Showing papers by "Peidong Yang published in 1999"

Block Copolymer Templating Syntheses of Mesoporous Metal Oxides with Large Ordering Lengths and Semicrystalline Framework

Abstract: A simple and general procedure has been developed for the syntheses of ordered largepore (up to 14 nm) mesoporous metal oxides, including TiO2, ZrO2 ,N b 2O5 ,T a 2O5 ,A l 2O3, SiO2, SnO2 ,W O 3, HfO2, and mixed oxides SiAlOy ,A l 2TiOy, ZrTiOy, SiTiOy, ZrW2Oy. Amphiphilic poly(alkylene oxide) block copolymers were used as structure-directing agents in nonaqueous solutions for organizing the network-forming metal oxide species. Inorganic salts, rather than alkoxides or organic metal complexes, were used as soluble and hydrolyzable precursors to the polymerized metal oxide framework. These thermally stable mesoporous oxides have robust inorganic frameworks and thick channel walls, within which high densities of nanocrystallites can be nucleated. These novel mesoporous metal oxides are believed to be formed through a mechanism that combines block copolymer self-assembly with alkylene oxide complexation of the inorganic metal species.

Mesocellular siliceous foams with uniformly sized cells and windows

Abstract: Molecular sieves with uniform large pores are desirable for chemical reactions and for use in separations involving large molecules.1 Periodic cubic and hexagonal mesoporous silica phases with uniform large pores have been synthesized by using nonionic triblock and star diblock copolymers as templates.2 Control over the pore size is achieved by adjusting the hydrophobic volumes of the self-assembled aggregates.2,3 In this paper, we describe how adding a sufficiently large amount of an organic cosolvent induces a phase transformation from the highly ordered p6mm mesostructure of SBA-15-type mesoporous silicas to remarkable mesostructured cellular foams (mesocellular foams, MCFs) composed of uniformly sized, large spherical cells that are interconnected by uniform windows to create a continuous 3-D pore system. The interconnected nature of the large uniform pores makes these new mesostructured silicas promising candidates for supports for catalysts and in separations involving large molecules, and they may be of interest in low-dielectric applications. The MCFs have been synthesized in aqueous acid by using dilute Pluronic P123 solutions in the presence of 1,3,5-trimethylbenzene (TMB) as organic cosolvent.4 X-ray diffraction (XRD) experiments5 reveal well-resolved peaks at small angles, as shown in Figure 1 for a sample with a cell diameter of 33 nm. Careful analyses of the scattering data for MCFs show that the higher order peaks cannot be indexed to any plane or space group (e.g., p6mm) or to a lamellar diffraction pattern. In fact, after subtraction of the background,6 the X-ray data are in good agreement with simulated scattering7 due to monodisperse spheres (cells) of diameter D (see Table 1), while attempts to fit the X-ray data to

Controlled growth and electrical properties of heterojunctions of carbon nanotubes and silicon nanowires

Abstract: Nanometre-scale electronic structures are of both fundamental and technological interest: they provide a link between molecular and solid state physics, and have the potential to reach far higher device densities than is possible with conventional semiconductor technology1,2. Examples of such structures include quantum dots,which can function as single-electron transistors3,4 (although theirsensitivity to individual stray charges might make them unsuitable for large-scale devices) and semiconducting carbon nanotubes several hundred nanometres in length, which have been used to create a field-effect transistor5. Much smaller devices could be made by joining two nanotubes or nanowires to create, for example, metal–semiconductor junctions, in which the junction area would be about 1 nm2 for single-walled carbon nanotubes. Electrical measurements of nanotube ‘mats’ have shown the behaviour expected for a metal–semiconductor junction6. However, proposed nanotube junction structures7 have not been explicitly observed, nor have methods been developed to prepare them. Here we report controlled, catalytic growth of metal–semiconductor junctions between carbon nanotubes and silicon nanowires, and show that these junctions exhibit reproducible rectifying behaviour.

Multiphase assembly of mesoporous-macroporous membranes

Abstract: A novel procedure has been developed for the synthesis of spongelike silica membranes with three-dimensional meso−macrostructures. The process utilizes multiphase media comprised of a mesoscopically ordered block copolymer/silica phase that macroscopically separates from an electrolyte phase. This results in hierarchically organized composite structures whose different characteristic length scales can be independently adjusted.

Fluoride-Induced Hierarchical Ordering of Mesoporous Silica in Aqueous Acid-Syntheses

Abstract: The acid-catalyzed synthesis of highly ordered mesostructured materials has led to a variety of twoand three-dimensional periodic symmetries, and has proven to be an effective route for the generation of fibers, spheres, thin films, and other monolithic forms of mesoporous materials. Zhao et al. recently used non-ionic poly(alkylene oxide) block copolymers, under acidic conditions, to prepare well-ordered, hexagonal mesoporous silica, denoted SBA-15, featuring uniform and adjustable large pore sizes combined with thick hydrothermally stable walls. The catalytic effect of fluoride in the synthesis of mesoporous silica at neutral to basic pH has been described by Voegtlin et al. Fluoride has been successfully used to extend the pH range over which anionic silica precursors can be utilized to create organized periodic structures; it has been used to diminish framework defects in zeolites, and to improve the organization in MCM-41 molecular sieves and MSU-X materials. However, to the best of our knowledge, no studies have been reported on the role of fluoride on cationic silica species in the aqueous acid-synthesis of ordered porous silica. In this communication, we describe the hierarchical ordering effects induced by small amounts of fluoride added during the synthesis of SBA-15-type mesoporous silica under acidic aqueous conditions. The non-ionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer EO20PO70EO20 (Pluronic P123) has been employed as the structure-directing agent. At low pH, remarkably well-ordered, hydrothermally stable, large hexagonal mesoporous silica rods with uniform channels extending over micrometer-sized length scales, and with few defects, have been synthesized. The fluoride-induced enhancement of order has enabled the preparation of SBA-15 materials at moderate acidity (~ pH 2.5±3) without compromising the long-range hexagonal symmetry. The mesoporous silicas possess narrow pore-size distributions, hydrothermally stable frameworks, large surface areas, and pore volumes of up to 0.92 cm/g. This work has been motivated by our interest in i) the patterning of mesoporous materials ranging from mesoscopic to macroscopic length scales while retaining molecular-level structural control and ii) understanding the underlying mechanism for the acid-catalyzed mesoporous silica synthesis. Addition of small amounts of fluoride (F:Si molar ratios of 0.008 and 0.03; fluoride source: NH4F or (NH4)2SiF6) during the aqueous acidic SBA-15-type silica synthesis induces substantial ordering that is manifested on different length scales: both the mesoscopic structure and the macroscopic morphology of the mesoporous silicas are significantly improved. Scanning electron microscopy (SEM) has revealed that small amounts of fluoride bring about the formation of large mesoporous silica rods (Fig. 1a) when pre-

Hierarchically ordered porous oxides

Abstract: A low-cost, efficient method of preparing hierarchically ordered structures by combining, concurrently or sequentially, micromolding, latex templating, and cooperative self-assembly of hydrolyzed inorganic species and amphiphilic block copolymers.

Mesocellular Siliceous Foams with Uniformly Sized Cells and Windows.

Abstract: Molecular sieves with uniform large pores are desirable for chemical reactions and for use in separations involving large molecules.1 Periodic cubic and hexagonal mesoporous silica phases with uniform large pores have been synthesized by using nonionic triblock and star diblock copolymers as templates.2 Control over the pore size is achieved by adjusting the hydrophobic volumes of the self-assembled aggregates.2,3 In this paper, we describe how adding a sufficiently large amount of an organic cosolvent induces a phase transformation from the highly ordered p6mm mesostructure of SBA-15-type mesoporous silicas to remarkable mesostructured cellular foams (mesocellular foams, MCFs) composed of uniformly sized, large spherical cells that are interconnected by uniform windows to create a continuous 3-D pore system. The interconnected nature of the large uniform pores makes these new mesostructured silicas promising candidates for supports for catalysts and in separations involving large molecules, and they may be of interest in low-dielectric applications. The MCFs have been synthesized in aqueous acid by using dilute Pluronic P123 solutions in the presence of 1,3,5-trimethylbenzene (TMB) as organic cosolvent.4 X-ray diffraction (XRD) experiments5 reveal well-resolved peaks at small angles, as shown in Figure 1 for a sample with a cell diameter of 33 nm. Careful analyses of the scattering data for MCFs show that the higher order peaks cannot be indexed to any plane or space group (e.g., p6mm) or to a lamellar diffraction pattern. In fact, after subtraction of the background,6 the X-ray data are in good agreement with simulated scattering7 due to monodisperse spheres (cells) of diameter D (see Table 1), while attempts to fit the X-ray data to

Siliceous Mesostructured Cellular Foams with Uniformly Sized and Shaped Pores

Abstract: Mesostructured siliceous cellular foams (mesocellular foams, MCFs) with homogeneous ultra-large mesopores are described. MCFs consist of uniform spherical cells 21-36 nm in diameter and possess surface areas up to 900 m2/g. Uniform windows, 7-18 nm in diameter, interconnect the cells to form a continuous 3-D pore system, which makes the MCFs attractive candidates for supports for catalysis and in separation and immobilization involving large molecules. They may be of interest in low-dielectric applications. The size of the cells can be controlled by the concentration of the added organic cosolvent. Adding small amounts of NH4F selectively enlarges the windows. We propose that the MCFs are templated by oil-inwater microemulsion droplets. The large-pore MCF materials resemble aerogels, with the benefit of a facilitated synthesis procedure in combination with well-defined pores and wall structure.

Multiphase Assembly of Mesoporous—Macroporous Membranes.

Abstract: A novel procedure has been developed for the synthesis of spongelike silica membranes with three-dimensional meso−macrostructures. The process utilizes multiphase media comprised of a mesoscopically ordered block copolymer/silica phase that macroscopically separates from an electrolyte phase. This results in hierarchically organized composite structures whose different characteristic length scales can be independently adjusted.

Fluoride‐Induced Hierarchical Ordering of Mesoporous Silica in Aqueous Acid‐Syntheses.

Abstract: The acid-catalyzed synthesis of highly ordered mesostructured materials has led to a variety of twoand three-dimensional periodic symmetries, and has proven to be an effective route for the generation of fibers, spheres, thin films, and other monolithic forms of mesoporous materials. Zhao et al. recently used non-ionic poly(alkylene oxide) block copolymers, under acidic conditions, to prepare well-ordered, hexagonal mesoporous silica, denoted SBA-15, featuring uniform and adjustable large pore sizes combined with thick hydrothermally stable walls. The catalytic effect of fluoride in the synthesis of mesoporous silica at neutral to basic pH has been described by Voegtlin et al. Fluoride has been successfully used to extend the pH range over which anionic silica precursors can be utilized to create organized periodic structures; it has been used to diminish framework defects in zeolites, and to improve the organization in MCM-41 molecular sieves and MSU-X materials. However, to the best of our knowledge, no studies have been reported on the role of fluoride on cationic silica species in the aqueous acid-synthesis of ordered porous silica. In this communication, we describe the hierarchical ordering effects induced by small amounts of fluoride added during the synthesis of SBA-15-type mesoporous silica under acidic aqueous conditions. The non-ionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer EO20PO70EO20 (Pluronic P123) has been employed as the structure-directing agent. At low pH, remarkably well-ordered, hydrothermally stable, large hexagonal mesoporous silica rods with uniform channels extending over micrometer-sized length scales, and with few defects, have been synthesized. The fluoride-induced enhancement of order has enabled the preparation of SBA-15 materials at moderate acidity (~ pH 2.5±3) without compromising the long-range hexagonal symmetry. The mesoporous silicas possess narrow pore-size distributions, hydrothermally stable frameworks, large surface areas, and pore volumes of up to 0.92 cm/g. This work has been motivated by our interest in i) the patterning of mesoporous materials ranging from mesoscopic to macroscopic length scales while retaining molecular-level structural control and ii) understanding the underlying mechanism for the acid-catalyzed mesoporous silica synthesis. Addition of small amounts of fluoride (F:Si molar ratios of 0.008 and 0.03; fluoride source: NH4F or (NH4)2SiF6) during the aqueous acidic SBA-15-type silica synthesis induces substantial ordering that is manifested on different length scales: both the mesoscopic structure and the macroscopic morphology of the mesoporous silicas are significantly improved. Scanning electron microscopy (SEM) has revealed that small amounts of fluoride bring about the formation of large mesoporous silica rods (Fig. 1a) when pre-