硅胶固载杂多酸离子液体催化剂bmim-PW12/SiO2的制备及其在酯化反应中的应用

采用溶胶-凝胶法将杂多酸功能化离子液体bmim-PW12(1)固载到硅胶上制得硅胶固载杂多酸功能化离子液体催化剂bmim-PW12/SiO2[2-x(x=5,15,25,35,50)],采用TG-DTG,FT-IR,N2低温吸附脱附,XRD和正丁胺电位滴定等方法表征2的结构、织构性能和酸性。结果表明,2-x保持了1的Keggin结构,且1被较好地固载在硅胶上;2-x具有大的比表面积和强酸性。用7%的2-35催化乙酸与正丁醇的酯化反应,收率88.5%,且2-35重复使用5次后收率仍可达到75.4%。     

中德高中化学教材比较研究*——以“氧化还原反应”为例

基于闫春更等建立的“二维度四指标”教材难度微观评价模型,选取德国巴登符腾堡州(Baden-Württemberg)《今日化学Ⅰ》和中国人教版《化学1》为研究对象,就“氧化还原反应”主题的教材难度进行了测评和比较,为我国教材编写提供建议。     

核心素养导向下的科学概念教学*——以“氧化还原反应”为例

“氧化还原反应”是化学学科的核心概念。氧化还原反应理论是对微观粒子发生变化的认识,其学习过程应从化学反应的宏观现象出发辨识物质种类,借助反应物微观粒子模型和生成物微观粒子模型探析粒子变化,从而得出发生氧化还原反应时反应物中原子是如何转化成生成物中原子的,通过分析典型反应对氧化还原反应本质有清晰的认识之后,可不直接研究反应,而间接分析化学方程式得出反应物到生成物是否有电子的转移。     

新手-熟手高中化学教师PCK个案比较研究* ——以“氧化还原反应”主题为例

采用访谈法与质性资料分析法,测查了6名(3名新手与3名熟手)高中化学教师关于氧化还原反应主题的PCK。结果表明:(1)新手教师与熟手教师在CTO,KoL与KoS组分上存在较明显的差异。新手教师倾向于采用“教师-传授”教学取向,对学生知识的把握相对不足,更强调使用习题巩固策略;而熟手教师倾向于采用“学生-建构”教学取向,对学生知识的把握更为全面,更强调学生自主建构知识的过程。(2)新手教师与熟手教师在KoC与KoA组分上存在较明显的相似之处。在课程知识方面,教师对课程标准与教材中氧化还原反应主题内容具有较好的理解,但对化学基本观念、学科核心素养认识尚浅;在评价知识方面,教师偏向于传统的评价方式,且集中在形成性评价和总结性评价,但相对缺乏对学生的课前诊断性评价。文末据此对我国化学教师教育及其研究提出相关建议。     

基于真实问题情境的化学活动课设计*——以“氧化铁与酸的反应”为例

基于联系生活实际的真实问题情境,设计化学活动课,让学生在探究“可乐可以除铁锈”本质原因的过程中学习“氧化铁与酸的反应”,从而发展化学学科核心素养,提高解决实际问题的能力。     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

构建K3PW12O40/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应(英文)

太阳能向化学能转化是能源催化研究领域中一项意义重大且具有挑战性的课题,实现由半导体光催化剂产生的电子和空穴同步高效利用是该领域的研究目标.在众多催化剂中, S型异质结具有高氧化还原能力和快速电荷分离能力,非常适合用于完成同步的光解水反应和有机氧化反应,使电子和空穴得到同步高效利用.苯甲醇(BA)氧化是一种典型的有机氧化反应, BA可被选择性氧化为苯甲醛(BAD),其在合成药物、维生素、香料和其他有价值的化学品等方面具有重要作用.本文采用水热法合成了keggin型多金属氧化物H3PW12O40空心十二面体(KPW),将15 nm的Cd S纳米颗粒原位集成在KPW壳体上,形成KPW@CdSS型核-壳异质结.由于CdS和KPW之间的紧密界面和费米能级差异,形成了一个巨大的内部电场(IEF),促使载流子形成S型电荷转移机制.采用能带结构分析(原位辐照X射线光电子能谱(ISI-XPS)、价带X射线光电子能谱(VB-XPS)和电子自旋共振(ESR))等方法确定了S型异质结界面上的有效电子转移途径.光照条件下原位辐照的XPS结果表明Cd、S和W元素的结合能发生了变化.与普通XPS光谱相比, Cd和S...     

超分子化合物{[8-hydroxyquinolineH]44+·[SiW12O40]4-·2H2O}的水热合成、晶体结构及热稳定性

A supermolecular compound, {[8-hydroxyquinolineH]₄⁴⁺·[SiW₁₂O₄₀]^4-·2H₂O} was synthesized by hydrothermal reaction with silico-tungstic acid and 8-hydroxyquinoline. The crystal of the compound belongs to monoclinic system, space group P2₁/n, with a=1.282 6(6) nm, b=2.292 7(4) nm, c=2.092 0(6) nm, β=95.495(2)°, Z=4, V=6.124 1(7) nm³, D_c=3.791 g·cm^-3, μ=22.568 mm^-1, F(000)=6 200, R₁=0.029 3, wR₂=0.069 3, GOF=1.079. Su-permolecular compound is composed of one SiW₁₂O₄₀^4- with Keggin structure, four protonated cations of 8-hydroxyquinoline, two hydrones. Thermal analysis results showed that the anionic skeleton construction of heteropoly acid in compound decomposed approximately at 349.0 ℃. CCDC: 622142.     

[M(2,2'–bpy)2]2SiW12O40（M=Mn,Co;bpy=联吡啶）的合成、结构及其电催化水产氧性能

用水热法合成了过渡金属联吡啶配阳离子硅钨杂多酸:[M(2,2’-bpy)2]2SiW12O40(M=Mn(1)和M=Co(2)),采用红外光谱、元素分析、热重和单晶X射线衍射对其进行了表征。结果表明,化合物1和2是异质同构体,具有二维格子框架结构。初步研究了2种化合物的电催化H2O析出O2性能,发现化合物1对电催化H2O析出O2有一定的催化作用。     

[SiCu(H2O)W11O39]6-在玻碳电极上的多层组装及电催化性能

The electrochemical behavior of SiCu W11 heteropolyacide in acidic aqueous solution was studied. The effect of solution pH on the electrochemical behavior of SiCu W11 was discussed and the mechanism was suggested. New electrode was modified by muhilayer films composed of heteropolyanion (SiCu W11 and cationic polymer poly (diallyldimethylammonium chloride). Cyclic vohammetry showed the uniform growth of the film. The modified electrodes exhibited some special electrochemical properties in the films, different from those in homogeneous aqueous solutions. The effect of pH on the redox behavior of SiCu W11 in the films was discussed in details. The muhilayer film electrodes have an excellent electrocatalytic response to the reduction of BrO3^- and NO2^-.     

Synthesis and characterization of hybrid materials based on 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and Dawson-type tungstophosphate K7[H4PW18O62]·18H2O and K6[P2W18O62]·13H2O

In this study, we synthesized hybrid materials using well-Dawson polyoxometalates (POMs), K₇[H₄PW₁₈O₆₂]·18H₂O or K₆[P₂W₁₈O₆₂]·13H₂O and a room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]). K, W, P and CHN elemental analysis showed that one mole of [H₄PW₁₈O₆₂]⁷⁻ reacts with 6 moles of BMIM⁺ and one mole of [P₂W₁₈O₆₂]⁶⁻ reacts with 4 moles of BMIM⁺ to form, respectively, K[BMIM]₆H₄PW₁₈O₆₂ and K₂[BMIM]₄P₂W₁₈O₆₂. X-ray diffraction illustrated amorphous structure of the hybrid materials. FT-IR spectra showed the presence of both 1-butyl-3-methylimidazolium cation and the Dawson anion. TG analysis displayed a relative thermal stability of the hybrid materials compared to the parents Dawson POMs. Cyclic voltammetry showed that the reduction peak potentials of the Dawson anion in the hybrid materials shift towards negative values and the shift is more pronounced for K[BMIM]₆H₄PW₁₈O₆₂ compared to K₂[BMIM]₄P₂W₁₈O₆₂. This was attributed to a decrease in the acidity of the Dawson POM anion in the hybrid material.     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5? as building blocks

A two-dimensional network compound [Ce(DMF)₄(H₂O)][α-BW₁₂O₄₀]·H₂O·(HDMA)₂ (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H₅BW₁₂O₄₀·nH₂O, Ce(NO₃)₃·6H₂O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P2₁/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R ₁ = 0.07710, wR ₂ = 0.1416. Structural analysis indicates that every [Ce(DMF)₄(H₂O)]³⁺ building block is surrounded by three adjacent [α-BW₁₂O₄₀]⁵⁻ polyanions, meanwhile, every [α-BW₁₂O₄₀]⁵⁻ polyanion interconnects with three neighboring [Ce(DMF)₄(H₂O)]³⁺ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560°C. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4–7 media.     

A new route to the synthesis of thieno[2,3-d]pyrimidin-4（3H）-one derivatives catalyzed by 12-tungstophosphoric acid （H3PW12040）

Heteropoly acid H3PW12040 （PW） has been used as an effective catalyst for the synthesis of thieno[2,3-d]pyrimidin-4（3H）-one derivatives. The present methodology offers several advantages, such as high yields, short reaction times, mild reaction condition and a recyclable catalyst with a very easy work up.     

Influence of Pd precursors on the catalytic performance of Pd–H4SiW12O40/SiO2 in the direct oxidation of ethylene to acetic acid

The effects of palladium precursors (PdCl₂, (NH₄)₂PdCl₄, Pd(NH₃)₂Cl₂, Pd(NO₃)₂ and Pd(CH₃COO)₂) on the catalytic properties in the selective oxidation of ethylene to acetic acid have been investigated for 1.0 wt% Pd–30 wt% H₄SiW₁₂O₄₀/SiO₂. The structures of the catalysts were characterized using X-ray diffraction, N₂ adsorption, H₂-pulse chemical adsorption, infrared spectrometry of the adsorbed pyridine, H₂ temperature-programmed reduction and X-ray photoelectron spectroscopy. The present study demonstrates that the different palladium precursors can lead to the significant changes in the dispersion of palladium. It is found that Pd dispersion decreases as follows: PdCl₂ > (NH₄)₂PdCl₄ > Pd(NO₃)₂ > Pd(NH₃)₂Cl₂ > Pd(C₂H₃O₂)₂, which is nearly identical to the catalytic activity. This indicates that the dispersion of palladium plays an important role in the catalytic activity. Furthermore, density of Lewis (L) and Brönsted (B) acid sites are also strongly dependent on the palladium precursors. It is also demonstrated that an effective catalyst should possess a well combination of Brönsted acid sites with dispersion of palladium.     

H3PW12O40–[bmim][FeCl4]: A novel and green catalyst-medium system for microwave-promoted selective interconversion of alkoxymethyl ethers into their corresponding nitriles, bromides and iodides

In the present work, the catalytic activity of 12-tungstophosphoric acid immobilized on [bmim][FeCl₄] ionic liquid as a highly efficient and eco-friendly catalytic system for rapid and chemoselective direct conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides and iodides under microwave irradiation is reported. In these reactions, the products are obtained in high yields. The catalyst exhibited remarkable reactivity and was reused several times.