Mesostructured germanium with cubic pore symmetry

Regular mesoporous oxide materials have been widely studied and have a range of potential applications, such as catalysis, absorption and separation. They are not generally considered for their optical and electronic properties. Elemental semiconductors with nanopores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. Here we describe cubic mesostructured germanium, MSU-Ge-1, with gyroidal channels containing surfactant molecules, separated by amorphous walls that lie on the gyroid (G) minimal surface as in the mesoporous silica MCM-48 (ref. 2). Although Ge is a high-melting, covalent semiconductor that is difficult to prepare from solution polymerization, we succeeded in assembling a continuous Ge network using a suitable precursor for Ge(4-) atoms. Our results indicate that elemental semiconductors from group 14 of the periodic table can be made to adopt mesostructured forms such as MSU-Ge-1, which features two three-dimensional labyrinthine tunnels obeying Ia3d space group symmetry and separated by a continuous germanium minimal surface that is otherwise amorphous. A consequence of this new structure for germanium, which has walls only one nanometre thick, is a wider electronic energy bandgap (1.4 eV versus 0.66 eV) than has crystalline or amorphous Ge. Controlled oxidation of MSU-Ge-1 creates a range of germanium suboxides with continuously varying Ge:O ratio and a smoothly increasing energy gap.     

Synthesis of the chiral spiro-cyclopropane derivative and its crystal structure

The spiro[ l-bromo-4-/-mentholoxy-5-oxo-6-oxabicyclo[3. 1.0] hexane-2, 3'-(4'-ethoxy-5'-/-men-thyloxybutyrolactone)] 4 was synthesized via the tandem double Michael addition/internal nucleophilic substitution of chiral synthon 1, 5-/-menthyloxy- 3-bromo-2 (5H)-furanone, with nucleophilic ethanol. The two synthetic routes to compound 4 and its analytical data of structure are reported. The absolute configuration of 4 was determined by X-ray crystallography. These results provide a valuable strategy for synthesizing some biologically active molecules.     

孔径可调介孔La-Co-Ce-O系复合氧化物的制备

采用有机模板剂去除法制备介孔La-Co-Ce-O系复合氧化物,研究溶液体系的pH值及模板剂十六烷基三甲基溴化铵(CTAB)浓度对晶态和孔径结构影响;对制备的样品采用XRD测试和N2吸脱附方法表征其晶态结构和孔径结构。研究结果表明:该介孔氧化物具有较高的比表面积(高达160m2/g)和均匀的孔径;当pH值和CTAB浓度变化时,实现介孔La-Co-Ce-O系复合氧化物的孔径在3.0～21.0nm之间可调;制备条件的变化对介孔氧化物样品的晶态结构稍有影响。     

孔径可调的介孔磷酸铈的合成

采用中性表面活性剂十八胺为模板剂、硫酸铈为铈源，在水热条件下合成具有介孔结构的磷酸铈。通过X-射线衍射、透射电镜、高倍透射电镜和液氮吸附手段对介孔磷酸铈的介观结构、微观形貌和孔道结构进行了表征。结果表明，该材料是的有序的层状相介孔，层间距为2～3nm。产物主晶相为结晶性良好的单斜晶系的独居石磷酸铈，次晶相为正交晶系的磷酸铈。调整无机铈源与表面活性剂的摩尔比，实现磷酸铈介孔孔径在5.5～9.8nm之间可调。该介孔材料的最大比表面积高达113m²/g，孔体积为0.25mL/g。     

Low-cost preparation of mesoporous silica with high pore volume

Mesoporous silica materials with high pore volume were successfully prepared by the chemical precipitation method, with water glass and a biodegradable nonionic surfactant polyethylene glycol (PEG). The obtained materials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermo gravimetric analyzer and differential scanning calorimetry (TG-DSC), nitrogen adsorption-desorption measurements, and X-ray diffraction (XRD). The results showed that the changes of the pore parameters depended on both the surfactant content and heat treatment temperature. When the content of PEG was 10wt% and the obtained PEG/SiO₂ composite was heated at 600℃, the mesoporous silica with a pore volume of 2.2 cma/g, a BET specific surface area of 361.55 m2/g, and a diameter of 2-4 μm could be obtained. The obtained mesoporous silica materials have potential applications in the fields of paint and plastic, as thickening, reinforcing, and flatting agents.     

Synthesis and characterization of chiral mesoporous silica

Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130-180 nm and length 1-6 micro m. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.     

Free-standing mesoporous silica films with tunable chiral nematic structures

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.     

Synthesis and characterization of nano/micro-structured crystalline germanium dioxide with novel morphology

Nano/micro-structured germanium oxide （GeO2） was prepared using GeCl4 and KOH by a simple solution method in alkalic alcoholic solution. Different morphologies of GeO2 were obtained by changing the reaction conditions. The effects of the reaction time, the concentration of the reactants, the reaction temperature and the dispersant upon the morphology of the deposited GeO2 have been investigated. The products were detected by X-ray diffraction （XRD）, atomic force microscope （AFM）, scanning electron microscope （SEM） and transmission electron microscope （TEM）. Novel cross-like structures were obtained by using n-butylamine as the dispersant. The formation of the cross-like structures has been discussed and a solution-liquid-solid （SLS） mechanism was proposed.     

生物模板剂合成介孔氧化铈及其催化性能

以无污染简单易得的天然材料壳聚糖为模板剂合成介孔氧化铈材料,并研究了材料的结构和催化性能.介孔Ce02的孔道结构由直径为5-8 nm的颗粒堆积形成,孔道孔径分布较为均匀,集中在5-10 nm,材料的比表面积约为102 m^2·g^-1.与氧化铈参比样相比,介孔氧化铈具有更好的氧化能力和催化活性,因为材料高比表面积导致了更多活性位点的暴露和表面活性氧的增多.介孔氧化铈的%T50转化率为50％时的温度点）约为300℃,远低于亚微米参比样的430℃.     

Syntheses and characterization of new chiral side-chain liquid crystalline polysiloxanes

A new serial chiral side-chain liquid crystal polysiloxanes containing L-Tyr structures were synthesized at room temperature. Both of them exhibited Sc phase at room temperature. Tang Hongding: born in 1972, Graduate student     

Ordered mesoporous tungsten oxide and titanium oxide composites and their photocatalytic degradation behavior

Highly ordered mesoporous WO3/TiO2 (MWTs) composite materials with tunable chemical compositions were obtained by a surfactant template-assisted evaporation-induced selfassembly (EISA) processes. The structure properties of the MWT materials were characterized by small angle XRD, TEM and N2 sorption. The resultant materials showed large amount of ordered mesopores and high chemical homogeneity. With increasing crystallinity degree, the order degrees of mesostructure turned worse gradually. The MWT hybrids exhibited excellent visible light response due to the addition of WO3 with narrow band gap. Photocatalytic performances of the MWT samples were determined by measuring the photo-degradation of rhodamine B dye and phenol under simulated solar light irradiation. The effect of material parameters such as surface area, crystallinity and chemical compositions in the binary heterostructured system on photocatalytic performance were discussed in details.     

大孔径多孔氧化铝膜的制备

本文使用磷酸和草酸的混合溶液为电解液,在90V电压下,控制电解液温度在5～10℃制备了平均孔径高达200nm,开孔密度为1.7×109pores/cm2的多孔阳极氧化铝（AAO）膜。与使用单一酸为电解质相比,使用混合酸制备大孔径氧化铝膜所需的电压较低,电流密度较小,对氧化温度的要求也不苛刻。     

涉及导函数的亚纯函数的惟一性

研究了亚纯函数与其导函数具有一个公共值时的性质,改进了R.Brück的有关结果,得到了若非常数亚纯函数f与其导函数f(k)以1为IM公共值,且     

Electronic connection to the interior of a mesoporous insulator with nanowires of crystalline RuO2

Highly porous materials such as mesoporous oxides are of technological interest for catalytic, sensing and remediation applications: the mesopores (of size 2-50 nm) permit ingress by molecules and guests that are physically excluded from microporous materials. Connecting the interior of porous materials with a nanoscale or 'molecular' wire would allow the direct electronic control (and monitoring) of chemical reactions and the creation of nanostructures for high-density electronic materials. The challenge is to create an electronic pathway (that is, a wire) within a mesoporous platform without greatly occluding its free volume and reactive surface area. Here we report the synthesis of an electronically conductive mesoporous composite--by the cryogenic decomposition of RuO4--on the nanoscale network of a partially densified silica aerogel. The composite consists of a three-dimensional web of interconnected (approximately 4-nm in diameter) crystallites of RuO2, supported conformally on the nanoscopic silica network. The resulting monolithic (RuO2//SiO2) composite retains the free volume of the aerogel and exhibits pure electronic conductivity. In addition to acting as a wired mesoporous platform, the RuO2-wired silica aerogel behaves as a porous catalytic electrode for the oxidation of chloride to molecular chlorine.     

模板剂对介孔碳孔道结构及有序性的影响

分别以三嵌段聚合物F127、P123以及P123/F127作为模板剂,酚醛树脂为有机碳源,采用溶剂挥发自组装法制备有序介孔碳材料。采用XRD,TEM和N2吸/脱附等手段对有序介孔碳进行表征,研究F127、P123及P123/F127复合模板剂对介孔碳孔道结构及有序性的影响。结果表明,使用单一模板剂时,F127较P123更易产生有序六方介孔结构;使用P123/F127复合模板剂,介孔碳有较好的二维六方有序性,介孔孔容和比表面积较单独使用F127作模板分别提高了50%与31%;当m(P123)/m(F127)=1/3时,所得介孔碳BET比表面积为498.5 m2/g,介孔孔容和比表面积分别为0.173 cm3/g和167m2/g,平均孔径为3.41 nm。     

介孔玻璃粉末的制备及其与空穴基板复合研究

以阳离子表面活性剂CTAB(十六烷基三甲基溴化铵)与非离子型表面活性剂(嵌段聚合物P123)互配的混合表面活性剂作为模板剂,以正硅酸乙酯为硅源,运用水热合成法制成了平均孔径达8.8nm,比表面积为508.6m2/g和孔容为1.129cm3/g的SiO2介孔材料,对其结构和性能运用氮气吸附和透射电镜进行了表征,分析得出最佳偶合条件为:偶合温度130℃,偶合时间2h.通过介孔玻璃粉末与空穴基板的复合研究,可以制备出生物芯片复合玻璃载体材料.     

具有介孔结构的锐钛矿型C,Co-MTiO2抗菌性能研究

为了开发不需要人造光源激发,只需要微弱室内光线且改性离子不易泄漏的新型无机抗菌材料,以钛酸异丙酯为钛源,表面活性剂十二胺为模板剂,通过水热合成和超声波联用技术,合成了非金属元素C和金属元素Co共掺杂的具有介孔结构的锐钛矿型二氧化钛(C,Co-MTiO2).用N2等温吸附-解吸附、X-射线衍射(XRD)、高分辨透射电镜(HRTEM)、紫外可见吸收光谱(UV-Vis)和X-射线光电子能谱(XPS)对材料进行了表征,结果表明,该材料为热稳定性好,比表面积高,具有较大介孔孔径的锐钛矿型TiO2.在无人造光源激发的室内环境中,进行了材料的抗菌性能以及细菌吸附研究,结果表明这种材料在该环境中对大肠杆菌(E.colli)有很好的抑制作用和吸附作用,比Co-MTiO2的抑菌活性提高了20%,具有很好的应用前景.     

亚纯函数与其导数分担一个小函数

讨论了涉及亚纯函数与其导数分担一个小函数的唯一性问题。所得结果推广了Yu,Liu和Gu等人的有关定理。     

亚纯函数及其导数分担一个IM公共值

研究了亚纯函数f及其导数f′分担一个公共值的唯一性问题,当f和f′分担1I M时,若满足3N 〔r,1/f′〕+3N(r,f)+N(2〔r,1/f′-1〕(λ+o(1))T(r),得到f≡f′或f.f′≡1,改进了Gundersen的定理:设f是非常数的整函数,如果f和f′分担1CM,且N〔r,1/f′〕=S(r,f),则f′-1/f-1≡c,其中c为非零的常数.     

含两种不同手性基元侧链液晶聚合物的合成与性能研究

合成了两种含不同手性基元的液晶单体,6-(4-乙氧基)苯甲酰氧基-6-(4-(4-(4-十一烯酰氧基)苯甲酰氧基)苯基)苯基氧羰基戊酰氧基六氢-[3,2-b]呋喃酯(M1),丙烯酸胆甾醇酯(M2)。将两种单体与含氢聚硅氧烷(PMHS)接枝聚合得到了一系列侧链液晶聚合物。采用红外光谱(FT-IR)、核磁共振(1H-NMR)、差示扫描量热(DSC)、偏光显微镜(POM)、X-射线衍射(XRD)等手段对单体及聚合物的液晶性能进行了表征。结果表明,所有的聚合物都具有很宽的介晶区间。对于以含M1为主的聚合物为近晶相,随着M2在聚合物中含量的增加,破坏了原有聚合物的规整结构,聚合物由近晶相转为胆甾相;同时聚合物的最大选择性反射波长也随之增加,即螺距变大。