PEO-12-钨磷酸质子导电聚合物电解质膜

以聚氧乙烯(PEO)为基质, 在其中掺杂适量的钨磷酸, 制备PEO-H₃PW₁₂O₄₀质子导电聚合物电解质膜. XRD及IR测试表明体系中Keggin阴离子与PEO链相互作用形成新的化合物; Keggin阴离子的存在有利于水合质子的形成. PEO-H₃PW₁₂O₄₀复合膜的电导率室温最高可达4.0×10^－3 S•cm^－1.     

P、As为中心原子的杂多钼酸盐的合成、热稳定性及还原性研究

在合成(NH₄)₃PMo₁₂O₄₀和K₃PMo₁₂O₄₀的基础上,用改进的方法合成了(NH₄)₃AsMo₁₂O₄₀和K₃AsMo₁₂O₄₀,以FTIR、XRD、TG-DTA、ESR和TPR等手段对其结构、热稳定性和还原性进行了考查,当中心原子由P换成As后,杂多钼酸盐热稳定性下降,还原性提高.     

PEO-12-钨磷酸掺杂的质子导电聚合物电解质膜

以聚氧乙烯(PEO)为基质,在其中掺杂适量的钨磷酸,制备PEO-H3PW12O40质子导电聚合物电解质膜.XRD及IR测试表明体系中Keggin阴离子与PEO链相互作用形成新的化合物;Keggin阴离子的存在有利于水合质子的形成.PEO-H3PW12O40复合膜的电导率室温最高可达4.0×10-3S·cm-1.     

以PEO为基质的离子及质子导电聚合物电解质

本文以PEO-LiClO₄为基质,在其中加入适量的纳米氧化锌及氧化锡,制备PEO-LiClO₄-ZnO及PEO-LiClO₄-SnO₂离子导电聚合物电解质膜,测定了复合电解质膜的电导率,并探讨了纳米粒子与PEO链的相互作用,提出复合电解质膜的电导率提高的主要影响因素。本文还合成以PEO为基质的PEO-12-钨硅酸质子导电聚合物电解质膜,讨论12-钨硅酸的加入对PEO的构型及Keggin离子的影响并分析PEO-12-钨硅     

磷钼酸和磷钼钒酸及其盐的氧化还原特性

本文以硫酸为支持电解质,在水-1,4-二氧六环混合溶剂中,用电化学方法研究了Keggin结构的H₃PMo₁₂O₄₀、M₃PMo₁₂O₄₀(M=NH₄,Na,K)、H₄PMo₁₁VO₄₀及M_nH_4-nPMo₁₁VO₄₀(M=Na,La,K,Eu;对于Na和La,n=1～4,对于K,n=4;对于Eu,n=2)的氧化还原特性。还分析了钼和钒的氧化还原顺序及其可逆性。     

Li1.5Al0.5Ge1.5(PO4)3基固体复合电解质的制备及锂离子导电行为

将聚氧化乙烯(PEO)和二(三氟甲基磺酰)亚胺锂(LiTFSI)混合(固定EO/Li摩尔比为13)后, 采用溶液浇注法制备了一系列不同Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP)与PEO质量比的LAGP-PEO(LiTFSI)固体复合电解质体系. 结合电化学阻抗法、 表面形貌表征以及与惰性陶瓷填料(SiO₂, Al₂O₃) 性能的对比分析, 探讨了LAGP在固体复合电解质中的作用机理以及锂离子的导电行为. 结果表明, 在以LAGP为主相的固体复合电解质中, PEO主要处于无定形态, 整个体系主要为PEO与LiTFSI的络合相、 LAGP与PEO(LiTFSI)相互作用形成的过渡相和LAGP晶相. 其中LAGP作为主要的导电基体不仅起到降低PEO结晶度、 改善两相导电界面的作用; 同时自身也可以作为离子传输的通道, 降低锂离子迁移的活化能, 从而使离子电导率得到提高. 当LAGP与PEO的质量比为6:4时, 固体复合电解质的成膜性能最好, 离子电导率最高, 在30 ℃时为2.57×10^-5 S/cm, 接近LAGP的水平, 电化学稳定窗口超过5 V.     

两种砷钼杂化多酸盐的合成、 结构及变色性质

分别以2种V形羧酸[1,3-苯二甲酸(H₂BDC)和5-羟基-1,3-苯二甲酸(H₂OIP)]与钼酸铵进行反应, 得到了 2种有机酸根与无机酸根缩合构成的杂化砷钼酸盐： (NH₄)₁₇H₄[(AsMo₆O₂₁)₂(AsMo₆O₂₃)(BDC)₄]·28H₂O(1)和 (NH₄)₅Cs₈H₆[(AsMo₆O₂₁)₃(OIP)₅]·40H₂O(2). 利用单晶X射线衍射对2种化合物进行了结构分析, 发现二者均为三聚结构. 对2种化合物的光致变色及热致变色性质进行了研究, 发现在氙灯照射下2种化合物均可在5 min内变色. 当将2种化合物的样品加热到373 K时, 均出现颜色变化, 并随着温度升高颜色逐渐加深. 光致变色与热致变色过程前后的EPR检测结果均提示化合物的颜色变化与Mo^VI转化为Mo^V有关.     

多核多氧硫钼酸盐化合物的合成及质子传导性能

质子交换膜燃料电池(PEMFC)因能量转化率高、 污染小、 工作温度低、 启动速度快而被广泛应用. Nafion系列膜成本高、 结构特性模糊, 阻碍了质子传导性能的进一步提高和对传导机理的精确理解. 因此开发具有结构明确、 传导路径清晰的高质子传导率的晶态材料对于燃料电池领域具有重要意义. 本文利用有机配体5-羟基间苯二甲酸作为模板诱导[Mo₂S₂O₂]²⁺阳离子, 自组装成一种多核多氧硫钼酸盐簇[N(CH₃)₄]₂H₂· [(Mo₂S₂O₂)₈(OH)₁₆(C₈O₅H₄)₂]·22H₂O(Mo₁₆). 该化合物清晰明确的结构和结构中存在的密集氢键网络可用于进行质子传导性能的研究. 交流阻抗测试结果表明, Mo₁₆在宽温度范围内具有较高的质子传导性能. 在97%湿度(RH), 85 ℃条件下其质子传导率可达1.9×10^-2 S/cm, 表明该化合物具有作为高效质子导体的良好前景.     

NH3R++NHR2(R=H,CH3)体系质子传递反应的从头算研究

用从头计算法在HF/6-31G^*基组水平上研究了NH₄⁺+NH₃→NH₃+NH₄⁺,NH₄⁺+NH₂CH₃→NH₃+NH₃CH₃⁺,NH₄⁺+NH(CH₃)₂→NH₃+NH₂(CH₃)₂⁺以及NH₃CH₃⁺+NH₂CH₃→NH₂CH₃+NH₃CH₃⁺等4个体系的质子传递反应的机理.结果表明:(1)上述质子传递反应均具有双阱型的势能面,质子沿N(1)、N(2)连线直接传递;(2)质子受体分子中的甲基对质子传递起促进作用,而质子给体离子中的甲基则阻碍质子的传递。     

PEO-12-钨磷酸质子导电聚合物电解质膜

以聚氧乙烯(PEO)为基质, 在其中掺杂适量的钨磷酸, 制备PEO-H₃PW₁₂O₄₀质子导电聚合物电解质膜. XRD及IR测试表明体系中Keggin阴离子与PEO链相互作用形成新的化合物; Keggin阴离子的存在有利于水合质子的形成. PEO-H₃PW₁₂O₄₀复合膜的电导率室温最高可达4.0×10^－3 S•cm^－1.     

镶嵌钨硅酸的新型有机-无机纳米复合薄膜的制备及光致变色性能研究

将超分子自组装技术与Sol-gel过程相结合,制备了镶嵌Keggin结构钨硅酸的MAAM/VTEOS/TEOS纳米复合薄膜,并采用IR,XRD和TG-DSC等方法对薄膜进行了结构表征.在复合薄膜光照变蓝后,通过UV-Vis和ESR光谱对薄膜的光致变色性能及其机理进行了研究.结果表明,钨硅酸在复合网络中仍保持Keggin结构,与有机-无机复合基体中的-NH₂通过氢键发生强烈的相互作用,经紫外光照后发生电荷转移,[SiW₁₂O₄0]₄^-被还原为[SiW₁₂O₄0]₅^-,同时产生氨基自由基.褪色过程则与氧气存在与否有关,实验结果表明,该薄膜具有良好的光致变色性能,对光有较快的响应恢复速度和良好的可逆重复性.     

Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions

We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions. Unusually, the highly charged lacunary site remains uncoordinated to the Hf metal center but instead interacts with an ammonium cation. (31)P NMR indicates that complexation of the Keggin anion, [PMo 12O 40] (3-), to Hf (IV) and Zr (IV) will stabilize the Keggin anion to a much higher pH than usually observed.     

磷钼杂多酸-L-半胱氨酸自组装超分子pH敏感膜电位传感器

自组装超分子膜;pH电位传感器;磷钼杂多酸-L-半胱氨酸自组装超分子pH敏感膜电位传感器     

杂多酸/聚乙烯醇复合膜的制备及光催化性能研究

合成了过渡金属取代的硅钨酸盐K₆SiM(H₂O)W₁₁O₃₉(M=Co、Ni、Cu,简称为SiMW₁₁),利用硅钨酸(H₄SiW₁₂O₄₀·nH₂O,简称为SiW₁₂)与SiMW₁₁做母体,分别将它们负载于聚乙烯醇(polyvinyl alcohol,PVA)上,制成一系列杂多酸/聚乙烯醇复合膜光催化剂,利用IR、SEM进行了表征.以高压汞灯为光源,分别研究了SiW₁₂/PVA、SiCoW11/PVA、SiNiW₁₁/PVA、SiCuW₁₁/PVA复合膜对有机染料甲基橙的光催化脱色,它们都具有很高的催化活性,60 min内对甲基橙的脱色率均可达到90%以上,其中SiW₁₂/PVA复合膜效果最好,12 min内脱色率达100%.提高SiW₁₂负载量可有效提高膜的光催化活性,当SiW₁₂与PVA质量比为1:1时催化活性最高.     

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…     

Interaction of Keggin anions of 12-tungstophosphoric acid with Ce(x)Zr(1-x)O2 solid solutions

The interaction of 20 wt% 12-tungstophosphoric acid with Ce(x)Zr(1-x)O(2) solid solutions has been studied by PXRD, FTIR, FT-Raman, H(2)-TPR, NH(3)-TPD, diffuse reflectance UV-vis-NIR, and (31)P MAS NMR techniques. The study indicates that the Keggin anions are attached to Lewis metal ion centres and anion vacancies on Ce(x)Zr(1-x)O(2) supports through WO terminal bonds. The Keggin units at the interface are chemically perturbed as indicated by non-intrinsic IR bands observed at 958 cm(-1) (WO(ter) bond), and 1052, 1102 cm(-1) (PO bond). NH(3)-TPD shows that the Keggin anions fixed to Lewis sites and/or oxygen ion vacancies decrease the ammonia uptake on Ce(x)Zr(1-x)O(2) solid solutions. H(2)-TPR shows modified redox behaviour of Ce(x)Zr(1-x)O(2) solid solutions due to the simultaneous reduction of ceria, decomposition of Keggin anions and the reduction of WO(3). The broadening of (31)P MAS NMR and DR-UV-vis-NIR spectra demonstrate the existence of chemical interactions between the Keggin anions and Ce(x)Zr(1-x)O(2) supports.     

Functions of Acyclic Poly(ethylene Oxide) Homologs: Acceleration of Nucleophilic Reactions and Selective Ion Transport through Membranes

The acceleration effect of poly(ethylene oxide) on nucleophilic reactions was investigated. The enhancement of the reaction rate was interpreted by the cooperative solvation of alkali metal ions with ethereal oxygens of PEO resulting in active nucleophilic anions. In relation to the complex formation of alkali metal ions with PEO, the oligo(ethylene oxide) derivatives were prepared as the synthetic ionophores, which were able to transport alkali metal ions selectively through a liquid membrane against the alkali metal ion concentration.     

Keggin Polyoxotungstoborate with Uranium(IV)

A new uranium tungstoborate heteropolyanion K₁₂[U(BW₁₁O₃₉H)₂]·23 H₂O has been prepared and investigated by thermal analyses, IR, UV-Vis spectroscopy and magnetic susceptibility measurements. The compound obtained from Keggin monolacunary anions is 1:2 sandwich-type and exhibits a square antiprismatic stereochemistry for uranium (IV) ion.     

Polyoxometalates in solution: Molecular dynamics simulations on the alpha-PW12O40(3-) Keggin anion in aqueous media

The Keggin anion, PW12O40(3-), is one of the most representative polyoxometalates (POMs). In recent years increasing theoretical work focused on this family of compounds has explained or even predicted some of their properties using quantum mechanics methods. In this report we applied for the first time molecular dynamics (MD) to the title compound to analyze its interactions with water. We used three atomic charge definitions (Mulliken, ChelpG, and formal charges) to carry out MD simulations. The results show that the terminal oxygens of the cluster are invariably most effectively solvated by water because of their prominent position within the framework. On the other hand, bridging oxygens, which are confined in more internal positions, concentrate a smaller portion of the whole solvation. We investigated the hydrogen bonds existing between water and the cluster, confirming that the terminal positions form more contacts with H2O than any other site of the cluster. In the end, the lifetime of such contacts is longer with bridging oxygens, presumably due to their higher atomic charge.