybrid Anderson-type Mo-based POMs with organic ligands at a solid surface by Langmuir-Blodgett (LB) deposition and characterized the films by AFM, TEM, and X-ray diffraction. We have observed the formation of well-ordered monolayer or bilayer consisting of periodic arrangement of hybrid POM nanoclusters, showing a strong dependence on substrate chemistry and LB compression pressure. The controlled assembly of hybrid POM nanocluster films by LB deposition could be used as a template with stoichiometric crystalline nanostructure to the programmed assembly of novel multi-functional supramolecular complexes.

  18. Electrostatically self-assembled polyoxometalates on molecular-dye-functionalized diamond.

    PubMed

    Zhong, Yu Lin; Ng, Wibowo; Yang, Jia-Xiang; Loh, Kian Ping

    2009-12-30

    We have successfully immobilized phosphotungstic acid (PTA), a polyoxometalate, on the surface of boron-doped diamond (BDD) surface through electrostatic self-assembly of PTA on pyridinium dye-functionalized-BDD. The inorganic/organic bilayer structure on BDD is found to exhibit fast surface-confined reversible electron transfer. The molecular dye-grafted BDD can undergo controllable electrical stripping and regeneration of PTA which can be useful for electronics or sensing applications. Furthermore, we have demonstrated the use of PTA as a molecular switch in which the direction of photocurrent from diamond to methyl viologen is reversed by the surface bound PTA. Robust photocurrent converter based on such molecular system-diamond platform can operate in corrosive medium which is not tolerated by indium tin oxide electrodes.

  19. Light- and Solvent-Controlled Self-Assembly Behavior of Spiropyran-Polyoxometalate-Alkyl Hybrid Molecules.

    PubMed

    Chu, Yang; Saad, Ali; Yin, Panchao; Wu, Jiayingzi; Oms, Olivier; Dolbecq, Anne; Mialane, Pierre; Liu, Tianbo

    2016-08-08

    A molecular photochromic spiropyran-polyoxometalate-alkyl organic-inorganic hybrid has been synthesized and fully characterized. The reversible switching of the hydrophobic spiropyran fragment to the hydrophilic merocyanine one can be easily achieved under light irradiation at different wavelengths. This switch changes the amphiphilic feature of the hybrid, leading to a light-controlled self-assembly behavior in solution. It has been shown that the hybrid can reversibly self-assemble into vesicles in polar solvents and irreversibly into reverse vesicles in non-polar solvents. The sizes of the vesicles and the reverse vesicles are both tunable by the polarity of the solvent, with the hydrophobic interactions being the main driving force. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Photoelectrocatalytic Oxidation of Formic Acid at Titania@Polyoxometalate/Gold Nanocomposite Material Modified Electrode.

    PubMed

    Pandiyarajan, Chinnappan; Pandikumar, Alagarsamy; Ramaraj, Ramasamy

    2015-09-01

    Amine functionalized silicate sol-gel stabilized titania (P25)-polyoxometalate (PTA)-gold (Au) nanocomposite materials (APS/(P25-PTA-Au)(NCM)) were prepared by a simple chemical reduction method and were used to fabricate modified photoelectrode for the photoelectrocatalytic oxidation of formic acid. The APS/(P25-PTA-Au)(NCM) photoelectrode showed synergistic photoelectrocatalytic behavior towards the oxidation of formic acid. The photoresponse of the APS/(P25-PTA-Au)(NCM) modified photoelectrode was found to be higher when compared to the controlled photoelectrodes. The present study shows that the loading of Au(nps) on APS/P25-PTA is more beneficial to enhance the photoinduced interfacial charge transfer process, which leads to increased photocurrent generation. The present study concludes that the photoelectrocatalytic oxidation of formic acid at the APS/(P25-PTA-Au)(NCM) photoelectrode will boost the formic acid fuel cell performance.