Co-reporter:Xin-Bao Han, Zhi-Ming Zhang, Teng Zhang, Yang-Guang Li, Wenbin Lin, Wansheng You, Zhong-Min Su, and En-Bo Wang
Journal of the American Chemical Society April 9, 2014 Volume 136(Issue 14) pp:5359-5366
Publication Date(Web):March 24, 2014
DOI:10.1021/ja412886e
A series of all-inorganic, abundant-metal-based, high-nuclearity cobalt–phosphate (Co–Pi) molecular catalysts [{Co4(OH)3(PO4)}4(SiW9O34)4]32– (1), [{Co4(OH)3(PO4)}4(GeW9O34)4]32– (2), [{Co4(OH)3(PO4)}4(PW9O34)4]28– (3), and [{Co4(OH)3(PO4)}4(AsW9O34)4]28– (4) were synthesized and shown to be highly effective at photocatalytic water oxidation. The {Co16(PO4)4} cluster contains a Co4O4 cubane which is structurally analogous to the [Mn3CaO4] core of the oxygen-evolving complex (OEC) in photosystem II (PSII). Compounds 1–4 were shown to be the first POM-based Co–Pi-cluster molecular catalysts for visible light-driven water oxidation, thus serving as a functional model of the OEC in PSII. The systematic synthesis of four isostructural analogues allowed for investigating the influence of different heteroatoms in the POM ligands on the photocatalytic activities of these Co–Pi cluster WOCs. Further, the POM-based photocatalysts readily recrystallized from the photocatalytic reaction systems with the polyoxoanion structures unchanged, which together with the laser flash photolysis, dynamic light-scattering, 31P NMR, UV–vis absorption, POM extraction, and ICP-MS analysis results collectively confirmed that compounds 1–4 maintain their structural integrity under the photocatalytic conditions. This study provides not only a valuable molecular model of the “Co–Pi” catalysts with a well-defined structure but also an unprecedented opportunity to fine-tune high-nuclearity POM clusters for visible light-driven water splitting.
Co-reporter:Zhu-Jun Liu, Xin-Long Wang, Chao Qin, Zhi-Ming Zhang, Yang-Guang Li, Wei-Lin Chen, En-Bo Wang
Coordination Chemistry Reviews 2016 Volume 313() pp:94-110
Publication Date(Web):15 April 2016
DOI:10.1016/j.ccr.2015.12.006
The {Mn4O5Ca} cluster of photosystem II is a well-known cubane-like transition-metal (TM) cluster that plays important roles in solar energy conversion. The artificial synthesis of cubane-like TM clusters and their interesting potential applications have been widely studied. Most of them were isolated by use of organic ligands, and therefore their potential applications were essentially restricted to organic solvents because of their limited stability in aqueous solution. In recent decades, lacunary polyoxometalates (POMs) composed of WVI/MoVI centers have been used to replace organic ligands as stable and oxidative-resistant pure-inorganic multidentate ligands to construct water-soluble and water-stable molecular clusters. In the course of the mimicking of the {Mn4O5Ca} subsite of photosystem II, significant advances have already been made in POM-assisted artificial synthesis of TM cubanes. Compared with classic cubane-like TM clusters, these POM-based TM cubane clusters can not only dissolve in organic solvents by virtue of a simple phase-transfer reaction but also display excellent aqueous stability. Consequently, the synthesis of these pure-inorganic cubane clusters offers a great opportunity for expanding the applications of cubane-like TM clusters. This review focuses on the synthetic strategies for, structures of, and applications of these POM-based TM cubane clusters, particularly highlighting how POMs can be used as the inorganic ligands to construct cubane-like TM clusters. The purpose of this review is to give a representative and comprehensive overview of the work done so far in this emerging field.
Co-reporter:Chun-Jie Wang, Ting-Ting Wang, Qing Lan, Shuang Yao, Hong-Li Wu, Yang-Yang Zhou, Zhi-Ming Zhang and En-Bo Wang
RSC Advances 2016 vol. 6(Issue 19) pp:15513-15517
Publication Date(Web):01 Feb 2016
DOI:10.1039/C5RA23830G
A new polyrotaxane structure, {Ag8O(Htrz)4(4,4′-bpy)2}{AgPMo12O40} (Htrz = 1,2,4-triazole, 4,4′-bpy = 4,4′-bipyridine) (1), was obtained by the reaction of Ag+, H5PMo10V2O40 and mixed organic linking ligands under hydrothermal conditions. The structure has been characterized by IR, TG analysis, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction. In 1, a purely inorganic 1D chain composed of Keggin-type polyoxoanions and Ag+ linkers, interluded into the 2D Ag–organic layers, resulting in the polyrotaxane structure. This is the first polyrotaxane compound constructed from a POM-based purely inorganic 1D chain and Ag-Htrz-4,4′-bpy 2D networks. The ratio of the mixed ligands played a crucial role in the synthesis of the title compound. Moreover, compound 1 exhibited efficient catalytic activity for the oxidation of desulfurization, and possessed electrocatalytic activity for the reduction of H2O2 and BrO3−.
Co-reporter:Yang-Yang Zhou, Shuang Yao, Jing-Hui Yan, Li Chen, Ting-Ting Wang, Chun-Jie Wang and Zhi-Ming Zhang
Dalton Transactions 2015 vol. 44(Issue 47) pp:20435-20440
Publication Date(Web):16 Oct 2015
DOI:10.1039/C5DT03397G
Two purely inorganic three-dimensional (3D) frameworks [Mn4(H2O)11VIV18O42(PO4)]7− (1) and [Mn2(H2O)7VIV18O42(PO4)]11− (2) were synthesized under hydrothermal conditions and fully characterized by single-crystal X-ray structural analysis, IR spectroscopy, thermogravimetric analysis and PXRD. Structural analysis revealed that these two compounds contained a similar all reduced polyoxoanion [VIV18O42(PO4)]15− linked by different amounts of manganese centers to form 3D framework materials. The V centers in these two compounds were all reduced to the +IV oxidation state, resulting in an all reduced polyoxoanion, which was firstly used as the building block for constructing 3D framework materials. The all reduced typical polyoxoanion [VIV18O42(PO4)]15− with 15 negative charges supplied enough charge amount to accept TM cations. In these two structures, the anions were surrounded by 12 and 5 Mn2+ ions, respectively, adjusted by varying the feeding amount of MnCl2·4H2O. An electrocatalytic study revealed that compound 1 exhibits electrocatalytic activity for reduction of H2O2.
Co-reporter:Hong-Li Wu, Zhi-Ming Zhang, Yang-Guang Li, Xin-Long Wang and En-Bo Wang
CrystEngComm 2015 vol. 17(Issue 33) pp:6261-6268
Publication Date(Web):19 Jun 2015
DOI:10.1039/C5CE00909J
Transition metal (TM) cations and clusters have been widely used to functionalize polyoxometalates (POMs) of tungsten, molybdenum and vanadium due to their acidic nature, which made them compatible with addendum TM cations. Together with the good understanding of their solution behavior, a number of TM-based POMs have been achieved, which exhibited potential applications in many fields. Comparably, fewer polyoxoniobates (PONs) were obtained due to the poor understanding of their solution behavior, and they could only exist in strong alkaline aqueous solutions, where most of the TM cations precipitate because of the formation of hydroxide or oxide. Recently, TM cations were introduced into PONs by protection of chelate organic ligands or via selection of alkaline-soluble TM cations. Further, lacunary POMs, composed of early TM cations, were used as polydentate ligands to isolate PONs, and they make the PON clusters stably exist in acidic solutions. The acidic nature of tungstoniobate (W–Nb) clusters allowed acid-soluble TM cations to directly functionalize the Nb–W clusters. This highlight focuses on discussing the roles of TM centers in constructing PON-based materials, including TM-cluster-containing PONs, TM–organic group-decorating PONs and niobate clusters isolated by lacunary POMs. This systematic compilation of TM-PON studies will reveal a promising direction for further functionalization of PONs, and it will disclose a richer and more diverse set of structures in PON chemistry.
Co-reporter:Shuang Yao, Jing-Hui Yan, Hui Duan, Qian-Qian Jia, Zhi-Ming Zhang and En-Bo Wang
RSC Advances 2015 vol. 5(Issue 93) pp:76206-76210
Publication Date(Web):03 Sep 2015
DOI:10.1039/C5RA16325K
A new heterometallic 3d–4f cluster-containing polyoxotungstate KNa5{K2Dy2Cu2(H2O)8(SbW9O33)2}·17H2O (1) was designed and synthesized by reaction of the preformed large cluster [N(CH3)4]10Na12[Na2Sb8W36O132(H2O)4]·26H2O ({Sb8W36}), transition-metal (TM) and Ln3+ cations. Compound 1 is the first 3d–4f heterometallic cluster-containing sandwich-type tungstoantimonite obtained by partial decomposition of a preformed large cluster. Further, the sandwich-type polyoxoanion combines with two additional 4p cations resulting in a ring-like 3d–4f–4p cluster {K2Dy2Cu2(H2O)8}-containing polyoxotungstate. The sandwich polyoxoanion {K2Dy2Cu2(H2O)8(SbW9O33)2} was structurally similar to the well-known anion {K3Cu3(H2O)10(SbW9O33)2}, in which one alkali metal cation and one TM cation were both replaced by the rare earth metal cations. Furthermore, the 3d–4f–4p cluster-containing polyoxoanions were bridged by the K+ ion located at their central metal belt into a one-dimensional (1D) wavelike chain. An electrochemical study revealed that compound 1 exhibited electrocatalytic activity for reduction of the NO2− and O2, and a direct 4-electron electrochemical reduction process of O2 was achieved in 1-containing aqueous solution.
Co-reporter:Qing Lan, Zhi-Ming Zhang, Yang-Guang Li and En-Bo Wang
RSC Advances 2015 vol. 5(Issue 55) pp:44198-44203
Publication Date(Web):11 May 2015
DOI:10.1039/C5RA08262E
Two novel transition-metal-cluster-containing arsenicniobates, [Cu(en)2(H2O)][Cu(en)2]4{AsNb9V7O44}·8H2O (1) and [Cu(en)2(H2O)][Cu(en)2]4H{AsNb8V8O44}·11H2O (2), were designed and synthesized by reaction of K7HNb6O19·13H2O, Cu(Ac)2·H2O, Na2VO3, As2O3, and en molecules. Structural analysis revealed that compounds 1 and 2 contained the structural similar [AsNb9V7O44]10− and [AsNb8V8O44]11− polyoxoanions, respectively, which are obtained by inserting a {NbV7} or {V8} ring into the tetravacant polyoxoniobate [AsNb8O36]27−. Polyoxoanions in 1 and 2 could be regarded as the Keggin polyoxoniobates [AsNb9V3O40] or [AsNb8V4O40] capped by four VO5 units. The high-nuclear vanadium clusters were firstly introduced into the Keggin-type arsenicniobates. Further, polyoxoanions in 1 and 2 were connected by the metal–organic linkers into the 1D chain and 2D layer-like framework, respectively. Photocatalytic studies indicated that compounds 1 and 2 are both active for photocatalytic degradation of organic dye in aqueous solution, and they are stable and easily separated from the photocatalytic system for reuse as well.
Co-reporter:Jian-Qiang Shen, Ying Zhang, Zhi-Ming Zhang, Yang-Guang Li, Yan-Qing Gao and En-Bo Wang
Chemical Communications 2014 vol. 50(Issue 45) pp:6017-6019
Publication Date(Web):17 Apr 2014
DOI:10.1039/C3CC49245A
Two phosphoniobate-based 3D frameworks were firstly constructed using the hexa-capped Keggin polyoxoniobates [PNb12O40(VO)6]3− and copper cations. Photocatalytic studies indicated that the hybrid materials exhibit photocatalytic hydrogen evolution activity.
Co-reporter:Ying Zhang, Jian-Qiang Shen, Li-Hua Zheng, Zhi-Ming Zhang, Yu-Xin Li, and En-Bo Wang
Crystal Growth & Design 2014 Volume 14(Issue 1) pp:110-116
Publication Date(Web):November 15, 2013
DOI:10.1021/cg401227g
Four novel heteropolyoxonibate-based inorganic–organic hybrids {Cu(en)2}6{GeNb12VIV2O42}·20H2O (1), {Cu(en)2}3K2Na4{GeNb12VIV2O42}·23H2O (2), {Cu(en)2}6{SiNb12VIV2O42}·18H2O (3), and {Cu(en)2}3K2Na4{SiNb12VIV2O42}·19H2O (4) (en = ethanediamine), composed of polyoxoanions [TNb12O40]16– (T = Si and Ge) and [Cu(en)2]2+ building blocks, were successfully synthesized under hydrothermal conditions by reaction of K7HNb6O19·13H2O, Cu(Ac)2·3H2O, Na2VO3, Na2SiO3, or GeO2 and en molecules. Polyoxoanion [TNb12VIV2O42]12– (T = Si and Ge) can be best described as a α-Keggin core [TNb12O40] with two [VO] units capping on its two “opened windows”. Compounds 1 and 3 are both composed of the bicapped heteropolyoxonibate core surrounded by a shell consisting of twelve [Cu(en)2]2+ groups, which represent a promising structural model toward core–shell nanostructures. Compounds 2 and 4 are also composed of a bicapped polyoxoanion [TNb12VIV2O42]12– (T = Si, Ge) decorated by three metal–organic fragments [Cu(en)2]2+, forming a trisupporting polyoxoanion {[Cu(en)2]3[TNb12O42VIV2]}6–. Antitumor, electrochemical study, and UV–vis spectra indicate that compounds 1–4 exhibit effective antitumor activity against SGC7901 cells and HepG2 cells and could keep the structural integrity in this process.
Co-reporter:Yan-Qing Gao, Zhi-Ming Zhang, Jian-Qiang Shen, Yue Jia, Zhu-Jun Liu and En-Bo Wang
CrystEngComm 2014 vol. 16(Issue 29) pp:6784-6789
Publication Date(Web):27 May 2014
DOI:10.1039/C4CE00536H
Two new hexavacant germanomolybdates, (H2enMe)3K2[Ge2Mo16O58]·4H3O·9H2O (1) (enMe = 1,2-propanediamine) and Na12[Ge2Mo16O58]·30H2O (2), were synthesized through the conventional aqueous method and characterized by X-ray crystallography, elemental analysis, IR spectra and thermogravimetry (TG) analysis. The polyoxoanions in compounds 1 and 2 contain two trivacant Keggin {β-A-GeMo9O34} units fused together by two {MoO6} octahedra. This structural type is different from that of the well-known basic structural types and rarely observed in the POM chemistry. Further, DODACl was used as the surfactant to encapsulate the hexavacant polyoxoanion, resulting in the surfactant-encapsulated cluster (SEC) [DODA]12[Ge2Mo16O58]·16H2O (SEC-Mo16). Polarized optical microscopy, differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VT-XRD) and transmission electron microscopy (TEM) revealed that SEC-Mo16 exhibits characteristic thermotropic liquid crystal properties.
Co-reporter:Yue Liang, Zhi-Ming Zhang, Zhu-Jun Liu, Ying Zhang, Jun Zhang and En-Bo Wang
CrystEngComm 2014 vol. 16(Issue 6) pp:1187-1191
Publication Date(Web):02 Dec 2013
DOI:10.1039/C3CE41278D
A novel pseudosandwich-type polyoxovanadate, CoII2{(VO2)CoIII(CoIIIL)2[V5O16]2}·23H2O (1) (L = 1,3-propanediamine, 1,3-pda), has been isolated using a conventional aqueous solution method and characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and magnetism. Single crystal X-ray diffraction analyses indicate that polyoxoanion 1 is composed of a {CoIII3(1,3-pda)2} cluster coordinated by two lacunary Lindqvist polyoxovanadates [V5O18]. Polyoxoanion 1 contains three CoIII centers in its central metal set, which was first observed in the polyoxometalate chemistry. Further, two CoIII ions in polyoxoanion 1 are functionalized by two 1,3-pda ligands resulting in a pseudosandwich-type polyoxovanadate-based organic–inorganic hybrid material, which represents the first pseudosandwich-type polyoxovanadate decorated by two 1,3-pda ligands.
Co-reporter:Hong-Li Wu, Zhi-Ming Zhang, Yang-Guang Li and En-Bo Wang
RSC Advances 2014 vol. 4(Issue 82) pp:43806-43810
Publication Date(Web):28 Aug 2014
DOI:10.1039/C4RA07525K
Dimethyldioctadecylammonium (DODA+) was used as a surfactant to react with the high-nuclear transition-metal cluster-containing polyoxometalate K5Na11[Ni9(OH)3(H2O)6(HPO4)2(PW9O34)3]·52H2O (POM-1), resulting in an organic–inorganic hybrid complex (DODA)16[Ni9(OH)3(H2O)6(HPO4)2(PW9O34)3]·36H2O (SEP-1), which exhibits characteristic thermotropic liquid crystalline behavior. Here, the high-nuclear transition-metal cluster-substituted polyoxoanions were firstly introduced into liquid crystalline materials. The chemical composition of the obtained SEP-1 was determined by IR spectra, elemental analysis, and thermogravimetric (TG) analysis. Also, polarized optical microscopy, differential scanning calorimetry (DSC), and variable temperature X-ray diffraction (VT-XRD) were performed on SEP-1 to confirm its thermotropic liquid crystalline behavior.
Co-reporter:Yi-Zhen Chen, Zhu-Jun Liu, Zhi-Ming Zhang, Huan-Yu Zhou, Xiao-Tao Zheng, En-Bo Wang
Inorganic Chemistry Communications 2014 Volume 46() pp:155-158
Publication Date(Web):August 2014
DOI:10.1016/j.inoche.2014.05.012
•A group of heterometal-substituted compounds•{LnMn4} appended cubanes•Tetravacant polyoxometalate {SiW8O31}-based sandwich polyoxotungstateExploration of the reactivity of the versatile polyoxometalate precursor [β2-SiW11O39]8 − with lanthanide cations, transition-metal cations, carbonate, and morpholine, afforded a group of new appended cubanes {LnMnIII4} (Ln = HoIII, TmIII, YbIII, SmIII, GdIII, ErIII and CeIV). The appended cubanes {LnMnIII4} were encapsulated by two inorganic polyoxometalate ligands, resulting in a series of heterometallic cluster-based sandwich-type compounds: K10Na3[{LnIIIMnIII4(μ3-O)2(μ2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·xH2O (Ln = HoIII, x = 24 for 1; Ln = TmIII, x = 22 for 2; Ln = YbIII, x = 21 for 3); K7Na6[{LnIIIMnIII4(μ3-O)2(μ2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·xH2O (Ln = SmIII, x = 22 for 4; Ln = GdIII, x = 20 for 5; Ln = ErIII, x = 22 for 6) and K7Na5[{CeIVMnIII4(μ3-O)2(μ2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·24H2O (7), which were characterized by single-crystal X-ray diffraction analyses, IR spectroscopy, and thermal gravimetric analysis. Electrocatalytic study reveals that these compounds exhibited the activity of electrocatalytic reduction of sodium nitrite.A series of Ln cations were introduced into the reaction system of [β2-SiW11O39]8 -, transition metal ions, organic ligand and CO32 − resulting in a group of {LnMnIII4} cubanes stabilized by inorganic polyoxometalate ligands.
Co-reporter:Yue Jia, Jun Zhang, Zhi-Ming Zhang, Qiu-Yu Li, En-Bo Wang
Inorganic Chemistry Communications 2014 Volume 43() pp:5-9
Publication Date(Web):May 2014
DOI:10.1016/j.inoche.2014.01.015
•The Waugh- and Silverton-type-based thermotropic liquid crystal materials.•The metal-centered polyoxometalates were introduced into the POM/surfactant system•The thermotropic liquid crystal materials exhibit typical smectic mesomorphic behaviors.Waugh- and Silverton-type polyoxometalates (POMs) K3(NH4)3[MnMo9O32] and H8[CeMo12O42] are enwrapped by dioctadecyldimethylammonium (DODA+) forming the surfactant-encapsulated POMs (SEPs) (DODA)6[MnMo9O32]·16H2O (DODA-MnMo9) and (DODA)8[CeMo12O42]·9H2O (DODA-CeMo12), which exhibit typical thermotropic liquid-crystalline properties. Here, the Waugh- and Silverton-type polyoxoanions centered by metal cation were firstly introduced into liquid crystal materials. The chemical composition of these SEP complexes was determined by IR spectra, elemental analysis and TG analysis. Also, the polarized optical microscopy, differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VT-XRD) and transmission electron microscopes (TEM) were performed to characterize their liquid-crystalline behavior.The metal-centered polyoxometalates were introduced into the POM/surfactant system resulting in the organic–inorganic hybrid materials with characteristic thermotropic liquid-crystalline behavior.Figure optionsDownload full-size imageDownload as PowerPoint slide
Co-reporter:Jun Zhang;Qing Lan;Zhu-Jun Liu;Yue Liang
Journal of Cluster Science 2014 Volume 25( Issue 1) pp:253-259
Publication Date(Web):2014 January
DOI:10.1007/s10876-013-0634-8
A new crown inorganic–organic hybrid material composed of the Keggin polyoxometalates and transition metal-amino acid coordination complexes, K2{[KCu4(gly)4(OH)2(H2O)2Cl][PW12O40]}2·19H2O (1), was synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis and single crystal X-ray diffraction. Compound 1 possesses of a 1D chain structure with a crown-type monomer, which is built up from [PW12O40]3− building blocks and tetranuclear [KCu4(gly)4(OH)2(H2O)2Cl] rings. The [KCu4(gly)4(OH)2(H2O)2Cl] ring consists of four Cu2+ ions and four gly ligands, which exhibits the crown ether feature binding a potassium ion in its center. Further, two [KCu4(gly)4(OH)2(H2O)2Cl] rings linked two Keggin polyoxoanions [PW12O40]3− into crown inorganic–organic hybrid material. Magnetic study shows the existence of ferromagnetic interactions in compound 1.
Co-reporter:Tian-Zhan Zhang;Dr. Shuang Yao;Dr. Zhi-Ming Zhang;Ying Lu; Yang-Guang Li; En-Bo Wang
ChemPlusChem 2014 Volume 79( Issue 8) pp:1153-1158
Publication Date(Web):
DOI:10.1002/cplu.201402094
Abstract
Two new transition-metal (TM)-containing polytantalotungstates, CsNa2H[Cu(bpy)(H2O)3]3{[Cu(bpy)2]2[Cu(bpy)(H2O)2]3[Ta4O6(SiW9Ta3O40)4]}⋅17 H2O (1) and K4Na4H4[Ta4O6(SiW9Ta3O40)4][Cu(apy)(H2O)2]4⋅42 H2O (2) (bpy=2,2′-bipyridine, apy=3-aminopyridine), have been synthesised under hydrothermal conditions. Both compounds 1 and 2 were determined and characterised by single-crystal X-ray diffraction analysis, thermogravimetric analysis, IR spectroscopy, UV/Vis spectroscopy and elemental analysis. Compounds 1 and 2 contain W/Ta mixed-addendum nanoclusters decorated by TM–organic fragments. Compounds 1 and 2 are the first TM-containing polytantalotungstates promise a more diverse set of structures of the polytantalotungstate family. The obtained materials can harvest a wide spectrum of solar light, from UV to near-infrared (NIR) wavelength. Photocatalytic study revealed that compounds 1 and 2 exhibited UV- and visible-light-driven photocatalytic water splitting activity. Compound 1 could also be used as a catalyst for the photocatalytic decomposition of 2,4-dichlorophenol in water with NIR-light irradiation. This is the first NIR photocatalyst obtained in polyoxometalate chemistry.
Co-reporter:Jian-Qiang Shen;Dr. Qiong Wu;Ying Zhang;Dr. Zhi-Ming Zhang; Yang-Guang Li;Dr. Ying Lu; En-Bo Wang
Chemistry - A European Journal 2014 Volume 20( Issue 10) pp:2840-2848
Publication Date(Web):
DOI:10.1002/chem.201303995
Abstract
Reactions of hexaniobate with vanadate in the presence of Ni2+, Zn2+, or Cu2+ have furnished three high-nuclear vanadium cluster-substituted heteropolyoxoniobates (HPNs): {Ni(en)3}5H{VVNb8VIV8O44}⋅9 H2O (1), (H2en)Na2[{Zn(en)2(Hen)}{Zn(en)2(H2O)}2{PNb8VIV8O44}]⋅11 H2O (2), and Na{Cu(en)2}3{[Cu(en)2]2[PNb8VIV8O44]}⋅11 H2O (3) (en=1,2-diaminoethane). Their structures have been determined and characterized by single-crystal X-ray diffraction analysis, thermogravimetric analysis (TGA), and elemental analysis. Structural analysis has revealed that compounds 1–3 contain similar {V8}-substituted [XVNb8VIV8O44]11− (X=P, V) clusters, obtained by inserting a {V8} ring into tetravacant HPN [XNb8O36]27−. To the best of our knowledge, compounds 1–3 represent the first high-nuclear vanadium cluster-substituted HPNs, and compound 1 is the largest vanadoniobate cluster yet obtained in HPN chemistry. Nickel and zinc cations have been introduced into HPNs for the first time, which might promise a more diverse set of structures in this family. Antitumor studies have indicated that compounds 1 and 2 exhibit high activity against human gastric cancer SGC-7901 cells, SC-1680 cells, and MG-63 cells.
Co-reporter:Ai-Xue Yan;Dr. Shuang Yao; Yang-Guang Li;Dr. Zhi-Ming Zhang;Dr. Ying Lu;Dr. Wei-Lin Chen; En-Bo Wang
Chemistry - A European Journal 2014 Volume 20( Issue 23) pp:6927-6933
Publication Date(Web):
DOI:10.1002/chem.201400175
Abstract
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 Cr3+ 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.
Co-reporter:Yue Jia, Hua-Qiao Tan, Zhi-Ming Zhang and En-Bo Wang
Journal of Materials Chemistry A 2013 vol. 1(Issue 23) pp:3681-3685
Publication Date(Web):11 Apr 2013
DOI:10.1039/C3TC30179F
By ion metathesis reactions, the dimethyldioctadecylammonium (DODA+) was used as the surfactant to encapsulate organic–inorganic hybrid polyoxometalates (POMs) (NH4)6{Mo2VO4[(Mo2VIO6)NH3CH2CH2CH2C(O)(PO3)2]2}·10H2O (POM-1) and (NH4)8{Mo2VO4[(Mo2VIO6)CH3C(O)(PO3)2]2}·14H2O (POM-2), resulting in two surfactant-encapsulated clusters (SECs) with characteristic thermotropic liquid-crystalline behavior. The chemical composition of the obtained SECs was determined by IR spectra, elemental analysis, TG analysis and NMR spectra. Also, polarized optical microscopy, differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VT-XRD) and TEM of the samples were also performed, which revealed that both SECs show thermotropic liquid crystal behavior.
Co-reporter:Tian-Zhan Zhang, Zhi-Ming Zhang, Ying Lu, Hai Fu and En-Bo Wang
CrystEngComm 2013 vol. 15(Issue 3) pp:459-462
Publication Date(Web):12 Nov 2012
DOI:10.1039/C2CE26400E
The sodalite-type metal–organic framework constructed from heterometallic alkali metal/V secondary building units with large internal cavity was firstly obtained. The organic amine cations within the channels can be replaced by transition metal ions through a cation exchange process, and subsequent gas adsorption measurements confirm the permanent porosity.
Co-reporter:Qing Lan, Jun Zhang, Zhi-Ming Zhang, Ying Lu and En-Bo Wang
Dalton Transactions 2013 vol. 42(Issue 47) pp:16602-16607
Publication Date(Web):10 Sep 2013
DOI:10.1039/C3DT51722E
Two new porous frameworks [Ni(bix)2][VW12O40]·(H2bix)·H2O (1) and [Co(bix)2][VW12O40]·(H2bix)·2H2O (2) (bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) composed of Keggin polyoxometalates (POMs) and metal–organic coordination polymer sheets have been successfully obtained, and characterized by elemental analysis, IR spectra, thermal gravimetric analysis, and single crystal X-ray diffraction. Structural analysis reveals that the 2D metal–organic coordination polymer sheets in the two compounds are constructed from the transition-metal (TM) cations and the flexible N-donor ligand bix, which are further pillared by POM clusters into the 3D porous frameworks. Powder X-ray diffraction (PXRD) patterns of 1 indicate the structural integrity of the framework in aqueous solution with a wide pH range of 1 to 11, and in common organic solvents (methanol, ethanol and DMF). Photocatalytic studies indicate that compounds 1 and 2 are not only active photocatalysts for degradation of rhodamine B (RB), but very stable and easily separated from the photocatalytic system for reuse as well.
Co-reporter:Jian-Qiang Shen, Shuang Yao, Zhi-Ming Zhang, Hai-Hong Wu, Tian-Zhan Zhang and En-Bo Wang
Dalton Transactions 2013 vol. 42(Issue 16) pp:5812-5817
Publication Date(Web):31 Jan 2013
DOI:10.1039/C3DT32855D
An unprecedented organic–inorganic hybrid germanoniobate compound Na4[Cu(en)2(H2O)2]5[Na6Ge8Nb32O108H8(OH)4]·41H2O (1) was synthesized under the hydrothermal condition. In compound 1, the {Nb16} cage containing four {GeO4} tetrahedra in its internal cavity results in a heteropolyniobate anion [H4Ge4Nb16O54(OH)2]10− ({Ge4Nb16}), which is connected by a {Na6} cluster into the first germanoniobate-based sandwich-type structure. Further, the sandwich germanoniobates are connected by [Na2Cu(en)2O6H8] groups into a porous network with one dimensional channels along the a-axis. Photocatalytic study reveals that compound 1 exhibits good photocatalytic activity for the degradation of methylene blue.
Co-reporter:Hai-Hong Wu, Shuang Yao, Zhi-Ming Zhang, Yang-Guang Li, You Song, Zhu-Jun Liu, Xin-Bao Han and En-Bo Wang
Dalton Transactions 2013 vol. 42(Issue 2) pp:342-346
Publication Date(Web):26 Oct 2012
DOI:10.1039/C2DT32318D
The heterometallic appended {MMnIII4} (M = Dy3+ and K+) cubanes were firstly trapped by two diamagnetic POM shells, which were robust enough to construct inorganic crystalline tubular materials. Magnetic study reveals the presence of a SMM-like slow magnetic relaxation feature in the heterometallic cluster-containing POM.
Co-reporter:Shuang Yao;Jing-Hui Yan;Hui Duan;Yang-Guang Li;Xin-Bao Han;Jian-Qiang Shen;Hai Fu;En-Bo Wang
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 27) pp:4770-4774
Publication Date(Web):
DOI:10.1002/ejic.201300655
Abstract
Reactions of lacunary polyoxometalate (POM), transition-metal (TM), and lanthanide-metal (Ln) cations with the assistance of additional small organic molecules under hydrothermal conditions led to the formation of a group of metal–POM frameworks (MPFs) with nanospaces: [Cu(enMe)2]13{Ln(SiW11O39)2}2·xH2O [Ln = Ho3+ (compound 1), Dy3+ (compound 2), Eu3+ (compound 3), Er3+ (compound 4), Sm3+ (compound 5), Pr3+ (compound 6); x = 18 for 1, 5, 6; x = 20 for 2, 3, 4; enMe = 1,2-diaminopropane). Single-crystal X-ray diffraction analyses reveal that all the compounds are composed of two monovacant POMs, which are linked by one Ln3+ ion into a dimeric structure. The dimeric structure acts as an inorganic polydentate ligand coordinated with Cu2+ ions, which results in 3D MPFs with two channels. As the individual components integrated in the MPF materials posess fluorescent and magnetic properties, the luminescence properties and magnetic behavior of the resulting MPFs were measured.
Co-reporter:Hui Duan, Zhi-Ming Zhang, Xin-Bao Han, Yi-Zhen Chen, Jian-Qiang Shen, Wei-Peng Wang, Xiao-Tao Zheng, Huan-Yu Zhou, En-Bo Wang
Inorganic Chemistry Communications 2013 Volume 33() pp:90-94
Publication Date(Web):July 2013
DOI:10.1016/j.inoche.2013.04.009
•3d–5p cluster-containing POM•Sandwich POM-based 2D supramolecular framework•Sandwich POM-based 2D frameworkA new sandwich-type tungstoantimonate (NH4)9{Cu3Sb(H2O)3(SbW9O33)2}·22H2O (1) was synthesized by reaction of the preformed large cluster [NaSb9W21O86]18 − ({Sb9W21}) and transition-metal cations. Compound 1 is a 3d–5p heterometallic cluster-containing sandwich-type tungstoantimonate, which was further connected by the H-bonding interactions into a (4, 4)-connected two dimensional (2D) supramolecular framework. Further, the introduction of the alkali metal cations into the reaction system leads to a 2D framework based on the sandwich-type tungstoantimonate by water substitution: Na(NH4)9{SbCu3Cl(SbW9O33)2}·14H2O (2).A new 3d–5p heterometallic cluster-containing sandwich-type tungstoantimonate was synthesized by reaction of the preformed large cluster [NaSb9W21O86]18 − and transition-metal cations.
Co-reporter:Ying Zhang, Xin-Bao Han, Zhi-Ming Zhang, Zhu-Jun Liu, En-Bo Wang
Chinese Chemical Letters 2013 Volume 24(Issue 7) pp:581-584
Publication Date(Web):July 2013
DOI:10.1016/j.cclet.2013.04.034
A {Ni7} cluster-substituted sandwich-type phosphotungstate Na10(NH4)4[{(B-a-PW9O34)Ni3(OH)(H2O)2(HAle)}2Ni]·22H2O (1) was synthesized using the conventional aqueous solution method. Compound 1 represents the first nickel-containing sandwich-type polyoxometalate functionalized by bisphosphonate ligands. Further, the sandwich-type polyoxoanions aggregated via the H-bonding interactions into a two-dimensional (2D) supramolecular framework.A {Ni7} cluster-containing sandwich-type phosphotungstate was obtained using the conventional aqueous method, which formed a 2D supramolecular structure via intermolecular H-bonding interactions.
Co-reporter:Ai-Xue Yan, Hua-Qiao Tan, Ding Liu, Zhi-Ming Zhang, En-Bo Wang
Inorganic Chemistry Communications 2013 Volume 29() pp:49-52
Publication Date(Web):March 2013
DOI:10.1016/j.inoche.2012.12.016
Two organic–inorganic hybrid compounds with the formula {[MnIII(Salen)(H2O)]4MoO4}·Cl2·16H2O (1) and {[MnIII(Salen)(H2O)]4WO4}·(CH3COO)2·11H2O (2) (Salen = Di-[2-hydroxyl-3-methoxyl-benzaldehyde] ethylenediamine) have been synthesized and structurally characterized by IR, UV–vis spectroscopy, TG analysis and single crystal X-ray diffraction. Structural analysis revealed that compounds 1 and 2 consist of a [MoO4]2 − or [WO4]2 − building unit and four {[MnIII(Salen)(H2O)]+ metal–organic moieties, respectively. In the crystal structure, the [MoO4]2 − or [WO4]2 − tetrahedra coordinated with four MnIII ions, resulting in the penta-nuclear heterometallic tetrahedra cluster compounds, which were rarely observed in the Mn-Salen system. Magnetic study revealed that there was antiferromagnetic coupling in the two compounds.A penta-nuclear {MMn4} (M = W and Mo) heterometallic clusters with four Mn-Salens exhibit the tetrahedron structural and a 3D supramolecular porous framework.Highlights► Two penta-nuclear {MMn4} heterometallic clusters are both tetrahedral structure. ► Compounds 1 and 2 are both based on four Mn-Salens. ► Compounds 1 and 2 both exhibit a 3D supramolecular porous framework.
Co-reporter:Zhu-Jun Liu, Zhi-Ming Zhang, Hai Fu, Yang-Guang Li, Wei-Lin Chen, Hai-Hong Wu and En-Bo Wang
Dalton Transactions 2012 vol. 41(Issue 38) pp:11700-11705
Publication Date(Web):01 Aug 2012
DOI:10.1039/C2DT30742A
Two new {P8W48} wheel-based compounds, Na12Li16{[Cu(H2O)]2[Cu4(OH)4(H2O)8]2P8W48O184}·55H2O (1), and K4Na24Li10{(MoO2)2(P8W48O184)}·61H2O (2) have been synthesized by a conventional aqueous solution method, and characterized by UV, IR, TG analysis, XPRD, 31P NMR, XPS, single-crystal X-ray diffraction analyses, magnetic study and electrochemistry study. In compound 1, a wheel-type {P8W48} containing two {Cu4} clusters and two isolated Cu cations results in a 10-Cu-containing polyoxotungstate, which represents the first {P8W48}-based compound trapping two transition metal (TM) clusters in its inner cavity. Further, the polyoxoanion was connected by Na+ and Li+ cations into a 3D framework. Compound 2 is a 2-Mo-containing {P8W48}-based polyoxotungstate. Magnetic study indicates that antiferromagnetic interactions exist in compound 1.
Co-reporter:Xin-Bao Han, Zhi-Ming Zhang, Zhi-Shu Wang, Huan Zhang, Hui Duan, En-Bo Wang
Inorganic Chemistry Communications 2012 Volume 18() pp:47-49
Publication Date(Web):April 2012
DOI:10.1016/j.inoche.2012.01.006
A purely inorganic porous framework based on Keggin polyoxoanions K2NaH2[BW12O40]·12H2O (1) has been prepared and characterized by single-crystal X-ray analysis, IR and XRD analysis. Compound 1 crystallized in a chiral space group P6(4)22 with hexagonal symmetry. In compound 1, the 3D inorganic porous framework possesses of the 1D hexagon channels along the c axis. Furthermore, the porous framework exhibits reversible water sorption capability.A new purely inorganic chiral 3D porous framework based on Keggin polyoxoanions K2NaH2[BW12O40]•12H2O (1) has been synthesized with the 1D hexagon channels along the c axis.Highlights► A purely inorganic porous framework was synthesized and characterized. ► Compound 1 represents a chiral example of MOFs based on POM building. ► The porous framework of 1 exhibits reversible water sorption capability.
Co-reporter:Zhi-Shu Wang, Zhi-Ming Zhang, Xin-Bao Han, Huan Zhang, En-Bo Wang
Inorganic Chemistry Communications 2012 20() pp: 196-200
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.007
Co-reporter:Xin-Bao Han ; Zhi-Ming Zhang ; Teng Zhang ; Yang-Guang Li ; Wenbin Lin ; Wansheng You ; Zhong-Min Su ;En-Bo Wang
Journal of the American Chemical Society () pp:
Publication Date(Web):March 24, 2014
DOI:10.1021/ja412886e
A series of all-inorganic, abundant-metal-based, high-nuclearity cobalt–phosphate (Co–Pi) molecular catalysts [{Co4(OH)3(PO4)}4(SiW9O34)4]32– (1), [{Co4(OH)3(PO4)}4(GeW9O34)4]32– (2), [{Co4(OH)3(PO4)}4(PW9O34)4]28– (3), and [{Co4(OH)3(PO4)}4(AsW9O34)4]28– (4) were synthesized and shown to be highly effective at photocatalytic water oxidation. The {Co16(PO4)4} cluster contains a Co4O4 cubane which is structurally analogous to the [Mn3CaO4] core of the oxygen-evolving complex (OEC) in photosystem II (PSII). Compounds 1–4 were shown to be the first POM-based Co–Pi-cluster molecular catalysts for visible light-driven water oxidation, thus serving as a functional model of the OEC in PSII. The systematic synthesis of four isostructural analogues allowed for investigating the influence of different heteroatoms in the POM ligands on the photocatalytic activities of these Co–Pi cluster WOCs. Further, the POM-based photocatalysts readily recrystallized from the photocatalytic reaction systems with the polyoxoanion structures unchanged, which together with the laser flash photolysis, dynamic light-scattering, 31P NMR, UV–vis absorption, POM extraction, and ICP-MS analysis results collectively confirmed that compounds 1–4 maintain their structural integrity under the photocatalytic conditions. This study provides not only a valuable molecular model of the “Co–Pi” catalysts with a well-defined structure but also an unprecedented opportunity to fine-tune high-nuclearity POM clusters for visible light-driven water splitting.
Co-reporter:Jian-Qiang Shen, Shuang Yao, Zhi-Ming Zhang, Hai-Hong Wu, Tian-Zhan Zhang and En-Bo Wang
Dalton Transactions 2013 - vol. 42(Issue 16) pp:NaN5817-5817
Publication Date(Web):2013/01/31
DOI:10.1039/C3DT32855D
An unprecedented organic–inorganic hybrid germanoniobate compound Na4[Cu(en)2(H2O)2]5[Na6Ge8Nb32O108H8(OH)4]·41H2O (1) was synthesized under the hydrothermal condition. In compound 1, the {Nb16} cage containing four {GeO4} tetrahedra in its internal cavity results in a heteropolyniobate anion [H4Ge4Nb16O54(OH)2]10− ({Ge4Nb16}), which is connected by a {Na6} cluster into the first germanoniobate-based sandwich-type structure. Further, the sandwich germanoniobates are connected by [Na2Cu(en)2O6H8] groups into a porous network with one dimensional channels along the a-axis. Photocatalytic study reveals that compound 1 exhibits good photocatalytic activity for the degradation of methylene blue.
Co-reporter:Yue Jia, Hua-Qiao Tan, Zhi-Ming Zhang and En-Bo Wang
Journal of Materials Chemistry A 2013 - vol. 1(Issue 23) pp:NaN3685-3685
Publication Date(Web):2013/04/11
DOI:10.1039/C3TC30179F
By ion metathesis reactions, the dimethyldioctadecylammonium (DODA+) was used as the surfactant to encapsulate organic–inorganic hybrid polyoxometalates (POMs) (NH4)6{Mo2VO4[(Mo2VIO6)NH3CH2CH2CH2C(O)(PO3)2]2}·10H2O (POM-1) and (NH4)8{Mo2VO4[(Mo2VIO6)CH3C(O)(PO3)2]2}·14H2O (POM-2), resulting in two surfactant-encapsulated clusters (SECs) with characteristic thermotropic liquid-crystalline behavior. The chemical composition of the obtained SECs was determined by IR spectra, elemental analysis, TG analysis and NMR spectra. Also, polarized optical microscopy, differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VT-XRD) and TEM of the samples were also performed, which revealed that both SECs show thermotropic liquid crystal behavior.
Co-reporter:Zhu-Jun Liu, Zhi-Ming Zhang, Hai Fu, Yang-Guang Li, Wei-Lin Chen, Hai-Hong Wu and En-Bo Wang
Dalton Transactions 2012 - vol. 41(Issue 38) pp:NaN11705-11705
Publication Date(Web):2012/08/01
DOI:10.1039/C2DT30742A
Two new {P8W48} wheel-based compounds, Na12Li16{[Cu(H2O)]2[Cu4(OH)4(H2O)8]2P8W48O184}·55H2O (1), and K4Na24Li10{(MoO2)2(P8W48O184)}·61H2O (2) have been synthesized by a conventional aqueous solution method, and characterized by UV, IR, TG analysis, XPRD, 31P NMR, XPS, single-crystal X-ray diffraction analyses, magnetic study and electrochemistry study. In compound 1, a wheel-type {P8W48} containing two {Cu4} clusters and two isolated Cu cations results in a 10-Cu-containing polyoxotungstate, which represents the first {P8W48}-based compound trapping two transition metal (TM) clusters in its inner cavity. Further, the polyoxoanion was connected by Na+ and Li+ cations into a 3D framework. Compound 2 is a 2-Mo-containing {P8W48}-based polyoxotungstate. Magnetic study indicates that antiferromagnetic interactions exist in compound 1.
Co-reporter:Qing Lan, Jun Zhang, Zhi-Ming Zhang, Ying Lu and En-Bo Wang
Dalton Transactions 2013 - vol. 42(Issue 47) pp:NaN16607-16607
Publication Date(Web):2013/09/10
DOI:10.1039/C3DT51722E
Two new porous frameworks [Ni(bix)2][VW12O40]·(H2bix)·H2O (1) and [Co(bix)2][VW12O40]·(H2bix)·2H2O (2) (bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) composed of Keggin polyoxometalates (POMs) and metal–organic coordination polymer sheets have been successfully obtained, and characterized by elemental analysis, IR spectra, thermal gravimetric analysis, and single crystal X-ray diffraction. Structural analysis reveals that the 2D metal–organic coordination polymer sheets in the two compounds are constructed from the transition-metal (TM) cations and the flexible N-donor ligand bix, which are further pillared by POM clusters into the 3D porous frameworks. Powder X-ray diffraction (PXRD) patterns of 1 indicate the structural integrity of the framework in aqueous solution with a wide pH range of 1 to 11, and in common organic solvents (methanol, ethanol and DMF). Photocatalytic studies indicate that compounds 1 and 2 are not only active photocatalysts for degradation of rhodamine B (RB), but very stable and easily separated from the photocatalytic system for reuse as well.
Co-reporter:Hai-Hong Wu, Shuang Yao, Zhi-Ming Zhang, Yang-Guang Li, You Song, Zhu-Jun Liu, Xin-Bao Han and En-Bo Wang
Dalton Transactions 2013 - vol. 42(Issue 2) pp:NaN346-346
Publication Date(Web):2012/10/26
DOI:10.1039/C2DT32318D
The heterometallic appended {MMnIII4} (M = Dy3+ and K+) cubanes were firstly trapped by two diamagnetic POM shells, which were robust enough to construct inorganic crystalline tubular materials. Magnetic study reveals the presence of a SMM-like slow magnetic relaxation feature in the heterometallic cluster-containing POM.
Co-reporter:Yang-Yang Zhou, Shuang Yao, Jing-Hui Yan, Li Chen, Ting-Ting Wang, Chun-Jie Wang and Zhi-Ming Zhang
Dalton Transactions 2015 - vol. 44(Issue 47) pp:NaN20440-20440
Publication Date(Web):2015/10/16
DOI:10.1039/C5DT03397G
Two purely inorganic three-dimensional (3D) frameworks [Mn4(H2O)11VIV18O42(PO4)]7− (1) and [Mn2(H2O)7VIV18O42(PO4)]11− (2) were synthesized under hydrothermal conditions and fully characterized by single-crystal X-ray structural analysis, IR spectroscopy, thermogravimetric analysis and PXRD. Structural analysis revealed that these two compounds contained a similar all reduced polyoxoanion [VIV18O42(PO4)]15− linked by different amounts of manganese centers to form 3D framework materials. The V centers in these two compounds were all reduced to the +IV oxidation state, resulting in an all reduced polyoxoanion, which was firstly used as the building block for constructing 3D framework materials. The all reduced typical polyoxoanion [VIV18O42(PO4)]15− with 15 negative charges supplied enough charge amount to accept TM cations. In these two structures, the anions were surrounded by 12 and 5 Mn2+ ions, respectively, adjusted by varying the feeding amount of MnCl2·4H2O. An electrocatalytic study revealed that compound 1 exhibits electrocatalytic activity for reduction of H2O2.
Co-reporter:Jian-Qiang Shen, Ying Zhang, Zhi-Ming Zhang, Yang-Guang Li, Yan-Qing Gao and En-Bo Wang
Chemical Communications 2014 - vol. 50(Issue 45) pp:NaN6019-6019
Publication Date(Web):2014/04/17
DOI:10.1039/C3CC49245A
Two phosphoniobate-based 3D frameworks were firstly constructed using the hexa-capped Keggin polyoxoniobates [PNb12O40(VO)6]3− and copper cations. Photocatalytic studies indicated that the hybrid materials exhibit photocatalytic hydrogen evolution activity.
![Tungstate(10-), [m9-[orthosilicato(4-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]pentadeca-m-oxopentadecaoxonona-, sodium (1:10)](http://img.cochemist.com/ccimg/64700/64684-57-7.png)
![Tungstate(10-), [m9-[orthosilicato(4-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]pentadeca-m-oxopentadecaoxonona-, sodium (1:10)](http://img.cochemist.com/ccimg/64700/64684-57-7_b.png)
![Tungstate(3-),tetracosa-m-oxododecaoxo[m12-[phosphato(3-)-kO:kO:kO:kO':kO':kO':kO'':kO'':kO'':kO''':kO''':kO''']]dodeca-,hydrogen (1:3)](http://img.cochemist.com/ccimg/1400/1343-93-7.png)
![Tungstate(3-),tetracosa-m-oxododecaoxo[m12-[phosphato(3-)-kO:kO:kO:kO':kO':kO':kO'':kO'':kO'':kO''':kO''':kO''']]dodeca-,hydrogen (1:3)](http://img.cochemist.com/ccimg/1400/1343-93-7_b.png)
