H4SiW12O40和双偶极Ru（Ⅱ）配合物形成的静电自组装多层膜

制备了含有H₄SiW₁₂O₄₀和双偶极Ru(Ⅱ)配合物交替层的一个新颖静电自组装多层膜.用紫外可见光谱、循环伏安学、原子力显微镜对薄膜进行了表征和性质研究.结果表明:膜沉积平稳、均匀,所制得的薄膜具有较好的电化学活性.AFM图像表明钌(Ⅱ)配合物和H₄SiW₁₂O₄₀层具有明显不同的微区结构.     

光催化还原制备Au/Ag核壳结构纳米粒子及其修饰电极的电催化性能

以Keggin结构硅钨杂多酸H4SiW12O40(SiW12)为光催化还原剂,通过光化学还原法制备Au/Ag核壳结构纳米粒子. 透射电子显微镜分析显示,所得纳米粒子粒径为30～40 nm,呈均匀分散的球形颗粒,该制备方法的特点是可以较好的避免单金属纳米粒子的形成. 将Au/Ag核壳纳米粒子修饰到具有PVP膜的玻碳电极表面,得到SiW12-(Au/Ag)-PVP多层膜修饰电极. 该修饰电极在0.5 mol/L H2SO4介质中具有良好的电化学响应,在0～-0.75 V电位范围内,出现了3对归属于SiW12的氧化还原峰,且电极性能稳定,灵敏度高. 对H2O2的电催化还原性能明显优于单金属Ag纳米粒子修饰电极,说明Au核的存在可以很好的改善Ag的电催化性能,Au和Ag之间存在相互协同催化作用.     

Keggin结构纳米硅钨酸铵的室温固相合成与物性

首次以H4SiW12O40 * 22H2O和(NH4)2C2O4 * H2O为原料,室温固相反应合成出(NH4)4SiW12O40纳米微粒;用元素分析、 FTIR确定产物的组成和结构; XRD、 TEM和BET对产物的形貌、晶粒尺寸和比表面积进行了表征; TG-DTA确定了产物的稳定温区.结果表明,产物为纳米粒子,平均粒径为60 nm,比表面积为108.7 m2/g,在430℃以下具有良好的热稳定性.在固相反应中,研磨和放热反应热效应能加快反应物扩散速率和生成物成核速率,使产物粒径减小;反应物含有结晶水和生成物H2C2O4 * 2H2O,对形成小粒径的(NH4)4SiW12O40纳米粒子起关键作用.     

Si取代Keggin型多酸催化光解水产氢机理

本文采用DFT和TD-DFT方法研究了Keggin型多酸[SiW12O40]4-光催化劈裂水产氢气机理。计算结果显示反应主要包括四个步骤：(i) 光激发,(ii) 电荷转移和生成单电子还原(OER)中间体,(iii) 生成双电子还原(TER)中间体,(iv)氢气从多酸表面解离和催化剂重生。当第一个电子从甲醇转移到多酸后,后续反应存在均为热力学上有利的放热途径,并推动第二个电子从甲醇自由基,H[SiW12O40]4-或[SiW12O40]5-转移到OER中间体H[SiW12O40]4-或[SiW12O40]5-生成TER中间体[SiW12O40]6-,H[SiW12O40]5-或H2[SiW12O40]4-,并伴随着H2产生。耦合的电子和质子转移路径在能量上最有利。甲醇和水分子的参与有利于H2产生。多酸在整个催化循环中,扮演了光敏剂、催化剂、电子的受体和给体。     

二茂铁与HnXW12O40.mH2O(X=P,Si, Ge)电荷转移配合物的室温固相合 成与性质

用室温固相反应法合成了三种具有非线性光学性质的二茂铁-多金属氧酸盐电荷转移配合物[Fe(C5H5)2H]3PW12O40(Ⅰ),[Fe(C5H5)2H]4SiW12O40(Ⅱ)和[Fe(C5H5)2H]4GeW12O40(Ⅲ)。用元素分析、紫外漫反射电子光谱、红外光谱、穆斯堡尔谱、ESR、XRD、循环伏安等手段对其进行了表征和研究,确定了该配合物的组成与结构,结果表明二茂铁与杂多阴离子之间发生了电荷转移,在形成配合物过程中杂多阴离子发生单电子还原反应,生成了混合价化合物,非线性光学性质研究表明电荷转移配合物的倍频效应强度分别为IⅠ^2ω=0.27I~KDP,IⅡ^2ω=0.06I~KDP,IⅢ^2ω=0.10I~KDP;三阶非线性光学χⅠ^(3)=2.4×10^-^13esu,χⅡ^(3)=3.1×10^-^12esu,χⅢ^(3)=6.5×10^-^12esu.     

STM image of tungstosilicic acid molecular layer on highly oriented pyrolytic graphite

Molecular layer of tungstosilicic acid (H4SiW12O40) deposited on freshly-cleaved highly oriented pyrolytic graphite (HOPG) was observed by scanning tunneling microscopy (STM) in air at room temperature.The molecular dimension (11.5 A) of H4SiWi2O4o measured by STM is consistent with known crystallographic parameter.We also imaged the boundary of H4SiW12O40 molecular layer on HOPG showing that molecular layer of H4SiW12O40 was formed.It has been proved that individual tungstosilicic acid species is imaged.The probable reason for the formation of the molecular layer is also discussed.     

一步催化合成二苯甲烷二氨基甲酸甲酯

研究了以H4SiW12O40-ZrO2/SiO2为催化剂,碳酸二甲酯(DMC)、苯胺和甲醛溶液为原料,一步催化合成二苯甲烷二氨基甲酸甲酯(MDC)的反应,考察了反应时间、反应温度和H4SiW12O40负载量等反应条件对催化性能的影响.适宜的反应条件是:DMC/苯胺/甲醛摩尔比为20/1/0.05,H4SiW12O40负载量为10%,443 K下反应7 h后降温到373 K下反应4.5 h.在此优化条件下,MDC的收率为24.9%.     

不同前驱体制备的Mn-H4SiW12O40/SiO2 催化剂对二甲醚催化氧化制取甲缩醛反应性能的影响

采用浸渍法分别用硫酸锰、醋酸锰、氯化锰和硝酸锰为原料制备了Mn-H4SiW12O40/SiO2 杂多酸催化剂。在常压连续流动固定床反应器中，考察了二甲醚选择氧化制取甲缩醛的反应活性。实验结果表明，催化剂的催化活性顺序为Mn-Cl2H4SiW12O40/SiO2>Mn(NO3)2H4SiW12O40/SiO2>MnSO4H4SiW12O40/SiO2>Mn(AC)2H4SiW12O40/SiO2。并进一步考察了反应温度对不同锰盐前驱体催化剂性能的影响。结果表明，随温度的升高，硫酸锰修饰的H4SiW12O40/SiO2 催化剂催化氧化比较剧烈，在613K时二甲醚转化率高达42.4%，但此时甲缩醛选择性仅为0.9%。采用氯化锰修饰的H4SiW12O40/SiO2催化剂，二甲醚催化氧化反应较缓和，并且甲缩醛的选择性明显高于分别采用硫酸锰、醋酸锰和硝酸锰改性的催化剂，在593K反应1h时，二甲醚转化率为8.6%，甲缩醛选择性达到37.5%。H2-TPR结果显示，硫酸锰改性的催化剂高温氧化性能明显强于另外三种催化剂，氯化锰的修饰使得催化剂的低温氧化性能变强。XRD结果表明，MnCl2 H4SiW12O40/SiO2催化剂的衍射特征峰明显强于其他三种催化剂，并且发现了MnO2衍射特征峰。     

含混合配体多酸超分子化合物的水热合成、晶体结构及催化活性

在水热条件下合成了四个含混合配体4,4’-bipy和2,2’-bipy/phen的多酸配位聚合物[Cu(4,4’-bipy)(2,2’-bipy)2]2[SiW12O40]?4H2O (1),[Ag4(4,4’-bipy)3(2,2’-bipy)2][SiW12O40]?2H2O (2),[Cu(4,4’-bipy)(phen)]2[H3O]2[SiW12O40]?8H2O (3)和[Cu(4,4’-bipy-Cl)(phen)]2[H3O][PW12O40]?H2O (4) (bipy = 联吡啶,phen = 邻菲罗啉),通过红外光谱、热重、元素分析、X-单晶衍射对聚合物进行了表征,在苯乙烯催化环氧化反应中,3和4显示了较高的催化活性,这与结构中存在配位不饱和金属中心有关.     

新型高分子-多酸电荷转移配合物的合成与表征

以Keggin结构的磷钨酸、硅钨酸为电子受体,高分子聚乙烯亚胺(PEI)为电子给体,合成了两种新型电荷转移配合物CH2CH2N(CH2CH2NH2)CH2CH2NHCH2CH2NH2.1H3PW12O40·10.6H2O(配合物Ⅰ)和CH2CH2N(CH2CH2NH2)CH2CH2NHCH2CH2NH1.3H4SiW12O40·8.3H2O(配合物Ⅱ)。采用元素分析、红外光谱和紫外光谱进行表征,并用扫描电镜观察产物形貌及其聚集形态。结果表明有机给体与杂多酸间有较强的相互作用。光致变色后,配合物中有机阳离子和杂多阴离子之间发生了电荷转移,导致杂多阴离子中WⅥ还原为WⅤ,同时有机阳离子被氧化,且该配合物有很高的耐溶剂性。     

Mechanistic analysis of the electrocatalytic properties of dissolved alpha and beta isomers of [SiW12O40]4- and solid [Ru(bipy)3]2[alpha-SiW12O40] on the reduction of nitrite in acidic aqueous media

Voltammetric studies on the reduction of alpha and beta isomers of the Keggin polyoxometalate anion [SiW12O40]4- reveal a series of electrochemically reversible processes in acidic aqueous media. In the presence of NO2-, catalytic current is detected in the potential region of the [SiW12O40]4-/5- process. Electronic spectroscopy and simulation of voltammetric data undertaken at variable [NO2-] and [H+] allow the following mechanism to be postulated, [SiW12O40]4- + e- <-->[SiW12O40]5-, H+ + HNO2 <--> NO+ + H2O, NO+ + [SiW12O40]5- --> NO + [SiW12O40]4-. The second-order rate constant for the rate-determining step is faster for the alpha isomer than for the beta one. This may be attributed to the different reversible potentials of -0.144 V (alpha isomer) and -0.036 V vs Ag/AgCl (beta isomer) and, hence, smaller driving force for an assumed outer sphere electron-transfer reaction in the case of beta isomer. A stable, water-insoluble, thin-film [Ru(bipy)3]2[alpha-SiW12O40] chemically modified electrode was generated electrochemically via ion-exchange of [Ru(bipy)3]2+ with Bu4N+ in the [Bu4N]4[alpha-SiW12O40] solid. The first reduction process with this modified electrode gives rise to the reaction [Ru(bipy)3]2[alpha-SiW12O40](solid) + H+(soln) + e- <--> H[Ru(bipy)3]2[alpha-SiW12O40](solid). The need to transfer a proton from the solution to the solid phase for charge neutralization purposes introduces a hydrogen-ion concentration dependence into this reaction, which is not found in the solution-phase study. Nevertheless, the voltammetric catalytic activity with respect to nitrite reduction is retained with the chemically modified electrode. However, nitrite catalysis with the [Ru(bipy)3]2[alpha-SiW12O40]-modified electrode is now independent of concentration of H+, rather than exhibiting a first-order dependence, and full mechanistic details for this process are unknown.     

双偶极半菁衍生物／H4SiW12O40自组装多层膜的研究

通过交替吸附H_4SiW_(12)O_(40)和双偶极半菁衍生物制备了一个新颖的无机- 有机杂化自组装多层膜。紫外可见光谱和X射线衍射研究证实了半菁衍生物 /H_4SiW_(12)O_(40)多层膜可被均匀沉积厚达至少12层，具有平均膜厚5.3nm(半菁 阳离子层加SiW_(12)O_(40)~(4-)层)的二维有序结构，膜中半菁衍生物与H_4SiW_ (12)O_(40)间发生了较强的电荷转移作用。循环伏安研究表明，薄膜具有较好的电 化学活性。     

Inorganic-organic hybrid materials with different dimensions constructed from copper-fluconazole metal-organic units and Keggin polyanion clusters

Inorganic-organic hybrid materials based on Keggin polyoxometalate building blocks combined with Cu(II)/Cu(I) and flexible fluconazole ligand [1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]methanol] (Hfcz) have been obtained by hydrothermal methods, namely, [Cu(II)(2)(Hfcz)(4)(SiW(12)O(40))].3H(2)O (1), [Cu(II)(4)(fcz)(4)(H(2)O)(4)(SiMo(12)O(40))].6H(2)O (2), [Cu(II)(2)(fcz)(2)][Cu(II)(4)(fcz)(4)(SiW(12)O(40))][Cu(II)(2)(fcz)(2)(H(2)O)(2)(SiW(12)O(40))].6H(2)O (3), (Et(3)NH)(2)[Cu(I)(2)(Hfcz)(2)(SiW(12)O(40))].2H(2)O (4), (Et(3)NH)(2)[Cu(I)(2)(Hfcz)(2)(SiW(12)O(40))].H(2)O (5) and [Cu(I)(4)(Hfcz)(4)(SiMo(12)O(40))] (6). Their structures have been determined by single-crystal X-ray diffraction analyses, and the compounds are further characterized by elemental analyses, IR spectra and thermogravimetric (TG) analyses. In 1, Cu(II) cations are bridged by fluconazole ligands to form a 3D lvt coordination polymeric network, which is connected by (SiW(12)O(40))(4-) anions to form a complicated 3D (4,6)-connected framework with the topology of (4(2).6(4))(4(6).6(7).8(2))(2). In 2, two fcz(-) anions chelate two Cu(2+) cations to form a [Cu(fcz)](2)(2+) dimer, which is bridged by (SiW(12)O(40))(4-) polyanions to generate a 2D (4,4) grid. Compound 3 is formed by three types of co-crystallizing subunits including a dimer [Cu(fcz)](2)(2+), a dumbbell molecule [Cu(4)(fcz)(4)(SiW(12)O(40))] and an infinite chain {[Cu(2)(fcz)(2)(H(2)O)(2)(SiW(12)O(40))](2-)}(infinity). In compounds 4 and 5, Hfcz ligands link Cu(+) cations to generate 1D coordination polymeric units, and (SiW(12)O(40))(4-) polyanions connect these metal-organic units to form two types of (6(3)) sheets which are topological isomerism. In compound 6, (SiMo(12)O(40))(4-) polyanions fixed in Cu(I)-Hfcz square rings are further extended into a 2D sheet via linking Cu(I) atoms of different rings. By carefully inspection of the structures of 1-6, it is believed that various transition-metal organic units and Keggin polyanions with different coordination modes are important for the formation of the different structures. In addition, electrochemical behaviors of compounds 1, 2, 5 and 6 have been investigated.     

Polynuclear complexes of main group and transition metals with polyaminopolycarboxylate and polyoxometalate

Six supramolecular compounds constructed by main group and transition metals, polyoxotungstates (SiW(12)O(40)(4-)) and trans-N,N,N',N'-1,2-cyclohexanediaminotetraacetic acid (H(4)CyDTA), (NH(4))(3)[Ni(4)Na(H(2)O)(10)(CyDTA)(2)][SiW(12)O(40)]·10H(2)O (1) (NH(4))(2)[Cu(3)Na(2)(HCyDTA)(2)(H(2)O)(13)][SiW(12)O(40)]·5H(2)O (2), (NH(4))(2)[Zn(5)(CyDTA)(2)(H(2)O)(16)][SiW(12)O(40)]·8H(2)O (3), (NH(4))(4)[Cd(4)(CyDTA)(2)(H(2)O)(8)][SiW(12)O(40)]·6H(2)O (4), (NH(4))(4)[Sr(3)(HCyDTA)(2)(H(2)O)(14)][SiW(12)O(40)]·2H(2)O (5) and [Ca(4)(H(2)CyDTA)(2)(H(2)O)(22)][SiW(12)O(40)]·8H(2)O (6), were synthesized in aqueous solution and characterized by IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction techniques. Single-crystal structure analyses indicate they are constructed by the complexes with different nuclearity and polyoxometalates. In the sequence of Ni, Cu, Zn the nuclearity of the homometallic complex units increases from 2 to 5. Cadmium ions gives a tetranuclear complex with a compact structure. In 5 and 6 the main group metal ions and CyDTA form polymeric chains. CyDTA exhibits rather different coordination patterns to main group metal ions and transition metal ions due to their ionic radii and electronic configuration. The complex units and polyoxometalates arrange in different patterns due to the different shapes of the complex units. The compounds exhibit different thermal decomposition processes and the formation of compounds 3 and 4 quenches ligand-centered emissions and gives a ligand-to-metal emission. The study on various temperature susceptibilities of 1 and 2 shows that there is an antiferromagnetic coupling in the two compounds but coupling patterns are different.     

钨硅酸/有机胺改性的二氧化硅纳米复合薄膜的制备和光致变色性质

光致变色材料由于在信息显示、传感器、调光器件和高密度存储等领域中具有显著的应用前景而备受关注[1] .杂多酸是一类含有氧桥的无机多核配合物 ,可作为电子受体与有机给体形成电子给 -受配合物 ,该类配合物在光激发下可发生电子转移 ,并表现出光致变色性 [2 ,3] .文献 [4,5 ]已报道了以杂多酸为电子受体设计制备光致变色化合物 ,并研究了其在固态和溶液中的光致变色性 ,但由于粉末和溶液本身的局限性而限制了其应用 .本文首次报道了由溶胶 -凝胶法将钨硅酸 ( Si WA)引入到有机胺改性的二氧化硅 ( APS)网络 ,得到 Si WA/APS纳米复合薄…     

Construction of polyoxometalates-based coordination polymers through direct incorporation between polyoxometalates and the voids in a 2D network

A series of polyoxometalates (POMs)-based coordination polymers, namely, {[Cu(2,3-Me2pz)(2,5-Me2pz)0.5]4(SiW12O40)(2,5-Me2pz)}n (2,3-Me2pz = 2,3-dimethylpyrazine; 2,5-Me2pz = 2,5-dimethylpyrazine; 1), {[Cu2(4,4'-bipy)4(H2O)4](SiW12O40)(H2O)18}n (4,4'-bipy = 4,4'-bipyridine; 2), {[Cu(2-Mepz)1.5]3(PMo12O40)(H2O)3.5}n (2-Mepz = 2-methylpyrazine; 3), {[Ag(2,3-Me2pz)1.5]4(SiW12O40}n (4), {[Cu(pz)1.5]4(SiW12O40)(H2O)3}n (pz = pyrazine; 5), {[Cu(2,3-Me2pz)1.5]4(SiW12O40)}n (6), {[Cu(4,4'-bipy)1.75]4(SiW12O40)(H2O)2}n (7), and {[Cu2(4,4'-bipy)4(H2O)4](SiW12O40)(4,4'-bipy)2(H2O)4}n (8), were synthesized through direct incorporation between POMs and the voids of the 2D network. Crystal structural analysis reveals that the relationship between the size of the void of the 2D network and that of POMs is of key importance for successful synthesis of POMs-based open metal-organic frameworks. Guest replacement shows that the pore size of the framework constructed through direct incorporation between POMs and the voids of the 2D network is very sensitive to guest molecules.     

A Novel Optical Complex between an Organic Substrate and a Polyoxometalate. Crystal and Molecular Structure of alpha-H(4)SiW(12)O(40).4HMPA.2H(2)O (HMPA = Hexamethylphosphoramide)

A solvated complex of alpha-H(4)SiW(12)O(40).4HMPA.2H(2)O composed the heteropolytungstate alpha-H(4)SiW(12)O(40) and the organic substrate hexamethylphosphoramide (HMPA) has been synthesised, purified, and characterized. The electronic spectra (lambda = 220-500 nm) as well as the (1)H NMR spectra for the title compound dissolved in CD(3)CN establish that this complex dissociates into free SiW(12)O(40)(4)(-) and HMPA moieties in solution unless the organic substrate HMPA is present in very high concentrations. The solid reflectance electronic spectra and IR spectra indicate that there is interaction between the alpha-H(4)SiW(12)O(40) and the organic substrate. The complex has no photosensitivity under irradiation of sunlight, but under the near-UV light result in a charge transfer by oxidation of the HMPA and the reduction of the polyoxometalate. Light yellow polyhedrons of the title compound crystallize from the aqueous solvent of acetonitrile and aqueous solution as the formula of alpha-H(4)SiW(12)O(40).4HMPA.2H(2)O in the monoclinic, space group P2(1). The unit cell has a = 12.791(3) ?, b = 22.103(6) ?, c = 15.532(4) ?, beta = 102.860(10) degrees, and Z = 2. From the bond-valence parameters, it was found that the four hydrogen atoms of the polyoxometalate were combined with the N atoms of the four HMPA respectively. The title compound shows a certain second-order and third-order nonlinear optical response of I(2)(omega) = 0.7I(2)(omega)(KDP) and chi((3)) = 2.63 x 10(-)(11) esu, respectively.