Modification of Surface and Structural Properties of Ordered Mesoporous Silicates

Two simple modification methods for ordered mesoporous silicas were examined and compared. MCM-41 molecular sieve was physically coated with 4-cyano-4-biphenyl [4(4-pentenyloxy)]benzoate (CBPB) and chemically modified using trimethylethoxysilane. The structural and surface properties of the obtained materials were characterized using elemental analysis, thermogravimetry and nitrogen adsorption over a wide pressure range.It was shown that the pore size of the MCM-41 material was not decreased significantly after the coating procedure, even for high loadings of CBPB. Moreover, low pressure adsorption measurements indicated that significant fractions of the MCM-41 surface were not covered by CBPB, even for high CBPB loadings, which suggests that the attained coverage may be very nonuniform. The chemical bonding procedure led to a marked decrease in the pore size and change of surface properties.It was demonstrated that nitrogen adsorption measurements provide a means of a thorough characterization of modified MCM-41 materials, allowing to estimate the surface area, pore volume and pore size distribution. Moreover, low pressure adsorption data can be used to qualitatively or semiquantitatively assess the surface coverage of the coated/bonded organic groups, which may be used to estimate the uniformity of the coverage and therefore, the usefulness of the modification procedure.     

纳米TiO_2-SnO_2介孔材料的制备及其对含氰废水的光催化降解性能

以TiCl4和SnCl4为原料,采用直接水解常压液相反应合成出了纳米TiO2-SnO2复合介孔材料.利用XRD和TEM及漫反射谱等对样品进行了表征,并研究了纳米TiO2-SnO2复合介孔材料对含氰废水的光催化降解性能.结果表明,纳米TiO2与SnO2复合后,导致材料的光谱响应拓宽;此种催化剂在日光灯下比在紫外灯下对废水中CN-的降解效果要好.     

Mercerization of primary wall cellulose and its implication for the conversion of cellulose I→cellulose II

The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with ¹³C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains.     

KIT-1介孔分子筛的化学修饰及吸附性能

介孔分子筛MCM-41具有较大、可调的孔径和较高的比表面积，其骨架组成具有较强的可调变性．为该材料的应用提供了很大的空间。但全硅MCM-41分子筛在潮湿空气中，即使在室温条件下也会发生水解反应，使其介孔结构遭到破坏。前人已针对MCM-41分子筛稳定性不足的问题相继合成了稳定性较高的介孔分子筛KIT-1,     

介孔分子筛MSU-1的合成

MSU X介孔分子筛具有三维立体交叉排列的蠕虫状孔道结构,有利于客体分子在其孔道内扩散[1]。目前合成MSU X的原料[2 4]TEOS水解速度慢,合成过程较易控制,但价高、易燃、有刺激性。本文采用文献[5 7]法,以水玻璃、A(EO)9为原料,在酸性至近中性的范围里合成了MSU 1介孔分子筛,与TEOS为原料的MSU 1合成进行了比较,考察了pH值和不同类型表面活性剂(脂肪醇聚氧乙烯醚和烷基酚聚氧乙烯醚)对产物结构性质的影响。1　实验部分1 1　试剂和仪器水玻璃(SiO2%≈26、Na2O%≈8),工业级,青岛海洋化工厂生产;脂肪醇聚氧乙烯醚非离子表面活性…     

A mesoporous Pt/TiO2 nanoarchitecture with catalytic and photocatalytic functions

A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film.     

Direct synthesis, characterization of Cu-SBA-15 and its high catalytic activity in hydroxylation of phenol by H2O2

Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N₂ adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H₂O₂ (30%). The substituting element (Cu²⁺) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H₂O₂ by a radical substitution mechanism.     

利用Triton X-100合成介孔二氧化硅及其形貌研究

以非离子型表面活性剂Triton X-100为模板剂,正硅酸乙酯为硅源,合成了介孔二氧化硅分子筛.利用XRD、N2吸附—脱附、SEM、以及TG-DTA对样品进行了表征,结果表明合成的材料具有有序介孔结构、高比表面积及高孔容。同时比较了不同条件下所得产物的形貌结构,并分析了它们的形成机理。     

PtRu纳米线的合成及其在直接甲醇燃料电池阳极中的催化活性

 分别以SBA-15和MCM-41介孔分子筛作模板剂,采用浸渍还原法制备了纵横比及合金度不同的双组元PtRu纳米线和纳米棒电催化剂. 透射电镜、 X射线衍射表征和电化学测试结果表明, PtRu纳米线具有较高的合金度和较大的纵横比,在甲醇硫酸溶液中表现出更好的电催化活性. 初步探讨了PtRu纳米线催化剂的合金度和纵横比对其电催化活性和电极性能的影响.     

Structural and Adsorptive Characteristics of Pyrocarbon/Silica Gel Si-60

Pyrocarbon/silica gel adsorbents (carbosils, CS) with mesoporous Si-60 (Merck, granule size 0.2–0.5 mm) modified by pyrolysis of CH₂Cl₂ at 823 K and reaction time from 0.5 to 6 h and then hydrothermally treated at 473 K for 6 h were studied by means of TEM, adsorption and ¹H NMR methods. Changes in the structural and adsorptive characteristics of hybrid adsorbents before and after hydrothermal treatment, which depend on pyrocarbon content (C _C), were analyzed on the basis of TEM micrographs and p-nitrophenol and nitrogen adsorption isotherms treated using a constrained regularization method. Interfacial water layers in aqueous suspension of CS were investigated by means of ¹H NMR with freezing-out of bulk water at T < 273 K showing nonlinear changes in the Gibbs free energy of interfacial water with increasing C _C because of nonlinear dependence of the structural characteristics of pyrocarbon deposits and CS as a whole on C _C.