三缺位杂多阴离子PW_9(O_(34))~(9-) 的二苯基硅衍生物的合成和表征

以Na8 H[PW9O3 4 ]·nH2 O与Ph2 SiCl2 为原料于乙腈中合成了三缺位杂多阴离子的二苯基硅衍生物(TBA)3[α-A -PW9O3 4 (Ph2 Si)3 ](TBA为四丁基铵盐的缩写)(记为I),并由元素分析、红外光谱、紫外光谱对化合物进行了表征,结果表明,二苯基硅通过六个Si-O -W桥键填充到三缺位杂多阴离子的骨架上,形成了开环的饱和笼形结构.热分析结果表明,该化合物的热分解温度在 4 95.2℃左右     

Evaluation of a PVC‐Based Thionine‐Zeolite and Zeolite Free Membranes as Sensing Elements in Ion Selective Electrode

The construction and performance characteristics of thionine electrodes based on the ion‐pair complex thionine‐tungstophosphate and thionine‐mordenite zeolite embedded in a polyvinyl chloride (PVC) matrix is described. Thionine electrode based on the ion‐pair is used for the indirect determination of ascorbic acid by standard addition method.     

三缺位α-9钨镓杂多酸盐的合成与性质

本文报道了一种新的三缺位杂多阴离子α-[GaW_9O_(34)H_2]~(9-)的钠、钾、四甲基铵盐的合成方法,并通过元素分析、红外、紫外、极谱、热分析等方法对它进行了表征。α-[GaW_9-O_(34)H_2]~(9-)是一具有三个空位的杂多阴离子,它能与过渡金属离子反应生成具有Keggin结构的三取代钨镓杂多阴离子[GaW_9O_(37)M_3(H_2O)_3]~(R-)。     

由四核Fe(Ⅱ)金属簇和三缺位Keggin型磷钨酸盐构筑的夹心型多金属氧酸盐(英文)

利用水热法合成了由四核FeⅡ簇和三缺位Keggin型磷钨酸盐共同构筑而成的夹心型多金属氧酸盐(H2dien)4H2[Fe4(H2O)2(α-B-PW9O34)2]·8H2O(1)(dien=二乙烯三胺);采用红外光谱、X-射线单晶衍射定性表征了产物的结构,利用元素分析测定了其组成.结果表明,化合物1属于三斜晶系,P-1空间群.其多阴离子[Fe4(H2O)2(α-B-PW9O34)2]10-由两个[α-B-PW9O34]9-单元通过Fe4O14(H2O)2簇连接而成;Fe2+离子采用六配位的八面体几何构型.同时,质子化的H2dien2+充当抗衡阳离子,经氢键与杂多阴离子[Fe4(H2O)2(α-BPW9O34)2]10-相互作用形成三维结构.     

过渡金属-联咪唑-Dawson型钨磷酸盐杂化化合物的酶固定化性能

利用水热法和直接沉淀法, 设计合成了5例由过渡金属(TM)-联咪唑配阳离子与Dawson型钨磷酸阴离子构成的多金属氧酸盐(POM)基有机-无机杂化化合物[Ni(H₂biim)₃]₄[Ni(H₂biim)₂(P₂W₁₈O₆₂)₂]·2H₂O(1), [Co^III(H₂biim)₃]₂[P₂W₁₈O₆₂]·8H₂O(2), [Cu(H₂biim)₂]₃[P₂W₁₈O₆₂]·4H₂O(3), [Co^II(H₂biim)₃]₂H₂[P₂W₁₈O₆₂]·9H₂O(4)和 [Ni(H₂biim)₃]₃[P₂W₁₈O₆₂]·2H₂O(5); 并利用X射线单晶衍射分析(SC-XRD)、 红外光谱(IR)和热重-差热分析 (TG-DTA)等对其进行了表征. 化合物1~5作为载体用于固定辣根过氧化物酶(HRP)时, 显示出了较高的酶固定化能力. 另外, 利用圆二色光谱(CD)和激光扫描共聚焦显微镜(LSCM)等方法评价了固定化酶HRP/1~HRP/5的重复使用性、 储存稳定性和检测过氧化氢(H₂O₂)的性能. 由于该类POMs与HRP间存在强的相互作用, 利用简单的物理吸附法即可实现POMs对HRP的固载. POMs对酶的固定不但提高了HRP对使用及储存环境的耐受性, 同时也拓展了POMs在酶固定化领域的应用.     

Construction and visible-light photocatalytic performance of carboxyethyltin/transition metal–functionalized wheel-like tungstophosphates

The wheel-like tungstophosphate ([P₈W₄₈O₁₈₄]⁴⁰⁻, abbreviated as P₈W₄₈) reacted with estertin trichloride (Cl₃SnRCH₃, R = CH₂CH₂COO) in aqueous solution, resulting in a new wheel-like polyoxometalate (POM) containing six SnR fragments, formulated as K₆Na₂₄[{(SnR(H₂O))₂(μ-OH)(μ-SnR(H₂O))}₂(P₈W₄₈O₁₈₄)]·59H₂O (abbreviated as Sn ₆ - P ₈ W ₄₈ ). Based on this, the transition metal (TM) was further introduced into the Sn ₆ - P ₈ W ₄₈ system, self-assembling three other wheel-like POMs with the general formula K_xNa_yH_{26 − x − y}[{TM(H₂O)₃(SnR(H₂O))₂(μ-OH)(μ-SnR(H₂O))}₂(P₈W₄₈O₁₈₄)]·nH₂O (abbreviated as TM ₂ - Sn ₆ - P ₈ W ₄₈ , TM = Mn, Co, Ni; x = 0, 1, 2; y = 19, 22, 15; n = 72, 85, 75, respectively). The structures of these new organometal and TM co-modified compounds were characterized using infrared, UV–Vis. spectroscopy, ¹¹⁹Sn NMR, and powder- and single-crystal X-ray diffraction analysis. The estertin precursor hydrolyzed into carboxyethyltin (SnR) fragment in these crystalline POM materials, which can improve their adhesion to titanium dioxide (TiO₂). The photocatalytic performance of Sn ₆ - P ₈ W ₄₈ , TM ₂ - Sn ₆ - P ₈ W ₄₈ , and their TiO₂ composites was examined by studying the degradation of a model dye pollutant Rhodamine B (RhB) under visible-light irradiation without adding hydrogen peroxide (H₂O₂), and the photocatalytic mechanism was also discussed. The experimental results show that the title compounds exhibit a quicker and better photocatalytic degradation effect on RhB compared with their parent compound, indicating that the introduced organotin groups play a significant role. Moreover, it was found that H₂O₂ was produced after illumination pretreatment for POM solution, promoting the photocatalytic reaction.     

Study on adsorption behavior of cesium using ammonium tungstophosphate (AWP)-calcium alginate microcapsules

A functional microcapsule was prepared by encapsulating the fine crystalline ammonium tungstophosphate(AWP) in calcium alginate polymer(CaALG).The characterization of AWP-CaALG microcapsule was examined by SEM and EPMA.The adsorption behavior of Cs(I),Rb(I),Sr(II),Pd(II),Ru(III),Rh(III),La(III),Ce(III),Dy(III) and Zr(IV) was investigated by the batch method.The batch experiments were carried out by varying the shaking times,HNO 3 concentration,and initial concentration of metal ions.Relatively large K d values above 10 5 cm 3 /g for Cs(I) were obtained in the range of 0.1-5 M HNO 3,resulting in a separation factor of Cs/Rb exceeding 10 2.In contrast,the K d values of Sr(II),Pd(II),Ru(III),La(III),Dy(III),Ce(III) and Zr(IV) were considerably lower than 50 cm 3 /g.The K d value of Cs(I) decreased in the order of the coexisting ions,H + > Na + >> NH 4 +,and a linear relationship with a slop of about 1 was obtained between log K d and log [NH 4 + ]([NH 4 + ] > 0.01 M).The adsorption of Cs(I) was found to be controlled by chemisorption mechanism,and followed a Langmuir-type adsorption equation.A high uptake percentage of 99.4% for Cs(I) was obtained by using the dissolved solutions of spent fuel from FBR-JOYO(JAEA).     

单铌和单过氧铌杂多配合物的合成、表征及催化性能

过氧铌钨磷杂多酸盐;催化活性;单铌和单过氧铌杂多配合物的合成、表征及催化性能     

三空位杂多阴离子XW_9O_(34)~(10-)(X=Si,Ge)取代衍生物的结构类型及其~(183)W NMR谱的特征模式

三空位阴离子SiW_9和GeW_9与金属离子反应可分别生成Keggin三取代型、夹心型及双聚型杂多阴离子.总结了三种结构类型取代衍生物的~(183)W NMR谱化学位移的特征模式.     

新型高聚合度钨磷多金属氧酸盐超分子化合物的水热合成与晶体结构

首次报道了新型高聚合度钨磷多金属氧酸盐超分子化合物H16{[P4W14Na3 (H2O)7O58]2[Na4(H2O)13]2[P4W14Na2(H2O)2O56]}·24H2O的水热合成方法,用元素分析、IR和单晶X射线衍射等手段进行了表征．晶体属三斜晶系,P1空间群,a= 1．551 5(3)nm,b=1．866 4(4)an],c=2.224 9nm,α=105.10(3)°,β=96.74(3)°,γ= 95．23(3)°,V=6．127(2)nm3,Z=1,Mr=12 418.36,Dc=3．365 g·cm-3,μ=19．843 mm-1, F(000)=5 516,R=0．0 829,Rw=0．2 020．测定结果表明,标题化合物是由两个[P4W14Na3 (H2O)7O58]9-和一个[P4W14Na2(H2O)2O56]6-阴离子通过O-Na-O桥键合而成．