Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)...Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.展开更多
By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68...By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).展开更多
Nanoporous anatase TiO2 crystalline particles coupled with Keggin or Wells-Dawson unit, H3PW12O40/TiO2 or H6P2W18O62/TiO2, were prepared at a low temperature （200℃ ） using sol-gel method combined with hydrothermal ...Nanoporous anatase TiO2 crystalline particles coupled with Keggin or Wells-Dawson unit, H3PW12O40/TiO2 or H6P2W18O62/TiO2, were prepared at a low temperature （200℃ ） using sol-gel method combined with hydrothermal treatment at programmed temperature. The as-prepared composites have uniform anatase phase, and they exhibit both micrand mesoporosities with pore sizes of 0.6 and 4.0 nm, respectively, and their average size is lower than 10 nm. Photocatalytic tests show the composites exhibit relatively higher photocatalytic activities to decompose the organocholorine pesticide hexachlorobenzene（HCB） than anatase TiO2, the starting polyoxotungstates, and EuEOa/TiO2 prepared by using sol-gel method, and this was attributed to （ 1 ） the synergistic effect of photoactive anatase TiO2 with the polyoxotungstate, and （2） the fascinating physical and chemical properties of the porous materials.展开更多
A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in ...A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.展开更多
Organothiophosphoryl polyoxotungstate derivatives α-C_6H_(11)P(S)]_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were obtained by the reactions of the monovacant α-_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were...Organothiophosphoryl polyoxotungstate derivatives α-C_6H_(11)P(S)]_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were obtained by the reactions of the monovacant α-_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were obtained by the reactions of the monovacant α-[X^(n+)W_(11)O_(39)]^((12-n)-)(X=P, Si, Ge, Ga) anions with electrophilic C_6H_(11)P(S)Cl_2 in acetonitrile. These new organic-inorganic hybrid anions were characterized by elemental analyses, IR, (()^(31)P) and (()^(183)W) NMR spectrometries. The six-line ()^(183)W NMR spectrum indicates that [C_6H_(11)P(S)]_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) anions possess true C_s symmetry in acetonitrile. According to the spectroscopic observation and the chemical analyses, it is known that each of the hybrid anions consists of an α-[XW_(11)O_(39)] framework on which two equivalent C_6H_(11)P(S) groups are grafted through P-O-W bridges.展开更多
A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray...A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray diffraction and electrochemistry.1 crystallizes in triclinic,space group P1 with a = 12.9077（14）,b = 14.8593（16）,c = 20.023（2）,α = 70.1620（10）,β = 80.8110（10）,γ = 64.3770（10）o,V = 3256.9（6）3,Z = 2,Dc = 4.790 g/cm3,μ = 31.975 mm-1,F（000） = 4080,R = 0.0412,and wR = 0.1039.X-ray single-crystal structural analysis indicates that the molecular structural unit of 1 consists of one saturated Dawson [α-P2W18O62]6-polyanion,one seven-coordinate [Ca（H2O）2]2＋ cation,one eight-coordinate [Ca（H2O）3]2＋ cation,two protons and nine lattice water molecules.Interestingly,adjacent Dawson [α-P2W18O62]6-polyanions are connected by [Ca（H2O）2]2＋ and [Ca（H2O）3]2＋ cations and hydrogen bonding interactions to form a 3D infinite framework.The electrochemistry property of 1 has been studied.展开更多
A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectros...A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectroscopy, and multinuclear 31P NMR.展开更多
A new supramolecular compound （4,4＇-bipyH）4[SiW12O40]（4,4＇-bipy） （4,4＇-bipy = 4,4＇-bipyridine） was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crysta...A new supramolecular compound （4,4＇-bipyH）4[SiW12O40]（4,4＇-bipy） （4,4＇-bipy = 4,4＇-bipyridine） was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767（12）, b = 21.1879（11）, c = 15.6942（8） A, β = 97.068（3）°, V = 7351.3（7） A3, Cs0H44N10040SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F（000） = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiWl2O40]4- anion, one 4,4＇-bipy and four protonated （4,4＇-bipyH）＋ cations. The [SiWl2O40]4- anion and protonated 4,4＇-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.展开更多
A new heteropolyoxotungstate [（C2H4N2）4（P4Co3W4O28H6）（H2C2O4）]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1...A new heteropolyoxotungstate [（C2H4N2）4（P4Co3W4O28H6）（H2C2O4）]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006（17）,b = 17.1006（7）,c = 10.7525（5）,V = 3144.2（2）3,Z = 4,Dc = 3.795 g·cm-3,F（000） = 3300,MoKα（λ = 0.71073 ）,μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.展开更多
The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave po...The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave potential of the complexes indicated that the effect of the functionallization of POMs increased the oxidizing ability of the polyoxoanions. The inhibitory effects of the CpTi polyoxocomplexes on tumor cells are higher than those of the corresponding titanium polyoxocomplexes, and the toxicity of the former is lower than that of the latter. The oxygenation reactions of cyclohexene, styrene, trans stilbene and maleic acid with PhIO or hydrogen peroxide(30% aqueous solution) catalyzed respectively by Ti and CpTi polyoxocomplexes were compared.展开更多
One new polyoxotungstate complex H6Na2K4（H2W12O42）Cl2·14H2O 1 has been prepared in the beaker solution and characterized by elemental analysis and IR spectroscopy. Crystal data： H36Cl2K4W12Na2O56, Mr = 3411.77...One new polyoxotungstate complex H6Na2K4（H2W12O42）Cl2·14H2O 1 has been prepared in the beaker solution and characterized by elemental analysis and IR spectroscopy. Crystal data： H36Cl2K4W12Na2O56, Mr = 3411.77, monoclinic, space group P21/c, a = 11.5734（16）, b = 14.3136（19）, c = 15.459（2）A, β = 105.601（2）°, V = 2466.5（6）A^3, Z = 2, Dc = 4.594 g/cm^3, F（000） = 3008, μ = 28.447 mm^-1, R = 0.0574 and wR = 0.1239 （Ⅰ〉 2σ（Ⅰ））. Single-crystal X-ray diffraction analysis results reveal that a three-dimensional architecture in the title compound is constructed from the H2W12O42^10- units linked by potassium.展开更多
A three-dimensional （3D） Keggin-type heteropolytungstate{Zn（phen）3}3[ZnW12O40]·9H2O 1 （phen = 1,10-phenanthroline） has been synthesized through a conventional hydrothermal synthesis and was characterized by...A three-dimensional （3D） Keggin-type heteropolytungstate{Zn（phen）3}3[ZnW12O40]·9H2O 1 （phen = 1,10-phenanthroline） has been synthesized through a conventional hydrothermal synthesis and was characterized by X-ray single-crystal diffraction analysis, X-ray powder diffraction （XRD）, IR, UV-DRS, thermogravimetric analysis （TGA）, thermal-dependent 2D-IR correlation spectroscopy （2D-COS IR） and Raman spectrum. Crystal data for compound 1： trigonal system, space group R3 with a = b = 25.268（4）, c = 17.462（5） A, ）, = 120°, V= 9655（4） A3 and Z = 3. Compound 1 is allomorphic to {Co（phen）3}3[CoW12O40]·9H2O 2, which has been reported by Feng Chai et al. In compound 2, its prominent feature is that the decisive role of water molecules （O-H…O） builds a 3D supramolecular structure. However, in the structure of compound 1, the interlayer space is filled by Zn（phen）3]2＋ cations which linked the layers via C-H…O hydrogen bonding interactions to construct a three-dimensional framework. Two compounds are different in weak interactions, so we identify them by Thermal-dependent 2D-COS IR. Moreover, the fluorescence of compound 1 was also described.展开更多
A novel P^(Ⅴ)-Sb^(Ⅲ) heteroatom-inserted poly(polyoxotungstate)(poly(POT))[H_(2)N(CH_(3))_(2)]_(5)Na_(11)H_(9)[(HEDATMPA)SbW_(15)O_(50)]{[PrW_(4)O_(10)][B-α-SbW_(9)O_(33)]_(2)}·38H_(2)O(1)was synthesized and i...A novel P^(Ⅴ)-Sb^(Ⅲ) heteroatom-inserted poly(polyoxotungstate)(poly(POT))[H_(2)N(CH_(3))_(2)]_(5)Na_(11)H_(9)[(HEDATMPA)SbW_(15)O_(50)]{[PrW_(4)O_(10)][B-α-SbW_(9)O_(33)]_(2)}·38H_(2)O(1)was synthesized and is composed of an attractive[(HEDATMPA)SbW_(15)O_(50)]^(14-)hybrid fragment and one sandwich-like Pr^(Ⅲ)-inserted[PrW4O10(B-α-SbW_(9)O_(33))2]^(11-)entity by using ethylenediamine tetramethylphosphoric acid(H8EDATMPA)with potential heteroatom sites and functional organic groups.Considering the advantages of poly(POT)clusters in storing and transferring electrons,we fabricated a 1-PEDOT(PEDOT=poly(3,4-ethylenedioxythiophene))hybrid film,which was used as an electrode-modified material to construct a 1-based genosensor(GS)for detecting the β-thalassemia gene.Research results show that this 1-based GS demonstrates high specificity,outstanding antijamming ability and low detection limit for β-thalassemia gene detection.This work not only provides a novel and feasible preparative strategy to construct poly(POT)clusters,but also promisingly promotes the development of poly(POT)-based GSs.展开更多
A neoteric inorganic-organic hybrid dual-heteroatom(HA)and lanthanide(Ln)cluster-bridged polyoxotungstate(POT)[H8BTHMMAP]_(1.5)[H_(2)N(CH_(3))_(2)]_(4)Na_(3)H[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)][(W_(...A neoteric inorganic-organic hybrid dual-heteroatom(HA)and lanthanide(Ln)cluster-bridged polyoxotungstate(POT)[H8BTHMMAP]_(1.5)[H_(2)N(CH_(3))_(2)]_(4)Na_(3)H[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)][(W_(5)O_(18))(B-α-BiW_(9)O_(33))_(2)]·44H_(2)O(1,H_(6)BTHMMAP=1,3-bis[tris-(hydroxymethyl)methylamino]propane,Hpdca=2-pyridinic acid)was prepared by the dual-HA template strategy.The skeleton of 1 possesses a threebladed propeller-shaped[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)]^(13+)core wrapped by two Keggin[B-α-BiW_(9)O_(33)]^(9−)and one Lindqvist[W_(5)O_(18)]^(6−)segments.Noteworthily,the intricate[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)]^(13+)unit consisting of a Bi-Te dual-HA-bridged Ln-W polynuclear cluster is rather attractive and rarely seen in POT crystal engineering.Prominently,1 exhibits an“ON-OFF”luminescence response triggered by Fe^(3+)based on dynamic quenching and competitive absorption,and the subsequent addition of pyrophosphate(PPi)leads to the recovery of luminescence due to the efficient interaction of Fe^(3+)and PPi.The developed“ON-OFF-ON”switch allows the consecutive discrimination of Fe^(3+)and PPi with low detection limits of 1.23μM and 2.16μM,respectively.This work provides a profound understanding of the dual-HA template approach in assembling complicated POTs,and shows the great potential of POT materials in environmental and biological detection.展开更多
Visible-white-light-driven selective aerobic oxidation of sulfides is highly attractive but challenging for modern organic and pharmaceutical synthesis.Thus,there is an urgent need for exploiting high-performance phot...Visible-white-light-driven selective aerobic oxidation of sulfides is highly attractive but challenging for modern organic and pharmaceutical synthesis.Thus,there is an urgent need for exploiting high-performance photocatalytic systems to reform the value-added organic transformation.Herein,we elucidated a bottom-up strategy to construct two robust zinc-imidazole metal–organic linker extended sandwichedtype polyoxotungstate-based open frameworks(POTOFs),{[Zn(1-pIM)_(3)]_(2)[Zn_(6)(AsW_(9)O_(33))_(2)(1-pIM)_(6)]·2(1-HpIM)·2H_(2)O}_(n)(LCU-20)and{[Zn(1-ipIM)_(3)]_(2)[Zn_(6)(SbW_(9)O_(33))_(2)(1-ipIM)_(6)]·2(1-HipIM)}_(n)(LCU-21)(1-pIM=1-propylimidazole,1-ipIM=1-isopropylimidazole)by tuning the substituent tails outside the imidazole.Interestingly,LCU-20 and LCU-21 exhibit 2D sql and 3D 2-fold interpenetrated lvt networks,respectively,although both nodes in LCU-20 and LCU-21 are similar 4-connected Zn_(6) ring seamed trivacant polyoxotungstate anions.Interestingly,the substituent tails of imidazole instead of the heteroatom in polyoxotungstates play a key role in determining the network propagation orientation that dictates the dimensionality of the final network of POTOFs.More importantly,the alliance of sandwich-type polyanions and zinc-imidazole metal–organic units can produce metal-to-metal charge transfer(MMCT)chromophores,endowing them with visible-light responsive features.Therefore,benefiting from the oxidative active species of O_(2)^(·−)and h_(+),LCU-20 exhibits efficient heterogeneous catalytic activities for the oxidation of sulfides with high yield(~99%)and excellent selectivity(~99%)under visible-white-light irradiation(>600 nm)in the ambient environment.This work not only presents a new approach for the construction of 3D POTOFs but also describes the white-light-driven oxidation of sulfides catalyzed by this type of material.展开更多
The chaotropic character of Keggin-type polyoxotungstate anions was evaluated with respect to their ability to bind toγ-cyclodextrin(γ-CD)by varying the global charge density of the nanometer-sized polyanion.
By a self-assembly reaction strategy accompanying the step-by-step introduction of simple reactants,a series of unprecedented mixed-heteroatom-oriented rare-earth-embedded heteropolyoxotungstates[H_(2)N(CH_(3))_(2)]_(...By a self-assembly reaction strategy accompanying the step-by-step introduction of simple reactants,a series of unprecedented mixed-heteroatom-oriented rare-earth-embedded heteropolyoxotungstates[H_(2)N(CH_(3))_(2)]_(12)Na_(2)[RE_(2)(H_(2)O)7(W_(4)O_(9))(HPSeW_(15)O_(54))(SeW_(9)O_(33))_(2)]·44H_(2)O(RE=Ce^(3+)(1),Pr^(3+)(2),Nd^(3+)(3),Sm^(3+)(4),Gd^(3+)(5),Tb^(3+)(6),Ho^(3+)(7),Er^(3+)(8))were successfully achieved.It is worth highlighting that their polyoxoanions were synergistically established by two trivacant Keggin SeIV-inserted[B-α-SeW_(9)O_(33)]^(8−)clusters and one trivacant Dawson PIII-and-SeIV-inserted[HPSeW_(15)O_(54)]^(10−)segment.Significantly,[HPSeW_(15)O_(54)]^(10−)is a rarely reported polyoxometalate(POM)unit and can be viewed as a new member derived from one plenary Dawson PIII-and-SeIV-inserted polyoxoanion by removing three{WO6}octahedra in the polar position.Moreover,the composite of 1 and carboxyl-functionalized multi-walled carbon nanotubes(CMWCNTs)was modified onto a glass carbon electrode(GCE)to construct the 1@CMWCNT-GCE electrochemical sensor(ECS).In PBS buffer(pH 7.00),we investigated the electrochemical sensing properties of 1@CMWCNT-GCE ECS toward simultaneously detecting dopamine(DA)and uric acid(UA).The 1@CMWCNT-GCE ECS exhibited good sensing performances toward DA and UA with a low detection limit(1.61μmol L^(−1) for DA and 5.41μmol L^(−1) for UA)and high stability.This work not only shows that the synergistic interaction of diverse heteroatoms(Has)can facilitate creating captivating structures of POMs,but also promotes the applications of POM-based materials in recognizing bioactive molecules.展开更多
The electrochemical NO reduction(NOER)is one of the most promising routes for ammonia synthesis and for simultaneously removing the air pollutant,NO.However,the current electro-catalysts are mainly metal based,and the...The electrochemical NO reduction(NOER)is one of the most promising routes for ammonia synthesis and for simultaneously removing the air pollutant,NO.However,the current electro-catalysts are mainly metal based,and the search for new and cost-efficient NOER catalysts is in the pipeline.Polyoxometalates,a class of metal–oxide clusters,exhibiting unique electrochemical redox behavior,have been widely applied to many electrocatalytic processes.展开更多
Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesiv...Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesive technology by enhancing the interfacial toughness and versatility of polyvinyl alcohol(PVA)through complexation with 1-nm Keggin-type polyoxotungstate clusters(POTs)carrying specific negative charges.The POT-PVA nanocomposites exhibit superior adhesion to hydrophilic surfaces,attributed to their high crosslinking densities and exceptional fracture energies surpassing 6.23 kJ·m^(-2).These adhesives,endowed with high flexibility and a wealth of surface hydroxyl groups,are uniquely suited for application on a wide array of substrates including glass,steel,aluminum,and beyond,demonstrating their broad applicability.Specifically,the reduction in PVA crystallinity due to the chaotropic effect of POTs,which significantly enhances polymer chain dynamics.This enhancement confers robust adhesive properties at extreme temperatures,from the cryogenic−196℃ to the high-temperature threshold of 100℃.By capitalizing on the chaotropic effects of charged POTs,the study achieves a notable enhancement in the adhesive capabilities of the POT-PVA nanocomposites,paving the way for the development of for eco-friendly and cost effective adhesives engineered to withstand extreme conditions.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.22109164 and 22371046)the Key Program of the Natural Science Foundation of Fujian Province(No.2021J02007)。
文摘Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.
基金financially supported by the National Natural Science Foundation of China(No.22071043).
文摘By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).
基金Project supported by the Natural Science Fund Council of Heilongjiang Province (B200608)
文摘Nanoporous anatase TiO2 crystalline particles coupled with Keggin or Wells-Dawson unit, H3PW12O40/TiO2 or H6P2W18O62/TiO2, were prepared at a low temperature （200℃ ） using sol-gel method combined with hydrothermal treatment at programmed temperature. The as-prepared composites have uniform anatase phase, and they exhibit both micrand mesoporosities with pore sizes of 0.6 and 4.0 nm, respectively, and their average size is lower than 10 nm. Photocatalytic tests show the composites exhibit relatively higher photocatalytic activities to decompose the organocholorine pesticide hexachlorobenzene（HCB） than anatase TiO2, the starting polyoxotungstates, and EuEOa/TiO2 prepared by using sol-gel method, and this was attributed to （ 1 ） the synergistic effect of photoactive anatase TiO2 with the polyoxotungstate, and （2） the fascinating physical and chemical properties of the porous materials.
基金This work was supported by the Natural Science Foundation of Fujian Province (No. E0420001) and the Science Foundation of Huaqiao University (No. 03HZR9)
文摘A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]?2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) ?, V = 11711(4) ?3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm?1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I). The crystal structure is composed of [{Cu(en)2}HPW12O40]2? anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions. The anionic [{Cu(en)2}HPW12O40]2? is formed by the mixed valance {HPWVI11WVO40}3? Keggin unit covalently linked by a {Cu(en)2}+ group.
基金Supported by the Natural Science Foundation of L iaoning Province of China(No.2 0 0 32 10 4 )
文摘Organothiophosphoryl polyoxotungstate derivatives α-C_6H_(11)P(S)]_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were obtained by the reactions of the monovacant α-_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) were obtained by the reactions of the monovacant α-[X^(n+)W_(11)O_(39)]^((12-n)-)(X=P, Si, Ge, Ga) anions with electrophilic C_6H_(11)P(S)Cl_2 in acetonitrile. These new organic-inorganic hybrid anions were characterized by elemental analyses, IR, (()^(31)P) and (()^(183)W) NMR spectrometries. The six-line ()^(183)W NMR spectrum indicates that [C_6H_(11)P(S)]_2X^(n+)W_(11)O_(39)^((8-n)-)(X=P, Si, Ge, Ga) anions possess true C_s symmetry in acetonitrile. According to the spectroscopic observation and the chemical analyses, it is known that each of the hybrid anions consists of an α-[XW_(11)O_(39)] framework on which two equivalent C_6H_(11)P(S) groups are grafted through P-O-W bridges.
基金supported by the National Natural Science Foundation of Chinathe Program for New Century Excellent Talent in Henan University+1 种基金the Foundation of Education Department of Henan Provincethe Natural Science Foundation of Henan Province
文摘A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray diffraction and electrochemistry.1 crystallizes in triclinic,space group P1 with a = 12.9077（14）,b = 14.8593（16）,c = 20.023（2）,α = 70.1620（10）,β = 80.8110（10）,γ = 64.3770（10）o,V = 3256.9（6）3,Z = 2,Dc = 4.790 g/cm3,μ = 31.975 mm-1,F（000） = 4080,R = 0.0412,and wR = 0.1039.X-ray single-crystal structural analysis indicates that the molecular structural unit of 1 consists of one saturated Dawson [α-P2W18O62]6-polyanion,one seven-coordinate [Ca（H2O）2]2＋ cation,one eight-coordinate [Ca（H2O）3]2＋ cation,two protons and nine lattice water molecules.Interestingly,adjacent Dawson [α-P2W18O62]6-polyanions are connected by [Ca（H2O）2]2＋ and [Ca（H2O）3]2＋ cations and hydrogen bonding interactions to form a 3D infinite framework.The electrochemistry property of 1 has been studied.
文摘A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectroscopy, and multinuclear 31P NMR.
基金Supported by the Natural Science Foundation of Fujina Province(No.2008I0013)the Foundation of Education Committee of Fujian Provinc(No.JB11002)
文摘A new supramolecular compound （4,4＇-bipyH）4[SiW12O40]（4,4＇-bipy） （4,4＇-bipy = 4,4＇-bipyridine） was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767（12）, b = 21.1879（11）, c = 15.6942（8） A, β = 97.068（3）°, V = 7351.3（7） A3, Cs0H44N10040SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F（000） = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiWl2O40]4- anion, one 4,4＇-bipy and four protonated （4,4＇-bipyH）＋ cations. The [SiWl2O40]4- anion and protonated 4,4＇-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.
基金supported by the Analysis and Testing Foundation of Northeast Normal University
文摘A new heteropolyoxotungstate [（C2H4N2）4（P4Co3W4O28H6）（H2C2O4）]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006（17）,b = 17.1006（7）,c = 10.7525（5）,V = 3144.2（2）3,Z = 4,Dc = 3.795 g·cm-3,F（000） = 3300,MoKα（λ = 0.71073 ）,μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.
基金Supported by the National Natural Science Foundation of China(No.39970 82 4 )
文摘The effect of the functionallization of POMs on their properties was examined by the comparison between both titanium and its corresponding cyclopentadienyl subsituted polyoxocomplexes. The polarographic half wave potential of the complexes indicated that the effect of the functionallization of POMs increased the oxidizing ability of the polyoxoanions. The inhibitory effects of the CpTi polyoxocomplexes on tumor cells are higher than those of the corresponding titanium polyoxocomplexes, and the toxicity of the former is lower than that of the latter. The oxygenation reactions of cyclohexene, styrene, trans stilbene and maleic acid with PhIO or hydrogen peroxide(30% aqueous solution) catalyzed respectively by Ti and CpTi polyoxocomplexes were compared.
基金The work was supported by NNSFC (No. 20501011)Liaocheng University (31801)
文摘One new polyoxotungstate complex H6Na2K4（H2W12O42）Cl2·14H2O 1 has been prepared in the beaker solution and characterized by elemental analysis and IR spectroscopy. Crystal data： H36Cl2K4W12Na2O56, Mr = 3411.77, monoclinic, space group P21/c, a = 11.5734（16）, b = 14.3136（19）, c = 15.459（2）A, β = 105.601（2）°, V = 2466.5（6）A^3, Z = 2, Dc = 4.594 g/cm^3, F（000） = 3008, μ = 28.447 mm^-1, R = 0.0574 and wR = 0.1239 （Ⅰ〉 2σ（Ⅰ））. Single-crystal X-ray diffraction analysis results reveal that a three-dimensional architecture in the title compound is constructed from the H2W12O42^10- units linked by potassium.
基金supported by the NNSFC(No.21473030,1371033)Fujian Provincial Natural Science Foundation(2013J01042)the Open Fund of State Key Laboratory of Structural Chemistry(20130015)
文摘A three-dimensional （3D） Keggin-type heteropolytungstate{Zn（phen）3}3[ZnW12O40]·9H2O 1 （phen = 1,10-phenanthroline） has been synthesized through a conventional hydrothermal synthesis and was characterized by X-ray single-crystal diffraction analysis, X-ray powder diffraction （XRD）, IR, UV-DRS, thermogravimetric analysis （TGA）, thermal-dependent 2D-IR correlation spectroscopy （2D-COS IR） and Raman spectrum. Crystal data for compound 1： trigonal system, space group R3 with a = b = 25.268（4）, c = 17.462（5） A, ）, = 120°, V= 9655（4） A3 and Z = 3. Compound 1 is allomorphic to {Co（phen）3}3[CoW12O40]·9H2O 2, which has been reported by Feng Chai et al. In compound 2, its prominent feature is that the decisive role of water molecules （O-H…O） builds a 3D supramolecular structure. However, in the structure of compound 1, the interlayer space is filled by Zn（phen）3]2＋ cations which linked the layers via C-H…O hydrogen bonding interactions to construct a three-dimensional framework. Two compounds are different in weak interactions, so we identify them by Thermal-dependent 2D-COS IR. Moreover, the fluorescence of compound 1 was also described.
基金supported by the National Natural Science Foundation of China(22371066,22071042,22171070,22201061)the China Postdoctoral Science Foundation(2022M721012)+2 种基金the Program for Kaifeng Innovation Teams of Science and Technology,the Key Project of Youth Interdisciplinary Foundation of Henan Universitythe Natural Science Foundation of Henan Province(222300420114,182102310815)the Innovation and Entrepreneurship Training Program for College Students of Henan University(202210475001).
文摘A novel P^(Ⅴ)-Sb^(Ⅲ) heteroatom-inserted poly(polyoxotungstate)(poly(POT))[H_(2)N(CH_(3))_(2)]_(5)Na_(11)H_(9)[(HEDATMPA)SbW_(15)O_(50)]{[PrW_(4)O_(10)][B-α-SbW_(9)O_(33)]_(2)}·38H_(2)O(1)was synthesized and is composed of an attractive[(HEDATMPA)SbW_(15)O_(50)]^(14-)hybrid fragment and one sandwich-like Pr^(Ⅲ)-inserted[PrW4O10(B-α-SbW_(9)O_(33))2]^(11-)entity by using ethylenediamine tetramethylphosphoric acid(H8EDATMPA)with potential heteroatom sites and functional organic groups.Considering the advantages of poly(POT)clusters in storing and transferring electrons,we fabricated a 1-PEDOT(PEDOT=poly(3,4-ethylenedioxythiophene))hybrid film,which was used as an electrode-modified material to construct a 1-based genosensor(GS)for detecting the β-thalassemia gene.Research results show that this 1-based GS demonstrates high specificity,outstanding antijamming ability and low detection limit for β-thalassemia gene detection.This work not only provides a novel and feasible preparative strategy to construct poly(POT)clusters,but also promisingly promotes the development of poly(POT)-based GSs.
基金supported by the National Natural Science Foundations of China(22371066,22101072,22071042,and 22171070)Henan Science and Technology Research Project(242102231046)+1 种基金China Postdoctoral Science Foundation(2021M701067)the Program for Kaifeng Innovation Teams of Science and Technology,and the Key Project of the Youth Interdisciplinary Foundation of Henan University.
文摘A neoteric inorganic-organic hybrid dual-heteroatom(HA)and lanthanide(Ln)cluster-bridged polyoxotungstate(POT)[H8BTHMMAP]_(1.5)[H_(2)N(CH_(3))_(2)]_(4)Na_(3)H[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)][(W_(5)O_(18))(B-α-BiW_(9)O_(33))_(2)]·44H_(2)O(1,H_(6)BTHMMAP=1,3-bis[tris-(hydroxymethyl)methylamino]propane,Hpdca=2-pyridinic acid)was prepared by the dual-HA template strategy.The skeleton of 1 possesses a threebladed propeller-shaped[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)]^(13+)core wrapped by two Keggin[B-α-BiW_(9)O_(33)]^(9−)and one Lindqvist[W_(5)O_(18)]^(6−)segments.Noteworthily,the intricate[Eu_(2)Bi_(3)(Hpdca)_(3)(H_(2)O)_(3)Te_(2)W_(3)O_(14)]^(13+)unit consisting of a Bi-Te dual-HA-bridged Ln-W polynuclear cluster is rather attractive and rarely seen in POT crystal engineering.Prominently,1 exhibits an“ON-OFF”luminescence response triggered by Fe^(3+)based on dynamic quenching and competitive absorption,and the subsequent addition of pyrophosphate(PPi)leads to the recovery of luminescence due to the efficient interaction of Fe^(3+)and PPi.The developed“ON-OFF-ON”switch allows the consecutive discrimination of Fe^(3+)and PPi with low detection limits of 1.23μM and 2.16μM,respectively.This work provides a profound understanding of the dual-HA template approach in assembling complicated POTs,and shows the great potential of POT materials in environmental and biological detection.
基金financially supported by the National Natural Science Foundation of China(no.21871125,22171139,21801145 and 21901122)the Natural Science Foundation of Shandong Province,China(no.ZR2019MB043 and ZR2019QB022)+1 种基金the Shandong Provincial Key R&D Program/Major Science and Technology Innovation Project of Shandong Province(2019JZZY020230)the Construction Project of Quality Curriculum for Postgraduate Education of Shandong Province(no.SDYKC19057).
文摘Visible-white-light-driven selective aerobic oxidation of sulfides is highly attractive but challenging for modern organic and pharmaceutical synthesis.Thus,there is an urgent need for exploiting high-performance photocatalytic systems to reform the value-added organic transformation.Herein,we elucidated a bottom-up strategy to construct two robust zinc-imidazole metal–organic linker extended sandwichedtype polyoxotungstate-based open frameworks(POTOFs),{[Zn(1-pIM)_(3)]_(2)[Zn_(6)(AsW_(9)O_(33))_(2)(1-pIM)_(6)]·2(1-HpIM)·2H_(2)O}_(n)(LCU-20)and{[Zn(1-ipIM)_(3)]_(2)[Zn_(6)(SbW_(9)O_(33))_(2)(1-ipIM)_(6)]·2(1-HipIM)}_(n)(LCU-21)(1-pIM=1-propylimidazole,1-ipIM=1-isopropylimidazole)by tuning the substituent tails outside the imidazole.Interestingly,LCU-20 and LCU-21 exhibit 2D sql and 3D 2-fold interpenetrated lvt networks,respectively,although both nodes in LCU-20 and LCU-21 are similar 4-connected Zn_(6) ring seamed trivacant polyoxotungstate anions.Interestingly,the substituent tails of imidazole instead of the heteroatom in polyoxotungstates play a key role in determining the network propagation orientation that dictates the dimensionality of the final network of POTOFs.More importantly,the alliance of sandwich-type polyanions and zinc-imidazole metal–organic units can produce metal-to-metal charge transfer(MMCT)chromophores,endowing them with visible-light responsive features.Therefore,benefiting from the oxidative active species of O_(2)^(·−)and h_(+),LCU-20 exhibits efficient heterogeneous catalytic activities for the oxidation of sulfides with high yield(~99%)and excellent selectivity(~99%)under visible-white-light irradiation(>600 nm)in the ambient environment.This work not only presents a new approach for the construction of 3D POTOFs but also describes the white-light-driven oxidation of sulfides catalyzed by this type of material.
基金supported by a public grant overseen by the French National Research Agency as part of the“Investissements d’Avenir”program(Labex Charm3at,ANR-11-LABX-0039-grant)as well as the CNRS-MOMENTUMThis research is also supported by the China Scholarship Council(CSC)to S.Y.(201904910419).The authors are grateful to Flavien Bourdreux and Cyrielle Rey for their help with elemental analyses.
文摘The chaotropic character of Keggin-type polyoxotungstate anions was evaluated with respect to their ability to bind toγ-cyclodextrin(γ-CD)by varying the global charge density of the nanometer-sized polyanion.
基金supported by the National Natural Science Foundation of China(22071042,21771052,21671054,21571048,21871077)the Program for Innovation Teams in Science and Technology in Universities of Henan Province(20IRTSTHN004)+1 种基金the Program of First-Class Discipline Cultivation Project of Henan University(2019YLZDYJ02,CJ1205A0240019)the College Students Innovation and Entrepreneurship Training Program of Henan University(202010475001).
文摘By a self-assembly reaction strategy accompanying the step-by-step introduction of simple reactants,a series of unprecedented mixed-heteroatom-oriented rare-earth-embedded heteropolyoxotungstates[H_(2)N(CH_(3))_(2)]_(12)Na_(2)[RE_(2)(H_(2)O)7(W_(4)O_(9))(HPSeW_(15)O_(54))(SeW_(9)O_(33))_(2)]·44H_(2)O(RE=Ce^(3+)(1),Pr^(3+)(2),Nd^(3+)(3),Sm^(3+)(4),Gd^(3+)(5),Tb^(3+)(6),Ho^(3+)(7),Er^(3+)(8))were successfully achieved.It is worth highlighting that their polyoxoanions were synergistically established by two trivacant Keggin SeIV-inserted[B-α-SeW_(9)O_(33)]^(8−)clusters and one trivacant Dawson PIII-and-SeIV-inserted[HPSeW_(15)O_(54)]^(10−)segment.Significantly,[HPSeW_(15)O_(54)]^(10−)is a rarely reported polyoxometalate(POM)unit and can be viewed as a new member derived from one plenary Dawson PIII-and-SeIV-inserted polyoxoanion by removing three{WO6}octahedra in the polar position.Moreover,the composite of 1 and carboxyl-functionalized multi-walled carbon nanotubes(CMWCNTs)was modified onto a glass carbon electrode(GCE)to construct the 1@CMWCNT-GCE electrochemical sensor(ECS).In PBS buffer(pH 7.00),we investigated the electrochemical sensing properties of 1@CMWCNT-GCE ECS toward simultaneously detecting dopamine(DA)and uric acid(UA).The 1@CMWCNT-GCE ECS exhibited good sensing performances toward DA and UA with a low detection limit(1.61μmol L^(−1) for DA and 5.41μmol L^(−1) for UA)and high stability.This work not only shows that the synergistic interaction of diverse heteroatoms(Has)can facilitate creating captivating structures of POMs,but also promotes the applications of POM-based materials in recognizing bioactive molecules.
基金financially supported by the National Natural Science Foundation of China(grant no.21771033,21671036,and 21901035)the Fundamental Research Funds for the Central Universities(grant no.2412018BJ001,2412018ZD007,and 2412018QD005)+5 种基金the China Postdoctoral Science Foundation funded project(grant no.2018M631849)the Foundation of Jilin Educational Committee(grant no.JJKH20190268KJ)the Scientific Development Project of Jilin Province(grant no.20190201206JC)the Shenzhen Nobel Prize Scientists Laboratory Project(grant no.C17783101)Start-up Fund From SUSTech(grant no.Y01216127 and Y01216227)The computational work was carried out at the LvLiang Cloud Computing Center of China,and the calculations were performed on TianHe-2.
文摘The electrochemical NO reduction(NOER)is one of the most promising routes for ammonia synthesis and for simultaneously removing the air pollutant,NO.However,the current electro-catalysts are mainly metal based,and the search for new and cost-efficient NOER catalysts is in the pipeline.Polyoxometalates,a class of metal–oxide clusters,exhibiting unique electrochemical redox behavior,have been widely applied to many electrocatalytic processes.
基金This study was financially supported by the National Natural Science Foundation of China(No.22101086)Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515140030 and 2024A1515030212).
文摘Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesive technology by enhancing the interfacial toughness and versatility of polyvinyl alcohol(PVA)through complexation with 1-nm Keggin-type polyoxotungstate clusters(POTs)carrying specific negative charges.The POT-PVA nanocomposites exhibit superior adhesion to hydrophilic surfaces,attributed to their high crosslinking densities and exceptional fracture energies surpassing 6.23 kJ·m^(-2).These adhesives,endowed with high flexibility and a wealth of surface hydroxyl groups,are uniquely suited for application on a wide array of substrates including glass,steel,aluminum,and beyond,demonstrating their broad applicability.Specifically,the reduction in PVA crystallinity due to the chaotropic effect of POTs,which significantly enhances polymer chain dynamics.This enhancement confers robust adhesive properties at extreme temperatures,from the cryogenic−196℃ to the high-temperature threshold of 100℃.By capitalizing on the chaotropic effects of charged POTs,the study achieves a notable enhancement in the adhesive capabilities of the POT-PVA nanocomposites,paving the way for the development of for eco-friendly and cost effective adhesives engineered to withstand extreme conditions.
