层柱催化剂Co2-Al-XW11Z的合成及氧化催化性能

过渡金属取代型Ｋｅｇｇｉｎ结构杂多金属氧酸盐（ＨＰＯＭ），由于它具有较高的稳定性和催化氧化活性，被誉为“无机金属卟啉”［１］．将这些ＨＰＯＭ阴离子嵌入类水滑石层间，不仅可提供一种ＨＰＯＭ的固载化手段，而且以层空间作为反应场，使反应物分子能够选择性地进...     

柱撑杂多阴离子粘土的合成及表征

采用水热合成及离子交换法将Keggin结构三铁九钨镓酸盐杂多阴离子GaW9Fe3（H2O）3嵌入Zn2Al型阴离子粘土层间，得到了新型层柱状微孔材料Zn2Al－GaW9Fe3．用元素分析、XRD、IR、XPS等手段对产物的组成和结构进行了表征．结果表明，杂多阴离子嵌入Zn2Al型阴离子粘土层间，使柱撑杂多阴离子粘土具有1．0nm的通道高度．     

新型层柱材料ZnAl─CuW11In的合成、表征及催化活性

本文用水热离子交换法首次将中心原子为铜的钨系取代型杂多阴离子［ＣｕＷ１１Ｏ３９Ｉｎ（Ｈ２Ｏ）］７－嵌入ＺｎＡｌ型阴离子粘土层间，通过ＸＲＤ、ＩＲ及ＥＳＲ等对柱撑产物进行了表征。ＸＲＤ研究表明柱撑产物的底面间距为１．７５ｎｍ，通道高度达１．２８ｎｍ。ＥＳＲ结果显示杂多阴离子进入粘土层间后ＣｕＯ４四面体中Ｃｕ－Ｏ键的共价性减弱。催化实验则表明柱撑产物对邻苯二甲酸二辛酯（ＤＯＰ）的合成反应有较高的催化活性     

新型层柱材料ZnAl─CuW11In的合成、表征及催化活性

本文用水热离子交换法首次将中心原子为铜的钨系取代型杂多阴离子［ＣｕＷ１１Ｏ３９Ｉｎ（Ｈ２Ｏ）］＾７－嵌入ＺｎＡｌ型阴离子粘土层间，通过ＸＲＤ、ＩＲ及ＥＳＲ等对柱撑产物进行了表征。ＸＲＤ研究表明柱撑产物的底面间距为１．７５ｎｍ，通道高度达１．２８ｎｍ。ＥＳＲ结果显示杂多阴离子进入粘土层间后ＣｕＯ４四面体中Ｃｕ－Ｏ键的共价性减弱。催化实验表明柱撑产物对邻苯二甲酸二辛酯（ＤＯＰ）的合成反应有较好的催化活     

杂多阴离子柱撑锰铝水滑石的合成、表征及催化性能

杂多阴离子柱撑锰铝水滑石的合成、表征及催化性能刘继广，孙铁，蒋大振（吉林大学化学系，长春１３００２３）关键词杂多阴离子，柱撑，锰铝水滑石，异丁烷，烷基化类水滑石化合物属于阴离子型粘土‘’‘，其中心金属离子Ｍ２＋或Ｍ３＋及平衡阴离子可根据需要进行改变．...     

柱撑化合物Zn2Al-PW11Z的结构模型及酯化活性

杂多化合物是性能优异的酸型和氧化型或双功能催化剂[1－4]，而通式为的阴离子粘土通常具有减催化或还原催化性能[5，6]．因此，从在分子及原子水平上设计催化剂，调控催化性能观点出发，人们期望将体积较大的杂多阴离子嵌入阴离子粘土层间，合成大层间距的新型柱撑微孔材料．1988年Pinnavaia等人[7]首次报导了Zn2Al－V10O28是具有2．0nm孔径分布的中微孔材料．最近，笔者将单取代型Keggin结构杂多阴离子GeW11O39Z（H2O）6－（其中Z＝Ni2 和Cu2 ）和缺位Keggin结构的GeW11O嵌入Zn2Al－NO3层间，合成了通道高度为0．9nm的新型柱撑…     

柱撑阴离子粘土的合成、表征及催化性能研I．ZnAl─SiW_（11）及ZnAl—SiW_（11）Z的合成

采用水热合成及离子交换方法将缺位及单取代型Ｋｅｇｇｉｎ结构钨硅杂多含氧酸根ＳｉＷ（１１）及ＳｉＷ（１１）Ｏ（３９）Ｚ（Ｈ２Ｏ）（６－）嵌入Ｚｎ─Ａｌ型阴离子粘土层间，得到了大层间距的新型层往状微孔材料ＺｎＡｌ─ＳｉＷ（１１）及ＺｎＡｌ—ＳｉＷ（１１）Ｚ（Ｚ＝Ｃｏ（２＋）、Ｎｉ（２十）和Ｃｕ（２＋）），ＸＲＤ与ＩＲ测试结果表明，它们只有９．７　的通道高度．     

磷钼酸掺杂的聚吡咯薄膜电极的表征

对离子在导电聚合物修饰电极中起着很重要的作用．因止匕自从导电聚合物薄膜修饰电极的研究开始以来，A们尝试了在导电聚合物膜中掺杂各种各样的离子［‘一句，以使导电聚合物膜向功能化方向发展．在这些众多的掺杂离子中，人们无感兴趣的是将那些电活性阴离子作对离子掺杂人导电聚合物膜中，如时C叫6【‘，司、杂多酸根离子”河等·将电活性阴离子作为对离子掺杂人导电聚合物膜修饰电极中，有助于人们对这种修饰电极的研究，因为这些对离子可以作为一种探针来检测对离子在腰中的传输情况．杂多酸掺杂的导电聚合物电极还具有电催化性能，对…     

新型层柱材料ZnAl－XW_（11）Co的合成、表征及催化活性

新型层柱材料ＺｎＡｌ－ＸＷ_（１１）Ｃｏ的合成、表征及催化活性胡长文，刘彦勇，王作屏，张继余，王恩波（东北师范大学化学系，长春１３００２４）关键词层柱化合物，杂多阴离子，Ｋｅｇｇｉｎ结构，乙酸，正了醇，酯化化学组成通式为的阴离子粘土具有独特的层柱结构?..     

新型层柱材料Zn2Al-SiW9M3的合成、表征及催化性能研究

杂多阴离子柱撑粘土是一类新型层柱催化材料.本文采用水热合成与离子交换方法首次将三取代Keggin结构杂多阴离子α-[SiW9O37M3(H2O)3]n-(简写为SiW9M3,M＝Mn2+,Cr3+,Ti3+,Fe3+)嵌入到Zn-Al型阴离子粘土层间,并通过XRD、IR、DTA和元素分析等手段对其结构进行了表征,考察了它们在顺丁烯二酸环氧化反应中的催化活性.     

Sandwich-type germanotungstates: structure and magnetic properties of the dimeric polyoxoanions [M4(H2O)2(GeW9O34)2]12 - (M = Mn2+, Cu2+, Zn2+, Cd2+)

The novel dimeric germanotungstates [M(4)(H(2)O)(2)(GeW(9)O(34))(2)](12)(-) (M = Mn(2+), Cu(2+), Zn(2+), Cd(2+)) have been synthesized and characterized by IR spectroscopy, elemental analysis, magnetic measurements, and (183)W-NMR spectroscopy. X-ray single-crystal analyses were carried out on Na(12)[Mn(4)(H(2)O)(2)(GeW(9)O(34))(2)].38H(2)O (Na(12)()-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.0419(8) A, b = 17.8422(10) A, c = 21.1626(12) A, beta = 93.3120(10) degrees, and Z = 2; Na(11)Cs(2)[Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)]Cl.31H(2)O (Na(11)()Cs-2) crystallizes in the triclinic system, space group P, with a = 12.2338(17) A, b = 12.3833(17) A, c = 15.449(2) A, alpha = 100.041(2) degrees, beta = 97.034(2) degrees, gamma = 101.153(2) degrees, and Z = 1; Na(12)[Zn(4)(H(2)O)(2)(GeW(9)O(34))(2)].32H(2)O (Na(12)()-3) crystallizes in the triclinic system, space group P, with a = 11.589(3) A, b = 12.811(3) A, c = 17.221(4) A, alpha = 97.828(6) degrees, beta = 106.169(6) degrees, gamma = 112.113(5) degrees, and Z = 1; Na(12)[Cd(4)(H(2)O)(2)(GeW(9)O(34))(2)].32.2H(2)O (Na(12)()-4) crystallizes also in the triclinic system, space group P, with a = 11.6923(17) A, b = 12.8464(18) A, c = 17.616(2) A, alpha = 98.149(3) degrees, beta = 105.677(3) degrees, gamma = 112.233(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[GeW(9)O(34)](10)(-) Keggin moieties linked via a rhomblike M(4)O(16) (M = Mn, Cu, Zn, Cd) group leading to a sandwich-type structure. (183)W-NMR studies of the diamagnetic Zn and Cd derivatives indicate that the solid-state polyoxoanion structures are preserved in solution. EPR measurements on Na(12)()-1 at frequencies up to 188 GHz and temperatures down to 4 K yield a single, exchange-narrowed peak, at g(iso) = 1.9949, typical of Mn systems, and an upper limit of |D| = 20.0 mT; its magnetization studies still await further theoretical treatment. Detailed EPR studies on Na(11)()Cs-2 over temperatures down to 2 K and variable frequencies yield g( parallel ) = 2.4303 and g( perpendicular ) = 2.0567 and A( parallel ) = 4.4 mT (delocalized over the Cu(4) framework), with |D| = 12.1 mT. Magnetization studies in addition yield the exchange parameters J(1) = -11 and J(2) = -82 cm(-)(1), in agreement with the EPR studies.     

Hydrothermal and solid-state transformation of ruthenium-supported Keggin-type heteropolytungstates [XW11O39{Ru(II)(benzene)(H2O)}]n- (X = P (n = 5), Si (n = 6), Ge (n = 6)) to ruthenium-substituted Keggin-type heteropolytungstates

A new pathway for the preparation of mono-ruthenium (Ru)(iii)-substituted Keggin-type heteropolytungstates with an aqua ligand, [PW(11)O(39)Ru(iii)(H(2)O)](4-) (1a), [SiW(11)O(39)Ru(iii)(H(2)O)](5-) (1b) and [GeW(11)O(39)Ru(iii)(H(2)O)](5-) (1c), using [Ru(ii)(benzene)Cl(2)](2) as a Ru source was described. Compounds 1a-1c were prepared by reacting [XW(11)O(39)](n-) (X = P, Si and Ge) with [Ru(ii)(benzene)Cl(2)](2) under hydrothermal condition and were isolated as caesium salts. Ru(benzene)-supported heteropolytungstates, [PW(11)O(39){Ru(ii)(benzene)(H(2)O)}](5-) (2a), [SiW(11)O(39){Ru(ii)(benzene)(H(2)O)}](6-) (2b) and [GeW(11)O(39){Ru(ii)(benzene)(H(2)O)}](6-) (2c), were first produced in the reaction media, and then transformed to 1a, 1b and 1c, respectively, under hydrothermal conditions. Calcination of Ru(benzene)-supported heteropolytungstates, 2a, 2b and 2c, in the solid state produced mixtures of 1a, 1b and 1c with CO (carbon monoxide)-coordinated complexes, [PW(11)O(39)Ru(ii)(CO)](5-) (4a), [SiW(11)O(39)Ru(ii)(CO)](6-) (4b) and [GeW(11)O(39)Ru(ii)(CO)](6-) (4c), respectively. From comparison of their catalytic activities in water oxidation reaction, it was indicated that ruthenium should be incorporated in the heteropolytungstate in order to promote catalytic activity.     

Two iron-containing tungstogermanates: [K(H2O)(beta-Fe2GeW10O37(OH))(gamma-GeW10O36)]12- and [{beta-Fe2GeW10O37(OH)2}2]12-

Interaction of the dilacunary polyanion precursor [gamma-GeW(10)O(36)](8-) with Fe(3+) ions in aqueous buffer medium (pH 4.8) results in the formation of two dimeric tungstogermanates depending on the reactant ratios. When using an Fe3+ to [gamma-GeW(10)O(36)](8-) ratio of 1:1, the asymmetric anion [K(H(2)O)(beta-Fe(2)GeW(10)O(37)(OH))(gamma-GeW(10)O(36))](12-) (1) is formed, whereas [{beta-Fe(2)GeW(10)O(37)(OH)2}2]12- (2) is formed when using a ratio of 2:1. Single-crystal X-ray analyses were carried out on Cs(3)K(9)[K(H(2)O)(beta-Fe(2)GeW(10)O(37)(OH))(gamma-GeW(10)O(36))].19H(2)O (CsK-1), which crystallizes in the triclinic system, space group P1, a = 11.4547(2), b = 19.9181(5), c = 21.0781(6) A, alpha = 66.7977(12), beta = 89.1061(12), gamma = 84.4457(11) degrees, and Z = 2 and on Cs(7)K(4)Na[{beta-Fe(2)GeW(10)O(37)(OH)(2)}(2)].39H(2)O (CsKNa-2), which crystallizes in the monoclinic system, space group C2/m, a = 32.7569(13), b = 12.2631(5), c = 14.2895(5) A, beta = 104.135(2) degrees , and Z = 2. Polyanion 1 consists of (beta-Fe(2)GeW(10)O(37)) and (gamma-GeW(10)O(36)) units linked via two Fe-O-W bridges and a central potassium ion. Two equivalent FeO(6) octahedra complete the belt of the beta-Keggin unit and link to the (gamma-GeW(10)O(36)) fragment. On the other hand, 2 consists of two {beta-Fe(2)GeW(10)O(37)(OH)(2)} units with four bridging hydroxo groups linking the four Fe(3+) ions, forming an eight-membered ring. The magnetic properties of CsK-1 and CsKNa-2 have been studied by magnetic susceptibility and magnetization measurements and fitted according to an isotropic exchange model. Both polyanions 1 and 2 exhibit diamagnetic ground states with a small amount of paramagnetic impurity. Electrochemistry studies on 1 and 2 were carried out in a pH 5 acetate medium. The two polyanions have in common the simultaneous reduction of all of their Fe(3+) centers. This observation suggests the existence of identical or almost-identical influences on these centers and their equivalence, especially in the reduced state. Controlled potential coulometry results indicate the presence of two Fe(3+) centers in 1 and four in 2. The splitting of the tungsten wave of 1 compared to the single tungsten wave of 2 is attributed to a difference in acid-base properties of the polyanions. Voltammetric peak-potential shifts as a function of pH were studied in the case of 2.     

Studies on Redox Properties of Heteropoly Compounds Containing Rare Earth Elements

The redox properties of four series of more than one handred acids and salts of rare earth heteropoly compounds, such as LnHSiMoi2O40, In (PMo11 O39)211-, Ln (PW11 O39)211-, Ln (AsW11 O39)211-, Ln(GeW11O39)213-, Ln(BW11O39)215-, Ln(GaW11O39)216-, Ln(P2Mo17O61)217-, Ln (As2W17O61)217-, Ln2P2Mo18O62and Ln2HP2Mo17VO62(Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, etc. ) which have Keggin, Daw-son and their derivative structures, were studied by means of potentiometric titration, polarography and cy-clovoltammetry. The mechanisms of the redox reactions were supposed-and the orders of redox ability of the heteropoly compounds were concluded. The periodic changes in reduction potentials of Ln(PMo11O39)211-and Ln(P2Mo17O61)2217- with Ln atomic numbers, and the correlation between E1/2 of Ln(XMo11O39)2(?)-(X =P, Ge, Si) and nq2(n is the main quantum number of the central atoms and q is their charges) were found.     

Emission Spectra of Some Heteropolytungstates Containing Europium

The emission spectra of some heteropolytungstates containing europium, K.[Eu(XW11 O39)2](X = P, Ge, As, or Ga), K17[EuCAs2W17O61)2] and K16H9EuAs4W40O140 have been investigated and the structures of these compounds are discussed. The emission spectra at room temperature are very similar to each other in terms of both the number of bands and transition frequencies, showing that they have the similar structures to those of K16[Ce(P2W17O61)2] and K12[U(GeW11O39)2].     

Hybrid inorganic-metalorganic compounds containing copper(II)-monosubstituted Keggin polyanions and polymeric copper(I) complexes

Four hybrid inorganic-metalorganic compounds containing copper(II)-monosubstituted Keggin polyoxotungstates, K3[Cu(I)(4,4'-bpy)]3[SiW11Cu(II)O39].11H2O (1), (paraquat)3[SiW11Cu(II)O39].6H2O (2; paraquat = N,N'-dimethyl-4,4'-bipyridinium), K3[Cu(I)(4,4'-bpy)]3[GeW11Cu(II)O39].11H2O (3), and Na2[Cu(I)(4,4'-bpy)]3[PW11Cu(II)O39(H2O)].4H2O (4), have been synthesized under autogenous pressure hydrothermal conditions and characterized by elemental analysis and infrared spectroscopy (FT-IR). The crystal structures of 1, 2, and 4 have been established by single-crystal X-ray diffraction. The crystal packings are characterized by the presence of monodimensional extended entities: either the polymeric polyanion [SiW11CuO39]n(6n-) (2), the cationic [Cu(4,4'-bpy)]n(n+) chain (4), or both simultaneously as in compound 1, where the inorganic and metalorganic sublattices are mutually perpendicular. To asses the influence of packing in the copper(I) complex structural diversity found in compounds 1 and 4, a search in the CSD database has been performed and the resulting geometrical features have been analyzed and compared with experimental crystallographic data and DFT calculations.     

Novel copper-complex-substituted tungstogermanates

Two copper-complex-substituted tungstogermanates [Cu5(2,2'-bpy)6(H2O)][GeW8O31].9H2O, 1, and {[Cu5(2,2'-bpy)5(H2O)][GeW9O34]}2.7H2O, 2 (2,2'-bpy = 2,2'-bipyridyl), have been hydrothermally synthesized and structurally characterized. X-ray structural analyses show that 1 is a rare tetralacunary Keggin anion of [B-beta-GeW8O31]10- substituted by copper complexes, while dimer 2 consists of two trilacunary [B-alpha-GeW9O34]10- Keggin units bridged by copper complexes. Magnetic measurement for 2 shows the presence of antiferromagnetic interactions within the dinuclear Cu2+ cations.     

Dimerization of mono-ruthenium substituted alpha-Keggin-type tungstosilicate [alpha-SiW11O39RuIII(H2O)]5- to micro-oxo-bridged dimer in aqueous solution: synthesis, structure, and redox studies

We report the dimerization of a mono-ruthenium(III) substituted alpha-Keggin-type tungstosilicate [alpha-SiW(11)O(39)Ru(III)(H2O)](5-) to a micro-oxo-bridged dimer [{alpha-SiW(11)O(39)Ru(m)}2O](n-) (m = III, n = 12; m = IV/III, n = 11; m = IV, n = 10). Single crystal X-ray structure analysis of Rb(10)[{alpha-SiW(11)O(39)Ru(IV)}2O].9.5H2O (triclinic, P1, with a = 12.7650(6) A, b = 18.9399(10) A, c = 20.2290(10) A, alpha = 72.876(3) degrees, beta = 88.447(3) degrees, gamma = 80.926(3) degrees, V = 4614.5(4) A(3), Z = 2) reveals that two mono-ruthenium substituted tungstosilicate alpha-Keggin units are connected through micro-oxo-bridging Ru-O-Ru bonds. Solution (183)W-NMR of [{SiW(11)O(39)Ru(IV)}2O](10-) resulted in six peaks (-63, -92, -110, -128, -132, and -143 ppm, intensities 2 : 2 : 1 : 2 : 2 : 2) confirming that the micro-oxo bridged dimer structure is maintained in aqueous solution. The dimerization mechanism is presumably initiated by deprotonation of the aqua-ruthenium complex [alpha-SiW(11)O(39)Ru(III)(H2O)](5-) leading to a hydroxy-ruthenium complex [alpha-SiW(11)O(39)Ru(III)(OH)](6-). Dimerization of two hydroxy-ruthenium complexes produces the micro-oxo bridged dimer [{alpha-SiW(11)O(39)Ru(III)}2O](12-) and a water molecule. The Ru(III) containing dimer is oxidized by molecular oxygen to produce a mixed valence species [{alpha-SiW(11)O(39)Ru(IV-III)}2O](11-), and further oxidation results in the Ru(IV) containing [{alpha-SiW(11)O(39)Ru(IV)}2O](10-).     

Catalytic mechanism of water oxidation with single-site ruthenium-heteropolytungstate complexes

Catalytic water oxidation to generate oxygen was achieved using all-inorganic mononuclear ruthenium complexes bearing Keggin-type lacunary heteropolytungstate, [Ru(III)(H(2)O)SiW(11)O(39)](5-) (1) and [Ru(III)(H(2)O)GeW(11)O(39)](5-) (2), as catalysts with (NH(4))(2)[Ce(IV)(NO(3))(6)] (CAN) as a one-electron oxidant in water. The oxygen atoms of evolved oxygen come from water as confirmed by isotope-labeled experiments. Cyclic voltammetric measurements of 1 and 2 at various pH's indicate that both complexes 1 and 2 exhibit three one-electron redox couples based on ruthenium center. The Pourbaix diagrams (plots of E(1/2) vs pH) support that the Ru(III) complexes are oxidized to the Ru(V)-oxo complexes with CAN. The Ru(V)-oxo complex derived from 1 was detected by UV-visible absorption, EPR, and resonance Raman measurements in situ as an active species during the water oxidation reaction. This indicates that the Ru(V)-oxo complex is involved in the rate-determining step of the catalytic cycle of water oxidation. The overall catalytic mechanism of water oxidation was revealed on the basis of the kinetic analysis and detection of the catalytic intermediates. Complex 2 exhibited a higher catalytic reactivity for the water oxidation with CAN than did complex 1.     

Hydrothermal synthesis and ab initio structural resolution from X-ray powder diffraction of a new open framework Cu(II) carboxyethylphosphonate: Na[Cu(O3P-(CH2)2-CO2)

Na[Cu(O3P-(CH2)2-CO2)], or MIL-39 (for Material of Institut Lavoisier), was synthesized hydrothermally at 443 K for 72 h under autogenous pressure. Its three-dimensional open structure was determined from X-ray powder diffraction. MIL-39 is monoclinic, it crystallizes in the space group P2(1)/m, (No. 11) with the following cell parameters at 293 K: a = 8.808(1) A, b = 6.4149(8) A, c = 5.3418(8) A, beta = 105.75(1) degrees, Z = 2. Its framework contains double rows built from isolated distorted CuO5 square pyramids linked by PO3C tetrahedral groups from (O3P-(CH2)2-CO2)3- organic moieties. At the other end of these latter moieties, the carboxylate group links two different Cu polyhedra of two neighboring chains. These connections define two types of channels along [010].