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     

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-)。     

PW11O39Co（Ⅱ）（H2O）5-的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B（RhB）的光降解为探针,评估了Keggin型钴取代杂多阴离子PW₁₁O₃₉Co（Ⅱ）（H₂O）^5-（PW₁₁Co）及其异相体系PW₁₁Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW₁₁Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW₁₁Co均相体系及其异相体系PW₁₁Co/D301R对RhB的可见光降解均有较高的光催化活性,但与PW₁₁Co相比,PW₁₁Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW₁₁Co均相体系相比,在PW₁₁Co/D₃₀₁R异相体系中由于PW₁₁Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

PW_(11)O_(39)Co(Ⅱ)(H_2O)~(5-)的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B(RhB)的光降解为探针,评估了Keggin型钴取代杂多阴离子PW11O39Co髤(H2O)5-(PW11Co)及其异相体系PW11Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW11Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW11Co均相体系及其异相体系PW11Co/D301R对RhB的可见光降解均有较高的光催化活性,但PW11Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW11Co均相体系相比,在PW11Co/D301R异相体系中由于PW11Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

X-ray structure of dodecasodium tricopper(II)bis[nonatungstabismuthate(III) hydrate, a polyoxometalate salt containing α-B-BiW9O33 units

The reaction of [Bi₂W₂₂O₇₄(OH)₂]^12– with Cu²⁺ in hot aqueous solution in the presence of Na⁺ affords the polyoxometalate salt Na₁₂[Cu₃Bi₂W₁₈O₆₆]32H₂O. Single-crystal X-ray analysis [monoclinic, space-group C2/m, a = 33.082(6) Å, b = 19.615(5) Å, c = 14.885(2) Å, = 90.632(12)°, Z = 4; R(F) = 0.065 for 6029 data with I> (I), wR(F ²) = 0.135 for all 8793 independent reflections] shows that the anion [{Cu(H₂O)}₃{BiW₉O₃₃}₂]^12–, on a crystal mirror-plane, has noncrystallographic symmetry close to D_3h. Two B--[Bi^IIIW₉O₃₃]^9– units are linked by an equatorial belt of three Cu(H₂O)²⁺ units. Three Na(H₂O)₂ ⁺ units are also attached in the equatorial plane. The bond geometry is square-pyramidal about each Cu atom and trigonal–prismatic about each Na.     

Comparative study between gas phase and liquid phase for the production of DMC from methanol and CO2

Direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide over Co1.5PW12O40 in liquid and in gas phase is investigated. The synthesized catalyst has been characterized by means of FTIR and XRD. Liquid phase experiment results showed that high pressures are favorable for the synthesis of DMC. However, DMC formation is limited by the reaction with co-produced water. DMC selectivity is more strongly dependent on the temperature than on the pressure of CO2. As for the reactions in gas phase, it has been found that both CH3OH conversion and DMC selectivity decreased with increasing temperature, owing to the decomposition of DMC at high temperatures. High temperatures and more amount of Co1.5PW12O40 catalyst favor the formation of dimethoxymethane (DMM) and methyl formate (MF).     

钒取代α-Keggin型杂多阴离子簇合物[PVnMo12－nO40](3＋n)－ (n＝1～3)氧化性能的DFT研究

运用密度泛函理论的离散变分(DFT-DVM)方法, 通过理论计算和模拟, 将不同个数V取代的α-Keggin型磷钼杂多阴离子簇合物以及它们的各个异构体区分开来, 探讨了V的取代效应对所形成物种[PVnMo12－nO40](3＋n)－ (n＝1～3)的氧化活性的影响. 研究表明, 单钒取代的簇阴离子的氧化活性最高, 其次是二钒取代的物种, 三钒取代的物种活性最低. 将计算得到的结果与实验测得的还原电势进行关联后发现, 这些杂多阴离子簇合物的费米能级(Ef)与其第一还原电势(ERP)之间呈现反比变化, 随着V取代个数n的增加, 簇阴离子所带的负电荷数逐渐增大, Ef值也随之增大, 而相应物种的ERP却逐渐减小. 进一步对含钨杂多阴离子簇合物[XW12O40]n－ (X＝CoII, FeIII, SiIV, PV)的计算分析证实, 这种关系具有一定的普适性; 在此基础上推测了杂多阴离子新物种[SW12O40]2－的存在, 并预测了其可能具有的氧化活性.     

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.     

铜取代Dawson结构杂多钨磷酸电荷转移配合物的合成与性质研究

Two new charge-transfer complexes, (DMAH)₁₀［CuP₂W₁₇O₆₂］·DMF·2H₂O and (DMAH)₁₄［Cu₂P₂W₁₆O₆₂］ have been prepared in aqueous solution from N,N′-dimethylaniline(DMA) and copper substituted polyoxotungstates with Dawson Structure, and characterized by elemental analysis, ICP, TG, IR, diffusion reflectance electronic spectra, polarography, and CV. The results indicate that the structure of anion has little change after the charge-transfer complexes are formed, but the characteristic vibrational bands have some red shift or blue shift. The charge transfer takes place under sunlight. There is a new absorption band at 625 nm in the solid reflectance electronic spectra of the complexes, it is ascribed to the IVCT (W(V)→W(Ⅵ) band of the reduced anion ［CuP₂W₁₇O₆₂］^10-. The conductivities at room temperature of title complexes are 3.6×10^-9 S·cm^-1 and 5.4×10^-9 S·cm^-1, respectively. Both of them are weak semiconductors.     

新型杂多酸阴离子层柱材料的合成、表征及性能的研究

采用离子交换法，将具有Keggin结构的磷钨醛、硅钨酸引入列Mg—Al、Mg—Al-Cu二元和三元的类水滑石(Hydrotalcite-like compounds,HTlcs)层间，成功制备了层有序度高，结晶度好的杂多酸阴离子水滑石，得到了通道高度达1．15nm的大层间的催化材料，并用红外、XRD表征了材料的结构．测定了对NOx的吸附性能．