微乳液法制备超细K2Ln2Ti3O10及其光催化活性研究

以钛酸四丁酯、氢氧化钾和镧系金属氧化物为原料。采用微乳液法制备了系列超细K2Ln2Ti3O10（Ln=La．Ce,Pr．Nd，Sm，Eu，Gd）光催化剂。并考察了其光催化活性。通过X射线衍射（XRD）、透射电镜（TEM）和紫外可见吸收光谱（UV—Vis）对其进行了表征。结果表明：用微乳液法制备催化剂可以在较低的温度下（900℃），用较短的烧结时间（3h）合成结晶度高、粒径较小（200Mm）的K2Ln2Ti3O10钙钛矿型层状结构化合物。催化剂在紫外光和可见光条件下均具有光催化降解甲基橙的活性。紫外光条件下可以明显提高光催化降解活性，降解率达到60％。     

无机层状复合氢氧化物中顺铂-DNA模型分子的选择性插入

药物分子的选择性包裹和控制释放是药物研究领域中具有挑战性的研究方向。本文研究表明:顺铂-DNA模型分子cis-[Pt(NH₃)₂(5′-GMP)₂](5′-GMP 5′-单磷酸鸟苷)可插入无机层状复合氢氧化物[Zn_0.68Al_0.32(OH)₂](NO₃)_0.32·mH₂O。但另一种层状复合氢氧化物[LiAl₂(OH)₆]Cl·H₂O由于其阳离子层中正电荷密度较高、阳离子层与层间阴离子之间静电作用较强,因而顺铂-DNA模型分子不能通过离子交换方式插入其层间。光谱数据证实插入层间的顺铂-DNA模型分子结构不变。这可能为铂-DNA分子的传递提供新的方法。     

ADVANCES IN STUDY OF A NEW CLASS OF PILLARED LAYERED MICROPOROUS MATERIALS?¤?¤POLYOXOMETALATE-TYPE HYDROTALCITE-LIKE CATALYSTS

In the present paper, on the basis of our work. advances in study of the catalysts of polyacid-type hydrotalcite-like are reported and reviewed. Using polyoxometalates (POM) as pillaring species and layered double hydroxides (LDH) as host matter, a new class of catalytic materials, LDHPOM, has been synthesized by five different methods. Their acidic and oxidative catalytic properties have been investigated by several research groups. The above mentioned information is given in this review.     

单斜层状LiMnO2的球磨-离子交换法合成及其电化学性能研究

通过球磨促进固相反应法合成出了具有单斜层状结构的前驱物NaMnO₂，随后通过离子交换得到了单斜层状LiMnO₂。XRD测试结果显示产物为单相。扫描电镜(SEM)和透射电镜(TEM)观测结果显示LiMnO₂的粒子尺寸为300～500 nm，HRTEM分析显示干扰条纹的间距为0.485 nm，基本对应于m-LiMnO₂的(001)晶面间距。红外吸收光谱(IR)和X射线光电子能谱(XPS)被用来测量m-LiMnO₂中Mn-O键的伸缩和弯曲振动吸收和Mn元素的价态。合成的m-LiMnO₂在电化学充放电循环初期表现了较好的电化学性能，但其循环寿命仍需要进一步改善。     

Cr(VI)在Mg-Al型类水滑石上的吸附-脱附性研究I.吸附性

研究了Cr(VI)在带结构正电荷的Mg-Al型类水滑石(HTlc)上的吸附性能,考察了pH、无机电解质添加剂NaCl,NaNO3,Na2SO4和Na3PO4及有机添加剂EDTA和柠檬酸等因素的影响,并结合红外光谱和XRD实验结果探讨了吸附机理.研究表明,Mg-Al型HTlc对Cr(VI)有很强的吸附能力,其吸附动力学和吸附等温线分别符合准二级速率方程和Langmuir方程,饱和吸附量达105mg/g,有望成为一种优良的含Cr(VI)污水处理剂和Cr(VI)污染土壤修复剂.初始pH增大,吸附量降低.无机电解质和有机添加剂均能明显抑制Cr(VI)在HTlc上的吸附,其抑制吸附作用的强弱顺序分别为Na3PO4≥Na2SO4≥NaCl>>NaNO3和柠檬酸>EDTA.Cr(VI)在HTlc上的吸附可分为层间的离子交换吸附和外表面的吸附,其中外表面的吸附层在微观上又可分为因化学键合作用而形成的内络合层和因静电作用而形成的外络合层.     

Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method

Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity.     

具有超大通道结构的介孔氧化硅柱层状钛酸的合成和催化应用初探

A mesoporous (d=2.3mm) silica-pillared layered tetratitanate with a super gallery (d₀₀₁=1.84mm)was prepared by first preswelling layered tetratitanate with n-dodecyl amine, then reacting with 20wt% NH₂(CH₂)₃Si(OC₂H₅)₃ aqueous solution, and finally calcinating the resultant solid product in air at 550℃. All the reaction was carried out hydrothermally in an autoclave at 130℃. The obtained material has a relatively high BET surface area of 204m²·g^-1 and a thermal stability beyond 600℃. The catalytic application of the material was also investigated by using the dehydration of isopropanol and the reform of n-hexane as two probing reactions.     

Direct and stepwise intercalation of alkylalcohols intoα-zirconium phosphate

Intercalation of alkylalcohols into -zirconium phosphate was investigated at 25°C and/or under reflux.n-Alcohols having two to five carbons and 2-propanol were taken up at 25°C. These alcohols, andn-hexanol and heptanol, also intercalated under reflux.n-Alcohols having eight to eighteen carbon atoms intercalated when a stepwise method was employed. 2-Butanol and tertiary amylalcohols intercalated under reflux using a butanol intercalate as a starting material. Ethanol-to-butanol intercalates were unstable at room temperature, losing alcohols and changing to -zirconium phosphate. The particle size of the -zirconium phosphate did not affect the intercalation of alcohols.     

Structure determination of homoleptic AuI, AgI, and CuI aryl/alkylethynyl coordination polymers by X-ray powder diffraction

This article describes the structure determination of five homoleptic d(10) metal-aryl/alkylacetylides [RC triple bond CM] (M=Cu, R=tBu 1, nPr 2, Ph 3; R=Ph, M=Ag 4; Au 5) by using X-ray single-crystal and powder diffraction. Complex 1.C6H6 reveals an unusual Cu20 catenane cluster structure that has various types of tBuC triple bond C-->Cu coordination modes. By using this single-crystal structure as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data, the structure of the powder synthesized from CuI and tBuC triple bond CH was found to have the same structure as 1. Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu4 subunits connected through bridging nPrC triple bond C groups. Complex 3 forms an infinite chain structure with extended Cu-Cu ladders (Cu-Cu=2.49(4)-2.83(2) A). The silver(I) congener 4 is iso-structural to 3 (average Ag-Ag distance 3.11 A), whereas the gold(I) analogue 5 forms a Au...Au honeycomb network with PhC triple bond C pillars (Au-Au=2.98(1)-3.26(1) A). Solid-state properties including photoluminescence, nu(C triple bond C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures.     

Synthesis and Characterization of PE-g-MA/MgAl-LDH Exfoliation Nanocomposite via Solution Intercalation

Anorgano modifiedMgAl layereddoublehydroxide (OMgAl LDH )wassuccessfullyexfoliatedinthexylenesolutionofpolyethylene grafted maleicanhydride (PE g MA )underre fluxingcondition .APE g MA/MgAl LDHexfoliationnano compositewasformedaftertheprecipitationofPE g MAfromthedispersionsystem .ThestructureandthermalpropertyofthePE g MA/MgAl LDHexfoliationnanocompositewerechar acterizedbyX raydiffraction (XRD ) ,transmissionelectronmicroscopy (TEM ) ,andthermogravimetryanalysis (TGA ) .The…