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Sample records for mesoporous metal oxide

  1. Mesoporous metal oxide graphene nanocomposite materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A.; Kou, Rong; Wang, Donghai

    2016-05-24

    A nanocomposite material formed of graphene and a mesoporous metal oxide having a demonstrated specific capacity of more than 200 F/g with particular utility when employed in supercapacitor applications. A method for making these nanocomposite materials by first forming a mixture of graphene, a surfactant, and a metal oxide precursor, precipitating the metal oxide precursor with the surfactant from the mixture to form a mesoporous metal oxide. The mesoporous metal oxide is then deposited onto a surface of the graphene.

  2. Ordered mesoporous metal oxides: synthesis and applications.

    PubMed

    Ren, Yu; Ma, Zhen; Bruce, Peter G

    2012-07-21

    Great progress has been made in the preparation and application of ordered mesoporous metal oxides during the past decade. However, the applications of these novel and interesting materials have not been reviewed comprehensively in the literature. In the current review we first describe different methods for the preparation of ordered mesoporous metal oxides; we then review their applications in energy conversion and storage, catalysis, sensing, adsorption and separation. The correlations between the textural properties of ordered mesoporous metal oxides and their specific performance are highlighted in different examples, including the rate of Li intercalation, sensing, and the magnetic properties. These results demonstrate that the mesoporosity has a direct impact on the properties and potential applications of such materials. Although the scope of the current review is limited to ordered mesoporous metal oxides, we believe that the information may be useful for those working in a number of fields.

  3. Mesoporous Transition Metal Oxides for Supercapacitors

    PubMed Central

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

  4. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGES

    Luo, Hongmei; Lin, Qianglu; Baber, Stacy; ...

    2010-01-01

    We demore » monstrate two approaches to prepare mesoporous metal oxide nanowires by surfactant assembly and nanoconfinement via sol-gel or electrochemical deposition. For example, mesoporous Ta 2 O 5 and zeolite nanowires are prepared by block copolymer Pluronic 123-templated sol-gel method, and mesoporous ZnO nanowires are prepared by electrodeposition in presence of anionic surfactant sodium dodecyl sulfate (SDS) surfactant, in porous membranes. The morphologies of porous nanowires are studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses.« less

  5. Thermally stable crystalline mesoporous metal oxides with substantially uniform pores

    SciTech Connect

    Wiesner, Ulrich; Orilall, Mahendra Christopher; Lee, Jinwoo; DiSalvo, Jr., Francis J

    2015-01-27

    Highly crystalline metal oxide-carbon composites, as precursors to thermally stable mesoporous metal oxides, are coated with a layer of amorphous carbon. Using a `one-pot` method, highly crystalline metal oxide-carbon composites are converted to thermally stable mesoporous metal oxides, having highly crystalline mesopore walls, without causing the concomitant collapse of the mesostructure. The `one-pot` method uses block copolymers with an sp or sp 2 hybridized carbon containing hydrophobic block as structure directing agents which converts to a sturdy, amorphous carbon material under appropriate heating conditions, providing an in-situ rigid support which maintains the pores of the oxides intact while crystallizing at temperatures as high as 1000 deg C. A highly crystalline metal oxide-carbon composite can be heated to produce a thermally stable mesoporous metal oxide consisting of a single polymorph.

  6. Aerosol-spray diverse mesoporous metal oxides from metal nitrates

    PubMed Central

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-01-01

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances. PMID:25897988

  7. Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

    PubMed

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-04-21

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.

  8. Nanocasted synthesis of mesoporous metal oxides and mixed oxides from mesoporous cubic (Ia3d) vinylsilica.

    PubMed

    Wang, Yangang; Wang, Yanqin; Liu, Xiaohui; Guo, Yun; Guo, Yanglong; Lu, Guanzhong; Schüth, Ferdi

    2008-11-01

    Mesoporous metal oxides and mixed oxides, such as NiO, CeO2, Cr2O3, Fe203, Mn2O3, NiFe2O4 and Ce(x)Zr(1-x)O2 (x=0.8 and 0.6) have been synthesized by nanocasting from mesoporous cubic (la3d) vinyl-functionalized silica (vinylsilica). Their structural properties were characterized by XRD, TEM, N2-sorption and Raman spectra. Thus-prepared mesoporous materials possess a high BET surface area (110-190 m2g(-1)), high pore volume (0.25-0.40 cm3g(-1)) and relatively ordered structures. The catalytic properties of Cr2O3 were tested in the oxidation of toluene. The mesoporous Cr2O3 exhibits unusually high catalytic activity in the complete oxidation of toluene as compared with commercial Cr2O3.

  9. Noble Metal Nanoparticle-loaded Mesoporous Oxide Microspheres for Catalysis

    NASA Astrophysics Data System (ADS)

    Jin, Zhao

    Noble metal nanoparticles/nanocrystals have attracted much attention as catalysts due to their unique characteristics, including high surface areas and well-controlled facets, which are not often possessed by their bulk counterparts. To avoid the loss of their catalytic activities brought about by their size and shape changes during catalytic reactions, noble metal nanoparticles/nanocrystals are usually dispersed and supported finely on solid oxide supports to prevent agglomeration, nanoparticle growth, and therefore the decrease in the total surface area. Moreover, metal oxide supports can also play important roles in catalytic reactions through the synergistic interactions with loaded metal nanoparticles/nanocrystals. In this thesis, I use ultrasonic aerosol spray to produce hybrid microspheres that are composed of noble metal nanoparticles/nanocrystals embedded in mesoporous metal oxide matrices. The mesoporous metal oxide structure allows for the fast diffusion of reactants and products as well as confining and supporting noble metal nanoparticles. I will first describe my studies on noble metal-loaded mesoporous oxide microspheres as catalysts. Three types of noble metals (Au, Pt, Pd) and three types of metal oxide substrates (TiO2, ZrO2, Al 2O3) were selected, because they are widely used for practical catalytic applications involved in environmental cleaning, pollution control, petrochemical, and pharmaceutical syntheses. By considering every possible combination of the noble metals and oxide substrates, nine types of catalyst samples were produced. I characterized the structures of these catalysts, including their sizes, morphologies, crystallinity, and porosities, and their catalytic performances by using a representative reduction reaction from nitrobenzene to aminobenzene. Comparison of the catalytic results reveals the effects of the different noble metals, their incorporation amounts, and oxide substrates on the catalytic abilities. For this particular

  10. Mesoporous metal oxide microsphere electrode compositions and their methods of making

    DOEpatents

    Parans Paranthaman, Mariappan; Bi, Zhonghe; Bridges, Craig A.; Brown, Gilbert M.

    2017-04-11

    Compositions and methods of making are provided for treated mesoporous metal oxide microspheres electrodes. The compositions include microspheres with an average diameter between about 200 nanometers and about 10 micrometers and mesopores on the surface and interior of the microspheres. The methods of making include forming a mesoporous metal oxide microsphere composition and treating the mesoporous metal oxide microspheres by at least annealing in a reducing atmosphere, doping with an aliovalent element, and coating with a coating composition.

  11. Container effect in nanocasting synthesis of mesoporous metal oxides.

    PubMed

    Sun, Xiaohong; Shi, Yifeng; Zhang, Peng; Zheng, Chunming; Zheng, Xinyue; Zhang, Fan; Zhang, Yichi; Guan, Naijia; Zhao, Dongyuan; Stucky, Galen D

    2011-09-21

    We report a general reaction container effect in the nanocasting synthesis of mesoporous metal oxides. The size and shape of the container body in conjunction with simply modifying the container opening accessibility can be used to control the escape rate of water and other gas-phase byproducts in the calcination process, and subsequently affect the nanocrystal growth of the materials inside the mesopore space of the template. In this way, the particle size, mesostructure ordering, and crystallinity of the final product can be systemically controlled. The container effect also explain some of the problems with reproducibility in previously reported results.

  12. Single crystal particles of a mesoporous mixed transition metal oxide with a wormhole structure.

    PubMed

    Lee, B; Lu, D; Kondo, J N; Domen, K

    2001-10-21

    A new type of mesoporous mixed transition metal oxide of Nb and Ta (NbTa-TIT-1) has been prepared through a two-step calcination, which consists of single crystal particles with wormhole mesoporous structure.

  13. Polymer/mesoporous metal oxide composites

    NASA Astrophysics Data System (ADS)

    Ver Meer, Melissa Ann

    Understanding the nature of the interfacial region between an organic polymer matrix and an inorganic filler component is essential in determining how this region impacts the overall bulk properties of the organic/inorganic hybrid composite material. In this work, polystyrene was used as the model polymer matrix coupled with silica-based filler materials to investigate the nature of structure-property relationships in polymer composites. Initial work was conducted on synthesis and characterization of colloidal and mesoporous silica particles melt blended into the polystyrene matrix. Modification of the interface was accomplished by chemically bonding the silica particles with the polystyrene chains through polymerization from the particle surface via atom transfer radical polymerization. High molecular weight polystyrene chains were formed and bulk test samples were evaluated with increased thermal stability of the grafted polymer composite system versus equivalent melt blended polymer composites. Polymer grafting was also conducted from the internal pores of mesoporous silica, further improving the thermal stability of the composite system without degrading dynamic mechanical properties. Characterization of the polymer composites was conducted with gel permeation chromatography, transmission electron microscopy, thermogravimetric analysis and dynamic mechanical analysis. It was also discovered during the polystyrene-silica composite studies that amorphous polystyrene can possess a less mobile phase, evident in a second peak of the loss tangent (tan delta). The long annealing times necessitated by the mesoporous silica composites were replicated in as received polystyrene. This new, less mobile phase is of particular interest in determining the mobility of polymer chains in the interfacial region.

  14. Mesoporous metal oxide microsphere electrode compositions and their methods of making

    DOEpatents

    Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

    2016-12-06

    Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

  15. Mesoporous metal oxide microsphere electrode compositions and their methods of making

    DOEpatents

    Parans Paranthaman, Mariappan; Bi, Zhonghe; Bridges, Craig A; Brown, Gilbert M

    2014-12-16

    Compositions and methods of making are provided for treated mesoporous metal oxide microspheres electrodes. The compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g, and wherein the composition has an electrical conductivity of at least 1.times.10.sup.-7 S/cm at 25.degree. C. and 60 MPa. The methods of making comprise forming a mesoporous metal oxide microsphere composition and treating the mesoporous metal oxide microspheres by at least one method selected from the group consisting of: (i) annealing in a reducing atmosphere, (ii) doping with an aliovalent element, and (iii) coating with a coating composition.

  16. Large-Scale, Three-Dimensional, Free-Standing, and Mesoporous Metal Oxide Networks for High-Performance Photocatalysis

    NASA Astrophysics Data System (ADS)

    Bai, Hua; Li, Xinshi; Hu, Chao; Zhang, Xuan; Li, Junfang; Yan, Yan; Xi, Guangcheng

    2013-07-01

    Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high-yield producing single- and multi-component large-scale three-dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter-sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large-scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large-scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials.

  17. Large-Scale, Three–Dimensional, Free–Standing, and Mesoporous Metal Oxide Networks for High–Performance Photocatalysis

    PubMed Central

    Bai, Hua; Li, Xinshi; Hu, Chao; Zhang, Xuan; Li, Junfang; Yan, Yan; Xi, Guangcheng

    2013-01-01

    Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high–yield producing single– and multi–component large–scale three–dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter–sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large–scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large–scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials. PMID:23857595

  18. Large-scale, three-dimensional, free-standing, and mesoporous metal oxide networks for high-performance photocatalysis.

    PubMed

    Bai, Hua; Li, Xinshi; Hu, Chao; Zhang, Xuan; Li, Junfang; Yan, Yan; Xi, Guangcheng

    2013-01-01

    Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high-yield producing single- and multi-component large-scale three-dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter-sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large-scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large-scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials.

  19. Mesoporous metallic rhodium nanoparticles

    NASA Astrophysics Data System (ADS)

    Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

    2017-05-01

    Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

  20. Fabrication of block copolymer templated mesoporous metal oxide composites for energy storage applications

    NASA Astrophysics Data System (ADS)

    Bhaway, Sarang M.

    Block copolymer templated mesoporous (2 nm-50 nm) metal oxides are considered promising electrode materials for energy storage devices such as electrochemical capacitors or lithium/sodium ion batteries. The mesoporous electrode morphology offers several advantages: (1) high surface area and porosity facilitate charge transfer across the electrolyte-electrode interface, (2) nanoscale-dimension of the oxide framework minimizes the solid state ion diffusion paths, and (3) interconnected porous morphology enables rapid electrolyte transport through the electrodes, leading to overall enhancement in charge storage capabilities. This research attempts to study the effect of mesoporosity and mesopore geometry on charge storage capabilities and cycling stability of ordered mesoporous metal oxide electrodes in energy storage devices. The first part of this dissertation focuses on fabrication of ordered mesoporous metal oxide composites utilizing the Evaporation Induced Self-Assembly (EISA) and the Block Copolymer Micelle Templating (BCMT) strategy. Firstly, we demonstrate fabrication of ordered mesoporous carbon-vanadium oxide composites utilizing EISA of phenolic resin oligomer (resol), VOCl3 and an amphiphilic triblock. We illustrate that carbon yield from resol carbonization can prevent break-out crystallization of vanadia during calcination and help maintain an ordered mesostructure. The mesoporous carbon-vanadia mesostructured thin films exhibit specific capacitance 7 times higher than their non-porous analog at high scan rates when tested as electrode in aqueous supercapacitor. The second part of this thesis focuses on BCMT technique to fabricate ordered mesoporous mixed-metal oxide electrodes for battery applications. Ordered mesoporous NixCo(3-x)O4 thin films with varying chemical composition are fabricated using a metal nitrate-citric acid complex and an amphiphilic PEGMA-b-PBA block copolymer template. This templating strategy is further extended to fabricate

  1. Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides

    PubMed Central

    Ren, Yuanhang; Yue, Bin; Gu, Min; He, Heyong

    2010-01-01

    Mesoporous silica molecular sieves are a kind of unique catalyst support due to their large pore size and high surface area. Several methods have been developed to immobilize heteropolyacids (HPAs) inside the channels of these mesoporous silicas. The mesoporous silica-supported HPA materials have been widely used as recyclable catalysts in heterogeneous systems. They have shown high catalytic activities and shape selectivities in some reactions, compared to the parent HPAs in homogeneous systems. This review summarizes recent progress in the field of mesoporous silica-supported HPAs applied in the heterogeneous catalysis area and preparation of nanostructured metal oxides using HPAs as precursors and mesoporous silicas as hard templates.

  2. Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

    SciTech Connect

    Wang Jun; Zhou Jideng; Li Zhanshuang; He Yang; Lin Shuangshuang; Liu Qi; Zhang Milin; Jiang Zhaohua

    2010-11-15

    We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs having different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted

  3. Sonochemical synthesis of mesoporous transition metal and rare earth oxides.

    PubMed

    Wang, Yanqin; Yin, Lunxiang; Gedanken, Arahon

    2002-11-01

    Straight-extended layered mesostructures based on transItion metal (Fe, Cr) and rare earth (Y, Ce, La, Sm, Er) oxides are synthesized by sonication for 3 h. After a longer period of sonication (6 h), hexagonal mesostructures based on Y- and Er-oxides are obtained. The surface areas of the Y-based hexagonal mesophases before and after extraction are 46.5, 256 m2/g, respectively. For Er-based hexagonal mesophases, the surface areas before and after extraction are 157 and 225 m2/g. The pore sizes after extraction are 5.0 and 2.2 nm for Y- and Er-based mesophases, respectively. Hexagonal mesostructures are also obtained for Zr-based material after sonication for 3 h and the hexagonal structure is still maintained after calcinations at 400 degrees C for 4 h, although the surface area is only 35 m2/g.

  4. Synthesis of Mesoporous Metal Oxides by Structure Replication: Thermal Analysis of Metal Nitrates in Porous Carbon Matrices

    PubMed Central

    Weinberger, Christian; Roggenbuck, Jan; Hanss, Jan; Tiemann, Michael

    2015-01-01

    A variety of metal nitrates were filled into the pores of an ordered mesoporous CMK-3 carbon matrix by solution-based impregnation. Thermal conversion of the metal nitrates into the respective metal oxides, and subsequent removal of the carbon matrix by thermal combustion, provides a versatile means to prepare mesoporous metal oxides (so-called nanocasting). This study aims to monitor the thermally induced processes by thermogravimetric analysis (TGA), coupled with mass ion detection (MS). The highly dispersed metal nitrates in the pores of the carbon matrix tend to react to the respective metal oxides at lower temperature than reported in the literature for pure, i.e., carbon-free, metal nitrates. The subsequent thermal combustion of the CMK-3 carbon matrix also occurs at lower temperature, which is explained by a catalytic effect of the metal oxides present in the pores. This catalytic effect is particularly strong for oxides of redox active metals, such as transition group VII and VIII metals (Mn, Fe, Co, Ni), Cu, and Ce.

  5. Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

    PubMed

    Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

    2013-11-01

    Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

  6. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide

    NASA Astrophysics Data System (ADS)

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-12-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

  7. Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide

    PubMed Central

    Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

    2015-01-01

    Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants. PMID:26681104

  8. Inkjet printing assisted synthesis of multicomponent mesoporous metal oxides for ultrafast catalyst exploration.

    PubMed

    Liu, Xiaonao; Shen, Yi; Yang, Ruoting; Zou, Shihui; Ji, Xiulei; Shi, Lei; Zhang, Yichi; Liu, Deyu; Xiao, Liping; Zheng, Xiaoming; Li, Song; Fan, Jie; Stucky, Galen D

    2012-11-14

    We describe an inkjet printing assisted cooperative-assembly method for high-throughput generation of catalyst libraries (multicomponent mesoporous metal oxides) at a rate of 1,000,000-formulations/hour with up to eight-component compositions. The compositions and mesostructures of the libraries can be well-controlled and continuously varied. Fast identification of an inexpensive and efficient quaternary catalyst for photocatalytic hydrogen evolution is achieved via a multidimensional group testing strategy to reduce the number of performance validation experiments (25,000-fold reduction over an exhaustive one-by-one search).

  9. Dehydrogenation of ethylbenzene with nitrous oxide in the presence of mesoporous silica materials modified with transition metal oxides.

    PubMed

    Kuśtrowski, Piotr; Chmielarz, Lucjan; Dziembaj, Roman; Cool, Pegie; Vansant, Etienne F

    2005-01-20

    The novel mesoporous templated silicas (MCM-48, SBA-15, MCF, and MSU) were used as supports for transition metal (Cu, Cr, or Fe) oxides. The catalysts were synthesized using the incipient wetness impregnation, and characterized by low-temperature N2 sorption, DRIFT, photoacoustic IR spectroscopy, UV-vis diffuse reflectance spectroscopy, and temperature-programmed desorption of ammonia. It was shown that the preparation method used results in different distributions and dimensions of the transition metal oxide clusters on the inert support surface. The prepared catalysts were tested in the reaction of oxidative dehydrogenation of ethylbenzene in the presence of nitrous oxide. The iron-containing catalysts showed the highest catalytic activity. The presence of isolated Fe3+ was found to be the most important factor influencing the ethylbenzene conversion. The undesirable effect of the increase in selectivity toward CO2 was observed for the samples with the highest concentrations of acidic surface sites.

  10. Rapid (<3 min) microwave synthesis of block copolymer templated ordered mesoporous metal oxide and carbonate films using nitrate-citric acid systems.

    PubMed

    Zhang, Yuanzhong; Bhaway, Sarang M; Wang, Yi; Cavicchi, Kevin A; Becker, Matthew L; Vogt, Bryan D

    2015-03-25

    Rapid chemical transformation from micelle templated precursors (metal nitrate and citric acid) to ordered mesoporous metal carbonates and oxides is demonstrated using microwave heating for cobalt, copper, manganese and zinc. Without aging requirements, <3 min of microwave processing yields highly ordered mesoporous films.

  11. KF-loaded mesoporous Mg-Fe bi-metal oxides: high performance transesterification catalysts for biodiesel production.

    PubMed

    Tao, Guiju; Hua, Zile; Gao, Zhe; Zhu, Yan; Zhu, Yan; Chen, Yu; Shu, Zhu; Zhang, Lingxia; Shi, Jianlin

    2013-09-21

    Using newly developed mesoporous Mg-Fe bi-metal oxides as supports, a novel kind of high performance transesterification catalysts for biodiesel production has been synthesized. More importantly, the impregnation solvent was for the first time found to substantially affect the structures and catalytic performances of the resultant transesterification catalysts.

  12. Superparamagnetic mesoporous Mg-Fe bi-metal oxides as efficient magnetic solid-base catalysts for Knoevenagel condensations.

    PubMed

    Gao, Zhe; Zhou, Jian; Cui, Fangming; Zhu, Yan; Hua, Zile; Shi, Jianlin

    2010-12-14

    Superparamagnetic mesoporous Mg-Fe bi-metal oxides with varied Mg-Fe atomic ratios have been successfully synthesized as solid base catalysts. The M2F-400 catalyst with Mg/Fe atomic ratio = 2 showed extraordinarily high activities for Knoevenagel reactions even at room temperature. It could be magnetically separated, recycled, and reused for at least five cycles.

  13. Self-arrangement of nanoparticles toward crystalline metal oxides with high surface areas and tunable 3D mesopores

    PubMed Central

    Lee, Hyung Ik; Lee, Yoon Yun; Kang, Dong-Uk; Lee, Kirim; Kwon, Young-Uk; Kim, Ji Man

    2016-01-01

    We demonstrate a new design concept where the interaction between silica nanoparticles (about 1.5 nm in diameter) with titania nanoparticles (anatase, about 4 nm or 6 nm in diameter) guides a successful formation of mesoporous titania with crystalline walls and controllable porosity. At an appropriate solution pH (~1.5, depending on the deprotonation tendencies of two types of nanoparticles), the smaller silica nanoparticles, which attach to the surface of the larger titania nanoparticles and provide a portion of inactive surface and reactive surface of titania nanoparticles, dictate the direction and the degree of condensation of the titania nanoparticles, resulting in a porous 3D framework. Further crystallization by a hydrothermal treatment and subsequent removal of silica nanoparticles result in a mesoporous titania with highly crystalline walls and tunable mesopore sizes. A simple control of the Si/Ti ratio verified the versatility of the present method through the successful control of mean pore diameter in the range of 2–35 nm and specific surface area in the ranges of 180–250 m2 g−1. The present synthesis method is successfully extended to other metal oxides, their mixed oxides and analogues with different particle sizes, regarding as a general method for mesoporous metal (or mixed metal) oxides. PMID:26893025

  14. Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds.

    PubMed

    Barakat, Tarek; Rooke, Joanna C; Tidahy, Haingomalala Lucette; Hosseini, Mahsa; Cousin, Renaud; Lamonier, Jean-François; Giraudon, Jean-Marc; De Weireld, Guy; Su, Bao-Lian; Siffert, Stéphane

    2011-10-17

    The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene.

  15. Adsorption and Wetting in Model Mesoporous Silicas and in Complex Metal Oxide Catalysts

    NASA Astrophysics Data System (ADS)

    Jayaraman, Karthik

    The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas adsorption measurements and characterization. Pore wetting is critical to many applications of mesoporous adsorbents, catalysts, and separation materials. In the work presented in Chapter 3, we employed the combined vapor adsorption study using nitrogen (77K) and water (293K) isotherms to evaluate the water contact angles for a series of ordered mesoporous silicas (ex:SBA-15). The proposed method of contact angle relies on the statistical film thickness (t-curve) of the adsorbed water. There were no t-curves for water for dehydroxylated or hydrophobic surfaces in literature and we addressed this issue by measuring t-curves for a series of model surfaces with known and varying silanol coverage. Using the radius of menisci ((H2O)), statistical film thickness t(H2O) from water isotherm, and the true radius of pores (rp(N 2)), from nitrogen isotherms, the water contact angle inside pores were calculated. As it was anticipated, the results obtained showed that the silica pore contact angles were strongly influenced by the number of the surface silanol groups and, therefore, by the thermal and hydration treatments of silicas. Phthalocyanines (Pcs) present an interesting class of catalytically active of molecules with unique spectroscopic, photoelectric, and sometimes magnetic properties. In the work presented in Chapter 4, we have undertaken a

  16. Effective Enrichment and Mass Spectrometry Analysis of Phosphopeptides Using Mesoporous Metal Oxide Nanomaterials

    PubMed Central

    Nelson, Cory A.; Szczech, Jeannine R.; Dooley, Chad J.; Xu, Qingge; Lawrence, Matthew J.; Zhu, Haoyue; Jin, Song; Ge, Ying

    2010-01-01

    Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium oxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium oxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as “a purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics. PMID:20704311

  17. A generalized method toward high dispersion of transition metals in large pore mesoporous metal oxide/silica hybrids.

    PubMed

    Bérubé, François; Khadraoui, Abdelkarim; Florek, Justyna; Kaliaguine, Serge; Kleitz, Freddy

    2015-07-01

    A series of transition metal acetylacetonates and acetates were used as precursors to generate high loadings of metal sites finely dispersed on SBA-15 silica. To achieve this, grafting of chelated transition metal precursors was performed directly to the surface of the as-synthesized SBA-15/P123 composite material. The thus-obtained metal/SBA-15 materials were studied by a variety of methods, e.g., elemental analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV-visible spectroscopy (DR-UV-vis), X-ray photoelectron spectroscopy (XPS) and N2 physisorption measurements at -196 °C. From the results, the proposed functionalization method was found to be a highly tunable and reproducible strategy to disperse transition metal oxides in mesoporous silica materials. The results from elemental analysis of the modified materials confirmed that the amount of grafted species is a function of the initial concentration of precursor in the solution used for grafting. The chelated complexes were found to strongly interact with the silanol groups of the silica material, resulting in a ligand-exchange process, as corroborated by FTIR. However, different metal precursors showed distinct reactivity towards the surface of mesoporous silica, owing to differences in the stability of the complexes under the conditions used for grafting. DR-UV-vis and XPS analyses suggest that when the stability of a given precursor decreases, the grafting procedure can lead to the formation of small clusters of the metal oxide on the silica surface. XRD and SEM also show that grafting of lower stability complexes, such as Mn(acac)3, Cu(acetate)2 and VO(acac)2, on the silica surface can result in the formation of large crystals on the external surface of the SBA-15 particles. Nevertheless, it was established by XPS analysis that only a small percentage of the grafted species leads to the formation of bulk

  18. Fabrication of mesoporous metal oxide coated-nanocarbon hybrid materials via a polyol-mediated self-assembly process

    NASA Astrophysics Data System (ADS)

    Feng, Bingmei; Wang, Huixin; Wang, Dongniu; Yu, Huilong; Chu, Yi; Fang, Hai-Tao

    2014-11-01

    After clarifying the formation mechanism of a typical metal glycolate precipitate, Ti glycolate, in a polyol-mediated synthesis using acetone as a precipitation medium, we describe a simple template-free approach based on an ethylene glycol-mediated synthesis to fabricate mesoporous metal oxide coated-nanocarbon hybrid materials including TiO2 coated-carbon nanotube (CNT), SnO2 coated-CNT, Cu2O/CuO coated-CNT and TiO2 coated-graphene sheet (GS). In the approach, metal oxide precursors, metal glycolates, were first deposited on CNTs or GSs, and subsequently transformed to the metal oxide coatings by pyrolysis or hydrolysis. By a comparison between the characterization of two TiO2-CNT hybrid materials using carboxylated CNTs and pristine CNTs without carboxyl groups, the driving force for initiating the deposition of metal glycolates on the carboxylated CNTs is confirmed to be the hydrogen bonding between the carboxyl groups and the polymer chains in metal glycolate sols. The electrochemical performances of the mesoporous TiO2 coated-carboxylated CNTs and TiO2-pristine CNT hybrid materials were investigated. The results show that the mesoporous TiO2 coated-carboxylated CNT with a uniform core-shell nanostructure exhibits substantial improvement in the rate performance in comparison with its counterpart from 0.5 C to 100 C because of its higher electronic conductivity and shorter diffusion path for the lithium ion. At the extremely high rate of 100 C, the specific capacity of TiO2 of the former reaches 85 mA h g-1, twice as high as that of the latter.After clarifying the formation mechanism of a typical metal glycolate precipitate, Ti glycolate, in a polyol-mediated synthesis using acetone as a precipitation medium, we describe a simple template-free approach based on an ethylene glycol-mediated synthesis to fabricate mesoporous metal oxide coated-nanocarbon hybrid materials including TiO2 coated-carbon nanotube (CNT), SnO2 coated-CNT, Cu2O/CuO coated-CNT and TiO2

  19. Synthesis of robust mesoporous metal oxide films by the rapid replication of block copolymer templates in supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Pai, Rajaram; Agarwal, Sumit; Hess, David; Watkins, James

    2004-03-01

    Ordered nanostructured materials are of great interest for applications in sensor and detection arrays, catalysis, separations and as low dielectric constant films in microelectronics. The optimization of electrical and mechanical properties requires strict control over porosity, pore structure, matrix composition and ultimately over long range order and patterning at the device level. Here we discuss a new approach to mesoporous solids that involves the infusion and selective condensation of metal oxide precursors within one phase domain of highly ordered, preformed block copolymer templates using supercritical carbon dioxide as the reaction medium. The template is then removed to produce the mesoporous oxide. To date we have replicated ordered spherical and cylindrical morphologies to yield silica, organosilicate and mixed silica/organosilicate mesostructures in films over 1 micron thick while maintaining all the structural details of the sacrificial copolymer template. The elimination of excess alcohol from the reaction media enables rapid and high degrees of network condensation. The implications of this process for the design and fabrication of ultra-low dielectric constant thin films are discussed. After post-processing, these films exhibit dielectric constants as low as 1.8.

  20. Hydrothermal synthesis of mesoporous metal oxide arrays with enhanced properties for electrochemical energy storage

    SciTech Connect

    Xiao, Anguo Zhou, Shibiao; Zuo, Chenggang; Zhuan, Yongbing; Ding, Xiang

    2015-01-15

    Highlights: • NiO mesoporous nanowall arrays are prepared via hydrothermal method. • Mesoporous nanowall arrays are favorable for fast ion/electron transfer. • NiO mesoporous nanowall arrays show good supercapacitor performance. - Abstract: Mesoporous nanowall NiO arrays are prepared by a facile hydrothermal synthesis method with a following annealing process. The NiO nanowall shows continuous mesopores ranging from 5 to 10 nm and grows vertically on the substrate forming a porous net-like structure with macropores of 20–300 nm. A plausible mechanism is proposed for the growth of mesoporous nanowall NiO arrays. As cathode material of pseudocapacitors, the as-prepared mesoporous nanowall NiO arrays show good pseudocapacitive performances with a high capacitance of 600 F g{sup −1} at 2 A g{sup −1} and impressive high-rate capability with a specific capacitance of 338 F g{sup −1} at 40 A g{sup −1}. In addition, the mesoporous nanowall NiO arrays possess good cycling stability. After 6000 cycles at 2 A g{sup −1}, a high capacitance of 660 F g{sup −1} is attained, and no obvious degradation is observed. The good electrochemical performance is attributed to its highly porous morphology, which provides large reaction surface and short ion diffusion paths, leading to enhanced electrochemical properties.

  1. Manganese Oxide Nanorod-Decorated Mesoporous ZSM-5 Composite as a Precious-Metal-Free Electrode Catalyst for Oxygen Reduction.

    PubMed

    Cui, Xiangzhi; Hua, Zile; Chen, Lisong; Zhang, Xiaohua; Chen, Hangrong; Shi, Jianlin

    2016-05-10

    A precious-metal-free cathode catalyst, MnO2 nanorod-decorated mesoporous ZSM-5 zeolite nanocomposite (MnO2 / m-ZSM-5), has been successfully synthesized by a hydrothermal and electrostatic interaction approach for efficient electrochemical catalysis of the oxygen reduction reaction (ORR). The active MnOOH species, that is, Mn(4+) /Mn(3+) redox couple and Brønsted acid sites on the mesoporous ZSM-5 matrix facilitate an approximately 4 e(-) process for the catalysis of the ORR comparable to commercial 20 wt % Pt/C. Stable electrocatalytic activity with 90 % current retention after 5000 cycles, and more importantly, excellent methanol tolerance is observed. Synergetic catalytic effects between the MnO2 nanorods and the mesoporous ZSM-5 matrix are proposed to account for the high electrochemical catalytic performance.

  2. Metal containing mesoporous silica materials: Synthesis, characterization, and applications

    NASA Astrophysics Data System (ADS)

    Gomez, Sinue

    The work presented here comprises the development of a new route for the incorporation of transition metals (TM = Mn, V, Cr) into the pores of mesoporous silica materials, the characterization, and the applications of the resulting materials. The mesoporous silica material used in this work is of the M41S family, known as MCM-48. The first part of the work is going to be focused on in the incorporation of manganese species. Characterization of the resulting materials will be sub-divided in two major parts: (1) Structural and textural properties and (2) Analysis of the Mn oxidation state, coordination and location in the mesoporous host. The process of incorporation of Mn into the mesoporous materials takes place by using high valence metal precursor anions. Then a mechanism to describe the process of loading the Mn species will be proposed. The method developed makes possible the incorporation of high loadings of transition metals while maintaining the properties of the host material, MCM-48. In the second part of the research the synthesis method developed in the first part is used to incorporate other transition metals such as vanadium and chromium. As in the first part, the nature of the TM species is investigated and their catalytic application in oxidation of styrene is also studied. The materials show good activity towards styrene oxidation with conversions as high as 100%. The catalysts can also be recycled without significant loss of activity. Finally, the last part of the research deals with the incorporation of tin oxide into mesoporous silica. A similar approach to the one used for transition metals was used to load tin in MCM-48, however, discrete tin oxide nanoparticles were formed on the surface of the mesoporous structure rather than inside of the pores. The sensing properties towards reducing gases such as hydrogen of these materials were tested, and the Sn containing mesoporous silica show promising properties for gas sensing applications.

  3. Photoinduced charge, ion & energy transfer processes at transition-metal coordination compounds anchored to mesoporous, nanocrystalline metal-oxide thin films

    NASA Astrophysics Data System (ADS)

    Ardo, Shane

    Photovoltaics provide a direct means of converting photons into useful, electric power; however traditional silicon-based technologies are too expensive for global commercialization. Dye-sensitized mesoporous semiconducting thin films, when utilized in regenerative photoelectrochemical cells, are one category of next generation photovoltaics that could eventually circumvent this issue. In fact, their architecture also affords a clear platform for implementation of a direct, solar fuel-forming system. The mechanisms involved in the myriad of molecular processes that occur in these molecular--solid-state hybrid materials are poorly understood. Thus, the overriding goal of this dissertation was to evaluate sensitized mesoporous, nanocrystalline metal-oxide thin films critically so as to elucidate mechanistic phenomena. Using transient and steady-state absorption and emission spectroscopies as well as (photo)electrochemistry, various previously unobserved processes have been identified. Chapter 2 demonstrates for the first time that the electric fields emanating from these charged thin films affect surface-anchored molecular sensitizers via a Stark effect. In most cases, further, but incomplete, ionic screening of the charged nanoparticles from the sensitizers, as non-Faradaic electrolyte redistribution, was spectroscopically inferred after rapid semiconductor charging. Chapter 3 highlights the reactivity of Co(I) coordination-compound catalysts anchored to anatase TiO2 thin-film electrodes. Visible-light excitation resulted in prompt excited-state electron injection into TiO2 while introduction of benzylbromide into the fluid solution surrounding the thin film led to a 2e--transfer, oxidative-addition reaction to Co1 forming a stable Co--benzyl product. Subsequent visible-light excitation initiated a photocatalytic cycle for C--C bond formation. Unique to the nanocrystalline thin films employed here, Chapter 4 demonstrates that traditional time-resolved polarization

  4. Designed synthesis of Graphene @titania @mesoporous silica hybrid material as size-exclusive metal oxide affinity chromatography platform for selective enrichment of endogenous phosphopeptides.

    PubMed

    Yao, Jizong; Sun, Nianrong; Deng, Chunhui; Zhang, Xiangming

    2016-04-01

    In this work, a novel size-exclusive metal oxide affinity chromatography (SE-MOAC) platform was built for phosphoproteome research. The operation for preparing graphene @titania @mesoporous silica nanohybrids (denoted as G@TiO2@mSiO2) was facile and easy to conduct by grafting titania nanoparticles on polydopamine (PD)-covered graphene, following a layer of mesoporous silica was coated on the outermost layer. The G@TiO2@mSiO2 nanohybrids exhibited high sensitivity with a low detection limit of 5 amol/μL (a total amount of 1 fmol) and high selectivity for phosphopeptides at a mass ratio of phosphopeptides to non-phosphopeptides (1:1000). The size-exclusive capability of the nanohybrids were also demonstrated by enriching the phosphopeptides from the mixture of Bovine Serum Albumin (BSA), α-casein, and β-casein digests with a high mass ratio (β-casein digests: α-casein: BSA, 1:500:500), which was attributed to the large surface area and ordered mesoporous channels. In addition, the G@TiO2@mSiO2 nanohybrids were employed to capture the endogenous phosphopeptides from human serum successfully.

  5. Mesoporous carbon-zirconium oxide nanocomposite derived from carbonized metal organic framework: A coating for solid-phase microextraction.

    PubMed

    Saraji, Mohammad; Mehrafza, Narges

    2016-08-19

    In this paper, a mesoporous carbon-ZrO2 nanocomposite was fabricated on a stainless steel wire for the first time and used as the solid-phase microextraction coating. The fiber was synthesized with the direct carbonization of a Zr-based metal organic framework. With the utilization of the metal organic framework as the precursor, no additional carbon source was used for the synthesis of the mesoporous carbon-ZrO2 nanocomposite coating. The fiber was applied for the determination of BTEX compounds (benzene, toluene, ethylbenzene and m, p-xylenes) in different water samples prior to gas chromatography-flame ionization detection. Such important experimental factors as synthesis time and temperature, salt concentration, equilibrium and extraction time, extraction temperature, desorption time and desorption temperature were studied and optimized. Good linearity in the concentration range of 0.2-200μgL(-1) and detection limits in the range of 0.05-0.56μgL(-1) was achieved for BTEX compounds. The intra- and inter-day relative standard deviations were in the range of 3.5-4.8% and 4.9-6.7%, respectively. The prepared fiber showed high capability for the analysis of BTEX compounds in different water and wastewater samples with good relative recoveries in the range of 93-107%.

  6. Simple Preparation of Novel Metal-Containing Mesoporous Starches †

    PubMed Central

    Ojeda, Manuel; Budarin, Vitaliy; Shuttleworth, Peter S.; Clark, James H.; Pineda, Antonio; Balu, Alina M.; Romero, Antonio A.; Luque, Rafael

    2013-01-01

    Metal-containing mesoporous starches have been synthesized using a simple and efficient microwave-assisted methodology followed by metal impregnation in the porous gel network. Final materials exhibited surface areas >60 m2 g−1, being essentially mesoporous with pore sizes in the 10–15 nm range with some developed inter-particular mesoporosity. These materials characterized by several techniques including XRD, SEM, TG/DTA and DRIFTs may find promising catalytic applications due to the presence of (hydr)oxides in their composition. PMID:28809249

  7. Simple Preparation of Novel Metal-Containing Mesoporous Starches.

    PubMed

    Ojeda, Manuel; Budarin, Vitaliy; Shuttleworth, Peter S; Clark, James H; Pineda, Antonio; Balu, Alina M; Romero, Antonio A; Luque, Rafael

    2013-05-10

    Metal-containing mesoporous starches have been synthesized using a simple and efficient microwave-assisted methodology followed by metal impregnation in the porous gel network. Final materials exhibited surface areas >60 m² g(-1), being essentially mesoporous with pore sizes in the 10-15 nm range with some developed inter-particular mesoporosity. These materials characterized by several techniques including XRD, SEM, TG/DTA and DRIFTs may find promising catalytic applications due to the presence of (hydr)oxides in their composition.

  8. Mesoporous Silica-Supported Metal Oxide-Promoted Rh Nanocatalyst for Selective Production of Ethanol from Syngas

    SciTech Connect

    Kraus, George

    2010-09-30

    The objective is to develop a process that will convert synthesis gas from coal into ethanol and then transform the ethanol into hydrogen. Principal investigators from Iowa State University include Dr. George Kraus, Dr. Victor Lin, Marek Pruski, and Dr. Robert Brown. Task 1 involves catalyst development and catalyst scale up. Mesoporous manganese silicate mixed oxide materials will be synthesized, characterized and evaluated. The first-and secondgeneration catalysts have been prepared and scaled up for use in Task 2. The construction of a high-pressure reactor system for producing synthetic liquid fuel from simulated synthesis gas stream has been completed as the first step in Task 2. Using the first- and second generation catalysts, the reactor has demonstrated the production of synthetic liquid fuel from a simulated synthesis gas stream.

  9. Corrosion behavior of mesoporous transition metal nitrides

    SciTech Connect

    Yang, Minghui; Allen, Amy J.; Nguyen, Minh T.; Ralston, Walter T.; MacLeod, Michelle J.; DiSalvo, Francis J.

    2013-09-15

    Transition metal nitrides (TMN) have many desirable characteristics such as high hardness and good thermal stability under reducing conditions. This work reports an initial survey of the chemical stability of mesoporous TMNs (TM=Nb, V, Cr and Ti) in water at 80 °C at neutral, acidic and alkaline pH. The mesoporous TMNs had specific surface areas of 25–60 m{sup 2}/g with average pore sizes ranging from 10 to 50 nm. The high surface areas of these materials enhance the rate of corrosion per unit mass over that of a bulk material, making detection of corrosion much easier. The products were characterized by Rietveld refinement of powder X-ray diffraction (PXRD) patterns and by scanning electron microscopy (SEM). Several nitrides have corrosion rates that are, within error, not distinguishable from zero (±1 Å/day). Of the nitrides examined, CrN appears to be the most corrosion resistant under acidic conditions. None of the nitrides studied are corrosion resistant under alkaline conditions. - Graphical abstract: Corrosion behavior of mesoporous transition metal nitrides (TM=Nb, V, Cr and Ti) in acidic and alkaline solutions at 80 °C for 2 weeks. Display Omitted - highlights: • Corrosion rates of mesoporous transition metal nitrides in aqueous solution is reported. • The mesoporous TMNs had surface areas of 25–60 m{sup 2}/g. • CrN is the most corrosion resistant under the conditions studied.

  10. Enhanced retention of aqueous transition metals in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Nelson, J.; Bargar, J.; Brown, G. E.; Maher, K.

    2013-12-01

    Mesoporosity (2-50 nm diameter pores) is abundant within grain coatings and primary silicate minerals in natural environments. Mesopores often contribute significantly to total specific surface area and act as gateways for the transport of subsurface solutes, including nutrients and contaminants, between mineral surfaces and ambient fluids. However, the physiochemical mechanisms of sorption and transport within mesopores cannot be assumed to be the same as for macropores (>50 nm), because of confinement-induced changes in water properties, the structure of electrical double layers, solvation shells and dehydration rates of aquo ions, and the charge and reactive site densities of mineral surfaces. Despite the ubiquity of confined spaces in natural and industrial porous media, few studies have examined the molecular-scale mechanisms and geochemical reactions controlling meso-confinement phenomena in environmentally relevant materials. We conducted batch Zn sorption experiments using synthetic, controlled pore-size (i.e., 7.5-300 nm), metal-oxide beads as model geologic substrates. Comparison of Zn adsorbed onto macroporous and mesoporous silica beads indicates Zn adsorption capacity is increased in mesopores when normalized to surface area. In the presence of a background electrolyte (i.e., NaCl), Zn sorption capacity to macroporous silica is reduced; however, no significant difference in Zn sorption capacity on mesoporous silica was observed between the presence and absence of a background electrolyte. The effect of competing cations is indirect evidence that mesopores promote inner-sphere complexation and reduce outer-sphere complexation. EXAFS characterization of adsorbed zinc to macroporous silica matches that reported for low Zn coverages on silica (Roberts et al., JCIS, 2003), whereas a different spectrum is observed for the mesoporous case. Shell-by-shell fitting indicates that Zn is dominantly in octahedral coordination in macropores, as opposed to

  11. Mesoporous tertiary oxides via a novel amphiphilic approach

    SciTech Connect

    Bennett, Natasha; Hall, Simon R. E-mail: Annela.Seddon@bristol.ac.uk; Seddon, Annela M. E-mail: Annela.Seddon@bristol.ac.uk; Hallett, James E.; Kockelmann, Winfried; Ting, Valeska P.; Sadasivan, Sajanikumari; Tooze, Robert P.

    2016-01-01

    We report a facile biomimetic sol-gel synthesis using the sponge phase formed by the lipid monoolein as a structure-directing template, resulting in high phase purity, mesoporous dysprosium- and gadolinium titanates. The stability of monoolein in a 1,4-butanediol and water mixture complements the use of a simple sol-gel metal oxide synthesis route. By judicious control of the lipid/solvent concentration, the sponge phase of monoolein can be directly realised in the pyrochlore material, leading to a porous metal oxide network with an average pore diameter of 10 nm.

  12. Double-Layer 3D Macro-Mesoporous Metal Oxide Modified Boron-Doped Diamond with Enhanced Photoelectrochemical Performance.

    PubMed

    Fan, Jiaqi; Shi, Huijie; Xiao, Hanshuang; Zhao, Guohua

    2016-04-22

    In this work, a TiO2/Sb-doped SnO2 electrode was prepared on the boron-doped diamond (BDD) substrate with double-layer three-dimensional macro-mesoporous (DL3DOM-m) structure, using the polystyrene sphere (PS) vertical deposition method. The as-prepared DL3DOM-m TiO2/SnO2/BDD was employed for organic contaminant removal, showing excellent photoelectrocatalytic performance. SEM, XRD and XPS indicated that DL3DOM-m electrode possessed a 3D macroporous layered framework with uniform pore size (about 400 nm), nanosized particles (4.5-5.8 nm), and high electroactive surface area (3-fold more than that of BDD). SA-XRD indicated the backbone of DL3DOM-m electrode had mesoporous structure. It was found that the as-prepared electrode exhibited remarkable electrocatalytic activity, high photocurrent and outstanding absorption capability (91.0 μg cm(-2)). Furthermore, bisphenol A (BPA) was completely decomposed after 3 h of reaction applying DL3DOM-m electrode as photoanode, and that on BDD was only 58.9%. It indicated that the modified electrode had great potential to be used in practical water treatment with high photoelectrochemical performance.

  13. Size-selective biocatalysis of myoglobin immobilized into a mesoporous metal-organic framework with hierarchical pore sizes.

    PubMed

    Chen, Yao; Lykourinou, Vasiliki; Hoang, Tran; Ming, Li-June; Ma, Shengqian

    2012-09-03

    The protein myoglobin has been successfully immobilized into a mesoporous metal-organic framework with hierarchical pore sizes, which demonstrates interesting size-selective biocatalysis as well as superior catalytic activities toward small substrate oxidation compared to its mesoporous silica material counterpart.

  14. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-01-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes. PMID:24548992

  15. Enantioselective recognition at mesoporous chiral metal surfaces

    NASA Astrophysics Data System (ADS)

    Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A.; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-02-01

    Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

  16. Mesoporous titanium dioxide coating for metallic implants.

    PubMed

    Xia, Wei; Grandfield, Kathryn; Hoess, Andreas; Ballo, Ahmed; Cai, Yanling; Engqvist, Håkan

    2012-01-01

    A bioactive mesoporous titanium dioxide (MT) coating for surface drug delivery has been investigated to develop a multifunctional implant coating, offering quick bone bonding and biological stability. An evaporation induced self-assembly (EISA) method was used to prepare a mesoporous titanium dioxide coating of the anatase phase with BET surface area of 172 m(2)/g and average pore diameter of 4.3 nm. Adhesion tests using the scratch method and an in situ screw-in/screw-out technique confirm that the MT coating bonds tightly with the metallic substrate, even after removal from bone. Because of its high surface area, the bioactivity of the MT coating is much better than that of a dense TiO(2) coating of the same composition. Quick formation of hydroxyapatite (HA) in vitro can be related to enhance bonding with bone. The uptake of antibiotics by the MT coating reached 13.4 mg/cm(3) within a 24 h loading process. A sustained release behavior has been obtained with a weak initial burst. By using Cephalothin as a model drug, drug loaded MT coating exhibits a sufficient antibacterial effect on the material surface, and within millimeters from material surface, against E.coli. Additionally, the coated and drug loaded surfaces showed no cytotoxic effect on cell cultures of the osteoblastic cell line MG-63. In conclusion, this study describes a novel, biocompatiblemesoporous implant coating, which has the ability to induce HA formation and could be used as a surface drug-delivery system.

  17. Synthesis of ternary metal nitride nanoparticles using mesoporous carbon nitride as reactive template.

    PubMed

    Fischer, Anna; Müller, Jens Oliver; Antonietti, Markus; Thomas, Arne

    2008-12-23

    Mesoporous graphitic carbon nitride was used as both a nanoreactor and a reactant for the synthesis of ternary metal nitride nanoparticles. By infiltration of a mixture of two metal precursors into mesoporous carbon nitride, the pores act first as a nanoconfinement, generating amorphous mixed oxide nanoparticles. During heating and decomposition, the carbon nitride second acts as reactant or, more precisely, as a nitrogen source, which converts the preformed mixed oxide nanoparticles into the corresponding nitride (reactive templating). Using this approach, ternary metal nitride particles with diameters smaller 10 nm composed of aluminum gallium nitride (Al-Ga-N) and titanium vanadium nitride (Ti-V-N) were synthesized. Due to the confinement effect of the carbon nitride matrix, the composition of the resulting metal nitride can be easily adjusted by changing the concentration of the preceding precursor solution. Thus, ternary metal nitride nanoparticles with continuously adjustable metal composition can be produced.

  18. Highly mesoporous metal-organic framework assembled in a switchable solvent.

    PubMed

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-22

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  19. Highly mesoporous metal-organic framework assembled in a switchable solvent

    NASA Astrophysics Data System (ADS)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  20. Preferential oxidation of carbon monoxide catalyzed by platinum nanoparticles in mesoporous silica.

    PubMed

    Fukuoka, Atsushi; Kimura, Jun-ichi; Oshio, Tadashi; Sakamoto, Yuzuru; Ichikawa, Masaru

    2007-08-22

    Preferential oxidation (PROX) of CO is an important practical process to purify H2 for use in polymer electrolyte fuel cells. Although many supported noble metal catalysts have been reported so far, their catalytic performances remain insufficient for operation at low temperature. We found that Pt nanoparticles in mesoporous silica give unprecedented activity, selectivity, and durability in the PROX reaction below 353 K. We also studied the promotional effect of mesoporous silica in the Pt-catalyzed PROX reaction by infrared spectroscopy using the isotopic tracer technique. Gas-phase O2 is not directly used for CO oxidation, but the oxygen of mesoporous silica is incorporated into CO2. These results suggest that CO oxidation is promoted by the attack of the surface OH groups to CO on Pt without forming water.

  1. Iron oxide nanoparticles stabilized inside highly ordered mesoporous silica

    NASA Astrophysics Data System (ADS)

    Bhaumik, A.; Samanta, S.; Mal, N. K.

    2005-11-01

    Nanosized iron oxide, a moderately large band-gap semiconductor and an essential component of optoelectrical and magnetic devices, has been prepared successfully inside the restricted internal pores of mesoporous silica material through in-situ reduction during impregnation. The samples were characterized by powder XRD, TEM, SEM/EDS, N_{2} adsorption, FT-IR and UV-visible spectroscopies. Characterization data indicated well-dispersed isolated nanoclusters of (Fe_{2}O_{3})_{n}, within the internal surface of 2D-hexagonal mesoporous silica structure. No occluded Fe/Fe_{2}O_{3} crystallites were observed at the external surface of the mesoporous silica nanocomposites. Inorganic mesoporous host, such as hydrophilic silica in the pore walls, directs a physical constraint necessary to prevent the creation of large Fe_{2}O_{3} agglomerates and enables the formation of nanosized Fe_{2}O_{3} particles inside the mesopore.

  2. Graphene nanosheets as a platform for the 2D ordering of metal oxide nanoparticles: mesoporous 2D aggregate of anatase TiO2 nanoparticles with improved electrode performance.

    PubMed

    Lee, Jang Mee; Kim, In Young; Han, Song Yi; Kim, Tae Woo; Hwang, Seong-Ju

    2012-10-22

    Graphene nanosheets are successfully applied as an effective platform for the 2D ordering of metal oxide nanoparticles. Mesoporous 2D aggregates of anatase TiO(2) nanoparticles are synthesized by the heat treatment of the uniformly hybridized nanocomposite of layered titanate-reduced graphene oxide (RGO) at elevated temperatures. The precursor layered titanate-RGO nanocomposite is prepared by self-assembly of anionic RGO nanosheets and cationic TiO(2) nanosols. The calcination of the as-prepared layered titanate-RGO nanocomposite at 500 °C induces a structural and morphological change of layered titanate nanoplates into anatase TiO(2) nanoparticles without significant modification of the RGO nanosheet. Increasing the heating temperature to 600 °C gives rise to elimination of the RGO component, leading to the formation of sheetlike porous aggregates of RGO-free TiO(2) nanoparticles. The nanocomposites calcined at 500-700 °C display promising functionality as negative electrodes for lithium ion batteries. Among the present calcined derivatives, the 2D sheet-shaped aggregate of TiO(2) nanoparticles obtained from calcination at 600 °C delivers the greatest specific discharge capacity with good capacity retention for all current density conditions applied. Such superior electrode performance of the nanocomposite calcined at 600 °C is attributable both to the improved stability of the crystal structure and crystal morphology of titania and to the enhancement of Li(+) ion transport through the enlargement of mesopores. The present findings clearly demonstrate the usefulness of RGO nanosheets as a platform for 2D-ordered superstructures of metal oxide nanoparticles with improved electrode performance.

  3. Textural manipulation of mesoporous materials for hosting of metallic nanocatalysts.

    PubMed

    Sun, Junming; Bao, Xinhe

    2008-01-01

    The preparation and stabilization of nanoparticles are becoming very crucial issues in the field of so-called "nanocatalysis". Recent developments in supramolecular self-assembled porous materials have opened a new way to get nanoparticles hosted in the channels of such materials. In this paper, a new approach towards monodisperse and thermally stable metal nanoparticles by confining them in ordered mesoporous materials is presented, and three aspects are illustrated. Firstly, the recent progress in the functional control of mesoporous materials will be briefly introduced, and the rational tuning of the textures, pore size, and pore length is demonstrated by controlling supramolecular self-assembly behavior. A novel synthesis of short-pore mesoporous materials is emphasized for their easy mass transfer in both biomolecule absorption and the facile assembly of metal nanocomposites within their pore channels. In the second part, the different routes for encapsulating monodisperse nanoparticles inside channels of porous materials are discussed, which mainly includes the ion-exchange/conventional incipient wetness impregnation, in situ encapsulation routes, organometallic methodologies, and surface functionalization schemes. A facile in situ autoreduction route is highlighted to get monodisperse metal nanoparticles with tunable sizes inside the channels of mesoporous silica. Finally, confinement of mesoporous materials is demonstrated to improve the thermal stability of monodisperse metal nanoparticles catalysts and a special emphasis will be focused on the stabilization of the metal nanoparticles with a low Tammann temperature. Several catalytic reactions concerning the catalysis of nanoparticles will be presented. These uniform nanochannels, which confine monodisperse and stable metal nanoparticles catalysts, are of great importance in the exploration of size-dependent catalytic chemistry and further understanding the nature of catalytic reactions.

  4. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    SciTech Connect

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  5. Nanorods of Various Oxides and Hierarchically Structured Mesoporous Silica by Sol-Gel Electrophoresis

    SciTech Connect

    Limmer, Steven J.; Hubler, Timothy L.; Cao, Guozhong

    2003-01-02

    In this paper, we report the template-based growth of nanorods of oxides and hierarchically structured mesoporous silica, formed by means of a combination of sol-gel processing and elecrophoretic deposition. Both single metal oxides (TiO2) and complex oxides (Pb(Zr0.52Ti0.48)O3) have been grown by this method. This method has also been applied to the growth of nanorods of mesoporous silica having an ordered pore structure, where the pores are aligned parallel to the long axis of the nanorod. Uniformly sized nanorods of about 125-200 nm in diameter and 10 um in length were grown over large areas with near unidirectional alignment. Appropriate sol preparation yielded the desired stoichiometric chemical composition and crystal structure of the oxide nanorods, with a heat treatment (500-700 C for 15-30 min) for crystallization, densification and any necessary pyrolysis.

  6. Mesoporous layer-by-layer ordered nanohybrids of layered double hydroxide and layered metal oxide: highly active visible light photocatalysts with improved chemical stability.

    PubMed

    Gunjakar, Jayavant L; Kim, Tae Woo; Kim, Hyo Na; Kim, In Young; Hwang, Seong-Ju

    2011-09-28

    Mesoporous layer-by-layer ordered nanohybrids highly active for visible light-induced O(2) generation are synthesized by self-assembly between oppositely charged 2D nanosheets of Zn-Cr-layered double hydroxide (Zn-Cr-LDH) and layered titanium oxide. The layer-by-layer ordering of two kinds of 2D nanosheets is evidenced by powder X-ray diffraction and cross-sectional high resolution-transmission electron microscopy. Upon the interstratification process, the original in-plane atomic arrangements and electronic structures of the component nanosheets remain intact. The obtained heterolayered nanohybrids show a strong absorption of visible light and a remarkably depressed photoluminescence signal, indicating an effective electronic coupling between the two component nanosheets. The self-assembly between 2D inorganic nanosheets leads to the formation of highly porous stacking structure, whose porosity is controllable by changing the ratio of layered titanate/Zn-Cr-LDH. The resultant heterolayered nanohybrids are fairly active for visible light-induced O(2) generation with a rate of ∼1.18 mmol h(-1) g(-1), which is higher than the O(2) production rate (∼0.67 mmol h(-1) g(-1)) by the pristine Zn-Cr-LDH material, that is, one of the most effective visible light photocatalysts for O(2) production, under the same experimental condition. This result highlights an excellent functionality of the Zn-Cr-LDH-layered titanate nanohybrids as efficient visible light active photocatalysts. Of prime interest is that the chemical stability of the Zn-Cr-LDH is significantly improved upon the hybridization, a result of the protection of the LDH lattice by highly stable titanate layer. The present findings clearly demonstrate that the layer-by-layer-ordered assembly between inorganic 2D nanosheets is quite effective not only in improving the photocatalytic activity of the component semiconductors but also in synthesizing novel porous LDH-based hybrid materials with improved chemical

  7. Generalised syntheses of ordered mesoporous oxides: the atrane route

    NASA Astrophysics Data System (ADS)

    Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

    2000-06-01

    A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

  8. Oxidative nanopatterning of titanium generates mesoporous surfaces with antimicrobial properties.

    PubMed

    Variola, Fabio; Zalzal, Sylvia Francis; Leduc, Annie; Barbeau, Jean; Nanci, Antonio

    2014-01-01

    Mesoporous surfaces generated by oxidative nanopatterning have the capacity to selectively regulate cell behavior, but their impact on microorganisms has not yet been explored. The main objective of this study was to test the effects of such surfaces on the adherence of two common bacteria and one yeast strain that are responsible for nosocomial infections in clinical settings and biomedical applications. In addition, because surface characteristics are known to affect bacterial adhesion, we further characterized the physicochemical properties of the mesoporous surfaces. Focused ion beam (FIB) was used to generate ultrathin sections for elemental analysis by energy-dispersive X-ray spectroscopy (EDS), nanobeam electron diffraction (NBED), and high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) imaging. The adherence of Staphylococcus aureus, Escherichia coli and Candida albicans onto titanium disks with mesoporous and polished surfaces was compared. Disks with the two surfaces side-by-side were also used for direct visual comparison. Qualitative and quantitative results from this study indicate that bacterial adhesion is significantly hindered by the mesoporous surface. In addition, we provide evidence that it alters structural parameters of C. albicans that determine its invasiveness potential, suggesting that microorganisms can sense and respond to the mesoporous surface. Our findings demonstrate the efficiency of a simple chemical oxidative treatment in generating nanotextured surfaces with antimicrobial capacity with potential applications in the implant manufacturing industry and hospital setting.

  9. Oxidative nanopatterning of titanium generates mesoporous surfaces with antimicrobial properties

    PubMed Central

    Variola, Fabio; Zalzal, Sylvia Francis; Leduc, Annie; Barbeau, Jean; Nanci, Antonio

    2014-01-01

    Mesoporous surfaces generated by oxidative nanopatterning have the capacity to selectively regulate cell behavior, but their impact on microorganisms has not yet been explored. The main objective of this study was to test the effects of such surfaces on the adherence of two common bacteria and one yeast strain that are responsible for nosocomial infections in clinical settings and biomedical applications. In addition, because surface characteristics are known to affect bacterial adhesion, we further characterized the physicochemical properties of the mesoporous surfaces. Focused ion beam (FIB) was used to generate ultrathin sections for elemental analysis by energy-dispersive X-ray spectroscopy (EDS), nanobeam electron diffraction (NBED), and high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) imaging. The adherence of Staphylococcus aureus, Escherichia coli and Candida albicans onto titanium disks with mesoporous and polished surfaces was compared. Disks with the two surfaces side-by-side were also used for direct visual comparison. Qualitative and quantitative results from this study indicate that bacterial adhesion is significantly hindered by the mesoporous surface. In addition, we provide evidence that it alters structural parameters of C. albicans that determine its invasiveness potential, suggesting that microorganisms can sense and respond to the mesoporous surface. Our findings demonstrate the efficiency of a simple chemical oxidative treatment in generating nanotextured surfaces with antimicrobial capacity with potential applications in the implant manufacturing industry and hospital setting. PMID:24872694

  10. Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

    SciTech Connect

    Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.; Armatas, Gerasimos S.

    2015-04-01

    Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the pore surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.

  11. Additive-Driven Self-Assembly of Well Ordered Mesoporous Carbon/Iron Oxide Nanoparticle Composites for Supercapacitors

    NASA Astrophysics Data System (ADS)

    Lin, Ying; Wang, Xinyu; Qian, Gang; Watkins, James; Department of Polymer Science and Engineering, University of Massachusetts Amherst Team

    2014-03-01

    Supercapacitors have attracted significant attention as energy storage devices for applications to meet the requirements of fast charge and discharge, high power density, and long cycle life. Recent research efforts demonstrate that the metal oxide- mesoporous carbon nanocomposite materials are indeed a class of promising electrode materials for high performance supercapacitors. However several major drawbacks for metal oxide-carbon nanocomposite materials remain, such as relatively low loadings of the metal oxide, aggregation of nanoparticles, and the lack of an ordered mesoporous structure. Here we demonstrate that well ordered mesoporous carbon/iron oxide composites can be prepared through simple carbonization of blends of block copolymers serving as the source of carbon and a porogen, e.g., poly(t-butyl acrylate)-block-polyacrylonitrile (PtBA-b-PAN), and iron oxide nanoparticles (NPs). Strong interactions between phenol-functionalized iron oxide NPs and polyacrylonitrile result in a preferential dispersion of the nanoparticles within the PAN domains and leads to ordered nanostructured mesoporous carbon framework containing upto 30 wt This work was supported by the NSF Center for Hierarchical Manufacturing at the University of Massachusetts (CMMI-1025020).

  12. Synthesis and characterization of mesoporous indium tin oxide possessing an electronically conductive framework.

    PubMed

    Emons, Theo T; Li, Jianquan; Nazar, Linda F

    2002-07-24

    The new mesoporous transparent conducting oxide based on indium-tin-oxide, meso-ITO, has been synthesized by a modified sol-gel method, using CTAB as the surfactant. Critical was the employment of triethanolamine to control the rate of hydrolysis and inhibit deposition of the bulk oxides. Removal of the surfactant by calcination yielded a relatively well-ordered worm-hole motif arrangement of pores visible in the TEM and stable to 400 degrees C. BET measurements revealed no hysteresis in the absorption-desorption isotherm, consistent with a narrow pore-size distribution (between 20 and 40 A depending on the In:Sn ratio); surface areas ranged between 270 and 310 m2/g. This colorless material is the first mesoporous oxide exhibiting substantial framework conductivity, with a conductivity at 25 degrees C of 1.2 x 10-3 S/cm. This distinguishes it from mesoporous mixed-valence transition-metal oxides that exhibit weak hopping semiconductor behavior and much lower conductivity.

  13. Heterogeneous Catalysis in Zeolites, Mesoporous Silica, and Metal-Organic Frameworks.

    PubMed

    Liang, Jie; Liang, Zibin; Zou, Ruqiang; Zhao, Yanli

    2017-08-01

    Crystalline porous materials are important in the development of catalytic systems with high scientific and industrial impact. Zeolites, ordered mesoporous silica, and metal-organic frameworks (MOFs) are three types of porous materials that can be used as heterogeneous catalysts. This review focuses on a comparison of the catalytic activities of zeolites, mesoporous silica, and MOFs. In the first part of the review, the distinctive properties of these porous materials relevant to catalysis are discussed, and the corresponding catalytic reactions are highlighted. In the second part, the catalytic behaviors of zeolites, mesoporous silica, and MOFs in four types of general organic reactions (acid, base, oxidation, and hydrogenation) are compared. The advantages and disadvantages of each porous material for catalytic reactions are summarized. Conclusions and prospects for future development of these porous materials in this field are provided in the last section. This review aims to highlight recent research advancements in zeolites, ordered mesoporous silica, and MOFs for heterogeneous catalysis, and inspire further studies in this rapidly developing field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  15. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    SciTech Connect

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-15

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol–gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated. - Graphical abstract: One-pot amorphous MnO{sub 2} supported on mesoporous anataseTiO{sub 2}. - Highlights: • Mesoporous manganese titanium oxides were synthesized using block copolymer. • Block copolymers form complexes with Mn{sup 2+} from MnCl{sub 2}. • With block copolymer, manganese oxide can be dispersed around the titania crystallites. • With Mn(acac){sub 2}, manganese is dispersed inside titania. • MnOOH crystallizes outside mesoporous titania during hydrothermal treatment.

  16. Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

    PubMed

    Liu, Xiao; Maegawa, Yoshifumi; Goto, Yasutomo; Hara, Kenji; Inagaki, Shinji

    2016-07-04

    Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods.

  17. Low-temperature, highly selective, gas-phase oxidation of benzyl alcohol over mesoporous K-Cu-TiO2 with stable copper(I) oxidation state.

    PubMed

    Fan, Jie; Dai, Yihu; Li, Yunlong; Zheng, Nanfeng; Guo, Junfang; Yan, Xiaoqing; Stucky, Galen D

    2009-11-04

    A newly developed mesoporous mixed metal oxide (K-Cu-TiO(2)) catalyst is capable of highly selective, gas-phase benzyl alcoholbenzaldehyde transformation at excellent yields (>99%) under surprisingly low temperatures (203 degrees C, bp of benzyl alcohol). The low-temperature reaction conditions and integration of K and Cu(I) components into the TiO(2) matrix are of vital importance for the stabilization of an active Cu(I) oxidation state and resultant stable, excellent catalytic performance.

  18. Gold nanocatalysts supported on heterostructured PbSO4-MCF mesoporous materials for CO oxidation

    SciTech Connect

    Li, Lin; Tian, Chengcheng; Chai, Songhai; Binder, Andrew J; Brown, Suree; Veith, Gabriel M; Dai, Sheng

    2014-01-01

    Metal oxides are commonly used as the supports of gold nanoparticles for catalytic CO oxidation, whereas metal salts are rarely considered suitable supports. In the present work, we developed a new kind of gold nanocatalyst supported on heterostructured PbSO4-MCF mesoporous materials that was prepared by an in situ growth method using dodecylbenzenesulfonate (SOBS) as a sulfonate precursor. It was found that an Au/PbSO4-MCF (SDBS) catalyst preheated at 300 degrees C showed high CO conversion below 100 degrees C. In addition, the stability of selected catalysts was studied as a function of time on stream. Because of the alteration of surface properties, these Au nanocatalysts were highly sinter-resistant. Published by Elsevier B.V.

  19. Electrochemical capacitor performance of hydrous ruthenium oxide/mesoporous carbon composite electrodes

    NASA Astrophysics Data System (ADS)

    Jang, Jong H.; Han, Sangjin; Hyeon, Taeghwan; Oh, Seung M.

    Ruthenium/carbon composite materials are prepared by impregnating ruthenium(III) acetylacetonate into a mesoporous carbon (average pore diameter=12 mn, pore volume=3.6 cm 3 g -1) and then heat treatment at 320 °C for 2 h under an argon atmosphere. The metallic ruthenium nanoparticles are converted to pseudo-capacitive hydrous ruthenium oxide by electrochemical oxidation at 0.75 V (versus SCE) for 2 h in 2.0 M H 2SO 4. The specific capacitance of the composite electrodes, which is the sum of the double-layer capacitance of mesoporous carbon and the pseudo-capacitance of hydrous ruthenium oxide, reaches 243 F g -1 with heavy loading. As the loading is increased, however, the degree of ruthenium utilization for a pseudo-capacitor becomes poorer, presumably due to a limited conversion to the hydrous oxide form. The rate capability of composite electrodes also decreases with increase in ruthenium loading, due to an increase in both the equivalent series resistance (ESR) and the overall capacitance value. The ESR enlargement is caused mainly an increase in the electrolyte resistance within pores which, in turn, results from a pore narrowing with ruthenium loading Hindered ionic motion in narrowed pores can explain this feature. An increase in the RC time constant with ruthenium loading is further verified by ac impedance measurements.

  20. Cyclic resistive switching effect in plasma electrolytically oxidized mesoporous Pt/TiO2 structures

    NASA Astrophysics Data System (ADS)

    Fullam, S.; Ray, N. J.; Karpov, E. G.

    2015-06-01

    Understanding the resistive switching phenomenon in metal oxide semiconductors is necessary in producing reliable resistive random access memory and other variable resistance devices. An alternative technique for fabricating resistive switching elements is presented. Using plasma electrolytic oxidation, 10-11 μ m thick oxide layers were galvanostatically grown on Ti substrates in a 3 M H2SO4 electrolyte. Analysis of the TiO2 layer by SEM, AFM, and XRD found the mesoporous titania surface to have a high ratio of rutile to anatase phases. The samples demonstrated pinched I-V hysteresis attributed to the resistive switching effect, when subjected to cyclic loading (±2.5, 1.6, 0.7 V; 23-736 μ Hz) at room temperature. Ratio with magnitude of 6 is reported for the resistance switching effect during 1.6 V 368 μ Hz loads.

  1. Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly.

    PubMed

    Park, Jinhee; Wang, Zhiyong U; Sun, Lin-Bing; Chen, Ying-Pin; Zhou, Hong-Cai

    2012-12-12

    Introduction of functionalized mesopores into microporous metal-organic frameworks (MOFs) can endow them with suitable properties for applications in gas storage, separation, catalysis, and drug delivery. However, common methods for functionalization (including pre- and post-synthetic modifications) of the internal surface of a MOF reduce the pore size of the MOF because the additional functional groups fill up the pores. We present a metal-ligand-fragment coassembly strategy for the introduction of (meso)pores functionalized with various substituent groups on the ligand fragments. Astonishingly, this new functionalization strategy increases the pore volume of a MOF instead of reducing it. Since the ligand fragments are often readily available or easily prepared, the new procedure for synthesis of the modified MOFs becomes much easier and more applicable than existing approaches. Remarkably, mesopores can be generated conveniently and controllably by the coassembly of a ligand and its fragment containing the desired functional groups. The fragment/ligand ratio has been optimized to preserve the parent structure and to promote maximum mesopore introduction, which has led to a systematic evaluation of the effectiveness of a series of functional groups for the adsorption of guest molecules.

  2. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides. (auth)

  3. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides.

  4. Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries.

    PubMed

    Oh, Si Hyoung; Black, Robert; Pomerantseva, Ekaterina; Lee, Jin-Hyon; Nazar, Linda F

    2012-12-01

    The lithium–O2 ‘semi-fuel’ cell based on the reversible reaction of Li and O2 to form Li2O2 can theoretically provide energy densities that exceed those of Li-ion cells by up to a factor of five. A key limitation that differentiates it from other lithium batteries is that it requires effective catalysts (or ‘promoters’) to enable oxygen reduction and evolution. Here, we report the synthesis of a novel metallic mesoporous oxide using surfactant templating that shows promising catalytic activity and results in a cathode with a high reversible capacity of 10,000 mAh g(−1) (∼1,000 mAh g(−1) with respect to the total electrode weight including the peroxide product). This oxide also has a lower charge potential for oxygen evolution from Li2O2 than pure carbon. The properties are explained by the high fraction of surface defect active sites in the metallic oxide, and its unique morphology and variable oxygen stoichiometry. This strategy for creating porous metallic oxides may pave the way to new cathode architectures for the Li–O2 cell.

  5. Spectroscopy of photonic band gaps in mesoporous one-dimensional photonic crystals based on aluminum oxide

    NASA Astrophysics Data System (ADS)

    Gorelik, V. S.; Voinov, Yu. P.; Shchavlev, V. V.; Bi, Dongxue; Shang, Guo Liang; Fei, Guang Tao

    2016-12-01

    Mesoporous one-dimensional photonic crystals based on aluminum oxide have been synthesized by electrochemical etching method. Reflection spectra of the obtained mesoporous samples in a wide spectral range that covers several band gaps are presented. Microscopic parameters of photonic crystals are calculated and corresponding reflection spectra for the first six band gaps are presented.

  6. Preparation of Mesoporous Silica Templated Metal Nanowire Films on Foamed Nickel Substrates

    SciTech Connect

    Campbell, Roger; Kenik, Edward A; Bakker, Martin; Havrilla, George; Montoya, Velma; Shamsuzzoha, Mohammed

    2006-01-01

    A method has been developed for the formation of high surface area nanowire films on planar and three-dimensional metal electrodes. These nanowire films are formed via electrodeposition into a mesoporous silica film. The mesoporous silica films are formed by a sol-gel process using Pluronic tri-block copolymers to template mesopore formation on both planar and three-dimensional metal electrodes. Surface area increases of up to 120-fold have been observed in electrodes containing a templated film when compared to the same types of electrodes without the templated film.

  7. High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

    SciTech Connect

    Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo; Soucek, Mark D.; Vogt, Bryan D.

    2015-09-16

    Micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous NixCo(3-x)(CO3)y and NixCo(3-x)O4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline NixCo(3-x)O4. The micelle templated mesopores are interconnected and provide transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g-1. Amongst the mixed-metal oxides, Ni2CoO4 exhibits the highest specific capacity of 239 mA h g-1 after galvanostatic cycling at a current density of 1 A g-1 for 10 cycles. We attribute the superior performance of Ni2CoO4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.

  8. Light-harvesting photocatalysis for water oxidation using mesoporous organosilica.

    PubMed

    Takeda, Hiroyuki; Ohashi, Masataka; Goto, Yasutomo; Ohsuna, Tetsu; Tani, Takao; Inagaki, Shinji

    2014-07-14

    An organic-based photocatalysis system for water oxidation, with visible-light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd-PMO), a visible-light harvesting antenna, was supported with [Ru(II)(bpy)3(2+)] complex (bpy = 2,2'-bipyridyl) coupled with iridium oxide (IrO(x)) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd-PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na2S2O8) to form Ru(3+) species. The Ru(3+) species extracts an electron from IrO(x) to oxidize water for oxygen production. The reaction quantum yield was 0.34 %, which was improved to 0.68 or 1.2 % by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem II, 1) light-harvesting, 2) charge separation, and 3) oxygen generation, were realized for the first time by using the light-harvesting PMO.

  9. Al-doped TiO2 mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

    NASA Astrophysics Data System (ADS)

    Zhu, Jing; Mu, Wentao; Su, Liqing; Li, Xingying; Guo, Yuyu; Zhang, Shen; Li, Zhe

    2017-04-01

    Pd catalysts supported on Al-doped TiO2 mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO2 to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction and increased the active sites of Pd oxides, enhanced the stabilized anatase TiO2, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen.

  10. Gd-Si oxide mesoporous nanoparticles with pre-formed morphology prepared from a Prussian blue analogue template.

    PubMed

    Cabrera-García, Alejandro; Vidal-Moya, Alejandro; Bernabeu, Ángela; Sánchez-González, Javier; Fernández, Eduardo; Botella, Pablo

    2015-08-21

    A novel approach to the synthesis of Gd-Si oxide mesoporous nanoparticles with a high Gd(3+) atom density and pre-formed morphology is presented. Prussian blue analogue Gd(H2O)4[Fe(CN)6], a metal organic framework that crystallizes in the orthorhombic system, is used for the first time as a sacrificial template by a reaction with soluble silicate. Simultaneous and stoichiometric condensation of gadolinium hydroxide and silica takes place, leading to dense and monodispersed nanoparticles that preserve the original shape and size of the Prussian blue analogue crystals. Then, porosity is developed by incorporation of cetyltrimethylammonium bromide under hydrothermal conditions. The obtained Gd-Si mesoporous oxide particles present a dual morphology of nanocrosses and nanorods and large surface areas.

  11. Hierarchically Macro-Mesoporous Pt/γ-Al2O3 Composite Microspheres for Efficient Formaldehyde Oxidation at Room Temperature

    PubMed Central

    Nie, Longhui; Meng, Aiyun; Yu, Jiaguo; Jaroniec, Mietek

    2013-01-01

    Room temperature catalytic oxidation by noble metals is considered to be the most promising strategy for the removal of HCHO, which is one of the major indoor air pollutants. Hierarchically macro-mesoporous structured Pt/γ-Al2O3 hollow spheres with open and accessible pores were synthesized and used for catalytic oxidative decomposition of HCHO at room temperature. The prepared composite hollow spheres showed higher catalytic activity than the conventional nanoparticle supports, which is mainly due to their hierarchical macro-mesoporous structure facilitating diffusion of reactants and products, and the high dispersion of accessible catalytic Pt nanoparticles. This work may contribute to the development of hierarchically structured materials and high-performance catalysts for indoor air purification and related catalytic processes. PMID:24225532

  12. Synthesis of Ordered Mesoporous CuO/CeO2 Composite Frameworks as Anode Catalysts for Water Oxidation

    PubMed Central

    Markoulaki, Vassiliki Ι.; Papadas, Ioannis T.; Kornarakis, Ioannis; Armatas, Gerasimos S.

    2015-01-01

    Cerium-rich metal oxide materials have recently emerged as promising candidates for the photocatalytic oxygen evolution reaction (OER). In this article, we report the synthesis of ordered mesoporous CuO/CeO2 composite frameworks with different contents of copper(II) oxide and demonstrate their activity for photocatalytic O2 production via UV-Vis light-driven oxidation of water. Mesoporous CuO/CeO2 materials have been successfully prepared by a nanocasting route, using mesoporous silica as a rigid template. X-ray diffraction, electron transmission microscopy and N2 porosimetry characterization of the as-prepared products reveal a mesoporous structure composed of parallel arranged nanorods, with a large surface area and a narrow pore size distribution. The molecular structure and optical properties of the composite materials were investigated with Raman and UV-Vis/NIR diffuse reflectance spectroscopy. Catalytic results indicated that incorporation of CuO clusters in the CeO2 lattice improved the photochemical properties. As a result, the CuO/CeO2 composite catalyst containing ~38 wt % CuO reaches a high O2 evolution rate of ~19.6 µmol·h−1 (or 392 µmol·h−1·g−1) with an apparent quantum efficiency of 17.6% at λ = 365 ± 10 nm. This OER activity compares favorably with that obtained from the non-porous CuO/CeO2 counterpart (~1.3 µmol·h−1) and pure mesoporous CeO2 (~1 µmol·h−1).

  13. Crystalline mesoporous tungsten oxide nanoplate monoliths synthesized by directed soft template method for highly sensitive NO{sub 2} gas sensor applications

    SciTech Connect

    Hoa, Nguyen Duc; Duy, Nguyen Van; Hieu, Nguyen Van

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Mesoporous WO{sub 3} nanoplate monoliths were obtained by direct templating synthesis. ► Enable effective accession of the analytic molecules for the sensor applications. ► The WO{sub 3} sensor exhibited a high performance to NO{sub 2} gas at low temperature. -- Abstract: Controllable synthesis of nanostructured metal oxide semiconductors with nanocrystalline size, porous structure, and large specific surface area is one of the key issues for effective gas sensor applications. In this study, crystalline mesoporous tungsten oxide nanoplate-like monoliths with high specific surface areas were obtained through instant direct-templating synthesis for highly sensitive nitrogen dioxide (NO{sub 2}) sensor applications. The copolymer soft template was converted into a solid carbon framework by heat treatment in an inert gas prior to calcinations in air to sustain the mesoporous structure of tungsten oxide. The multidirectional mesoporous structures of tungsten oxide with small crystalline size, large specific surface area, and superior physical characteristics enabled the rapid and effective accession of analytic gas molecules. As a result, the sensor response was enhanced and the response and recovery times were reduced, in which the mesoporous tungsten oxide based gas sensor exhibited a superior response of 21,155% to 5 ppm NO{sub 2}. In addition, the developed sensor exhibited selective detection of low NO{sub 2} concentration in ammonia and ethanol at a low temperature of approximately 150 °C.

  14. Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

    SciTech Connect

    Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho; Han, Jeong-Sik; Jeong, Byung-Hun; Park, Young-Kwon; Jeon, Jong-Ki

    2016-10-15

    Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those of the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.

  15. The oxidation of water by cerium(IV) catalysed by nanoparticulate RuO2 on mesoporous silica.

    PubMed

    King, Nicola C; Dickinson, Calum; Zhou, Wuzong; Bruce, Duncan W

    2005-03-21

    Mesoporous silicates are prepared by templating on the hexagonal (H1) mesophase of surfactant bipyridine complexes of ruthenium(II) using a true liquid-crystal templating approach. On calcination, the surfactant template is removed except for the central metal ion that is oxidised, forming nanoparticles of RuO2 that deposit within the pores. RuO2 is a known oxidation catalyst and, despite its anhydrous nature in these silicates, is found to be very active in catalyzing the oxidation of water by acidic CeIV.

  16. Comprehensive study of pore evolution, mesostructural stability, and simultaneous surface functionalization of ordered mesoporous carbon (FDU-15) by wet oxidation as a promising adsorbent.

    PubMed

    Wu, Zhangxiong; Webley, Paul A; Zhao, Dongyuan

    2010-06-15

    Fuctionalization of porous carbon materials through chemical methods orientates the development of new hybrid materials with specific functions. In this paper, a comprehensive study of pore evolution, mesostructural oxidation resistance, and simultaneous surface functionalization of ordered mesoporous carbon FDU-15 under various oxidation conditions is presented for the first time. The mesostructure and pore evolution with increasing oxidative strength are retrieved from XRD, TEM, and N(2) sorption techniques. The textural properties can be conveniently manipulated by changing the oxidation parameters, including different oxidative solution, temperature, and duration. It is revealed that the mesoporous carbon FDU-15 shows excellent structural stability under severe oxidation treatments by acidic (NH(4))(2)S(2)O(8), HNO(3), and H(2)O(2) solutions, much more stable than the mesostructural analogue CMK-3 carbon prepared by the nanocasting method. The surface area and porosity deteriorate to a large extent compared to the pristine carbon, with the micropores/small mesopores as the major contribution to the deterioration. The micropore/small mesopore can be blocked by the attached surface oxides under mild oxidation, while reopened with more carbon layer dissolution under more severe conditions. Simultaneously, high densities of surface oxygen complexes, especially carboxylic groups, can be generated. The contents and properties of the surface oxygen-containing groups are extensively studied by FTIR, TG, elemental analyses, and water and ammonia adsorption techniques. Such surface-functionalized mesoporous carbons can be used as a highly efficient adsorbent for immobilization of heavy metal ions as well as functional organic and biomolecules, with high capacities and excellent binding capabilities. Thus, we believe that the functionalized mesoporous carbon materials can be utilized as a promising solid and stable support for water treatment and organic

  17. Poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide)-templated synthesis of mesoporous alumina: effect of triblock copolymer and acid concentration.

    PubMed

    Materna, Kelly L; Grant, Stacy M; Jaroniec, Mietek

    2012-07-25

    Mesoporous alumina was synthesized via a one-pot self-assembly of aluminum isopropoxide and poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer in an acidic ethanol solution. The effects of the polymer concentration and nitric acid concentration, independently, on the adsorption properties (such as surface area, pore volume, microporosity, mesoporosity, and pore width) were studied. An increase in the specific surface area and the pore volume was seen for the samples containing a polymer/aluminum isopropoxide wt. ratio up to 0.71 and a polymer/acid wt ratio of 0.88. Titania isopropoxide was also added to the synthesis to illustrate the extension of this approach to alumina-based mixed metal oxides.

  18. Lanthanum cobaltite perovskite supported onto mesoporous zirconium dioxide: nature of active sites of VOC oxidation.

    PubMed

    Kustov, Alexander L; Tkachenko, Olga P; Kustov, Leonid M; Romanovsky, Boris V

    2011-08-01

    Novel catalytic nano-sized materials based on LaCoO(x) perovskite nanoparticles incapsulated in the mesoporous matrix of zirconia were prepared, characterized by physicochemical methods and tested in complete methanol oxidation. LaCoO(x) nanoparticles were prepared inside the mesopores of ZrO(2) by decomposition of bimetallic La-Co glycine precursor complexes. The catalysts have been studied by diffuse-reflectance FTIR-spectroscopy using such probe molecules as CO, CD(3)CN and CDCl(3) to test low-coordinated metal ions. At low temperatures of decomposition of complexes (up to 400°C), low-coordinated Co(3+) ions predominate in the LaCoO(x) nanoparticles, whereas basically Co(2+) ions are found upon increasing the decomposition temperature to 600°C. The novel nano-sized perovskite catalysts exhibit a very high catalytic activity in the abatement of volatile organic compounds present in air, like methanol and light hydrocarbons.

  19. Metal free nitrogen doped hollow mesoporous graphene-analogous spheres as effective electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Jing; Meng, Hui; Xie, Fangyan; Yuan, Xiaoli; Yu, Wendan; Lin, Worong; Ouyang, Wenpeng; Yuan, Dingsheng

    2014-01-01

    Nitrogen-doped hollow mesoporous carbon spheres has been synthesized from mesoporous silica spheres using glycine as carbon and nitrogen precursor. The wall of the spheres is composed by broken graphene. The metal free nitrogen-doped hollow mesoporous carbon spheres are proven to be active electrocatalyst for the oxygen reduction reaction in alkaline solution. A unique advantage of the nitrogen-doped hollow mesoporous carbon sphere is its methanol-tolerant property because of the absence of active metal. The catalytic activity is ascribed to the pyridinic-nitrogen formed during pyrolysis and the graphene-like structure. To the best of our knowledge this is the first report on the nitrogen-doped hollow mesoporous carbon sphere as a metal-free electrocatalyst for the oxygen reduction reaction which is an important reaction in fuel cell. The prepared mesoporous carbon material can also be used as catalyst support and find application both in the anode and cathode of fuel cell.

  20. Ordered Mesoporous Cobalt Phosphate with Crystallized Walls toward Highly Active Water Oxidation Electrocatalysts.

    PubMed

    Pramanik, Malay; Li, Cuiling; Imura, Masataka; Malgras, Victor; Kang, Yong-Mook; Yamauchi, Yusuke

    2016-04-06

    A hexagonally ordered mesoporous cobalt phosphate (CoPi) material is prepared by a facile one-pot soft-templating strategy using cetyltrimethylammonium bromide template. Because of its highly accessible surface area and crystalline framework with abundant active sites, the mesoporous CoPi shows a high catalytic activity for the oxygen evolution reaction compared to previously reported noble/transition-metal and nonmetal catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.

    PubMed

    Carlsson, Daniel O; Hua, Kai; Forsgren, Johan; Mihranyan, Albert

    2014-01-30

    TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery.

  2. Low Temperature CO oxidation over Iron Oxide Nanoparticles Decorating Internal Structures of a Mesoporous Alumina

    NASA Astrophysics Data System (ADS)

    Kim, Il Hee; Seo, Hyun Ook; Park, Eun Ji; Han, Sang Wook; Kim, Young Dok

    2017-01-01

    Using a chemical vapor deposition method with regulated sample temperatures under ambient pressure conditions, we were able to fully decorate the internal structure of a mesoporous Al2O3 bead (~1 mm in particle diameter) with iron oxide nanoparticles (with a mean lateral size of less than 1 nm). The iron oxide-decorated Al2O3 showed a high CO oxidation reactivity, even at room temperature. Very little deactivation of the CO oxidation activity was observed with increasing reaction time at ~100 °C. Additionally, this catalyst showed high CO oxidation activity, even after annealing at ~900 °C under atmospheric conditions (i.e., the structure of the catalysts could be maintained under very harsh treatment conditions). We show that our catalysts have potential for application as oxidation catalysts in industrial processes due to the simplicity of their fabrication process as well as the high and stable catalytic performance.

  3. Low Temperature CO oxidation over Iron Oxide Nanoparticles Decorating Internal Structures of a Mesoporous Alumina

    PubMed Central

    Kim, Il Hee; Seo, Hyun Ook; Park, Eun Ji; Han, Sang Wook; Kim, Young Dok

    2017-01-01

    Using a chemical vapor deposition method with regulated sample temperatures under ambient pressure conditions, we were able to fully decorate the internal structure of a mesoporous Al2O3 bead (~1 mm in particle diameter) with iron oxide nanoparticles (with a mean lateral size of less than 1 nm). The iron oxide-decorated Al2O3 showed a high CO oxidation reactivity, even at room temperature. Very little deactivation of the CO oxidation activity was observed with increasing reaction time at ~100 °C. Additionally, this catalyst showed high CO oxidation activity, even after annealing at ~900 °C under atmospheric conditions (i.e., the structure of the catalysts could be maintained under very harsh treatment conditions). We show that our catalysts have potential for application as oxidation catalysts in industrial processes due to the simplicity of their fabrication process as well as the high and stable catalytic performance. PMID:28091561

  4. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1994-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  5. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1997-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  6. Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures.

    PubMed

    Long, Jeffrey W; Logan, Michael S; Rhodes, Christopher P; Carpenter, Everett E; Stroud, Rhonda M; Rolison, Debra R

    2004-12-29

    We have developed crystalline nanoarchitectures of iron oxide that exhibit superparamagnetic behavior while still retaining the desirable bicontinuous pore-solid networks and monolithic nature of an aerogel. Iron oxide aerogels are initially produced in an X-ray-amorphous, high-surface-area form, by adapting recently established sol-gel methods using Fe(III) salts and epoxide-based proton scavengers. Controlled temperature/atmosphere treatments convert the as-prepared iron oxide aerogels into nanocrystalline forms with the inverse spinel structure. As a function of the bathing gas, treatment temperature, and treatment history, these nanocrystalline forms can be reversibly tuned to predominantly exhibit either Fe(3)O(4) (magnetite) or gamma-Fe(2)O(3) (maghemite) phases, as verified by electron microscopy, X-ray and electron diffraction, microprobe Raman spectroscopy, and magnetic analysis. Peak deconvolution of the Raman-active Fe-O bands yields valuable information on the local structure and vacancy content of the various aerogel forms, and facilitates the differentiation of Fe(3)O(4) and gamma-Fe(2)O(3) components, which are difficult to assign using only diffraction methods. These nanocrystalline, magnetic forms retain the inherent characteristics of aerogels, including high surface area (>140 m(2) g(-1)), through-connected porosity concentrated in the mesopore size range (2-50 nm), and nanoscale particle sizes (7-18 nm). On the basis of this synthetic and processing protocol, we produce multifunctional nanostructured materials with effective control of the pore-solid architecture, the nanocrystalline phase, and subsequent magnetic properties.

  7. Aerobic oxidative coupling of resveratrol and its analogues by visible light using mesoporous graphitic carbon nitride (mpg-C(3)N(4)) as a bioinspired catalyst.

    PubMed

    Song, Tao; Zhou, Bo; Peng, Guang-Wei; Zhang, Qing-Bao; Wu, Li-Zhu; Liu, Qiang; Wang, Yong

    2014-01-13

    The first aerobic oxidative coupling of resveratrol and its analogues by mesoporous graphitic carbon nitride as a bioinspired catalyst with visible light has been developed. With this method, δ-viniferin and its analogues were synthesized in moderate to high yield. The metal-free conditions, visible-light irradiation, and the ideal oxidant, molecular oxygen, make this coupling reaction environmental friendly and practical. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metallic WO2-Carbon Mesoporous Nanowires as Highly Efficient Electrocatalysts for Hydrogen Evolution Reaction.

    PubMed

    Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Liu, Dali; Zhang, Bin

    2015-06-10

    The development of electrocatalysts to generate hydrogen, with good activity and stability, is a great challenge in the fields of chemistry and energy. Here we demonstrate a "hitting three birds with one stone" method to synthesize less toxic metallic WO2-carbon mesoporous nanowires with high concentration of oxygen vacancies (OVs) via calcination of inorganic/organic WO3-ethylenediamine hybrid precursors. The products exhibit excellent performance for H2 generation: the onset overpotential is only 35 mV, the required overpotentials for 10 and 20 mA/cm(2) are 58 and 78 mV, the Tafel slope is 46 mV/decade, the exchange current density is 0.64 mA/cm(2), and the stability is over 10 h. Further studies, in combination with density functional theory, demonstrate that the unusual electronic structure and the large amount of active sites, generated by the high concentration of OVs, as well as the closely attached carbon materials, were key factors for excellent performance. Our results experimentally and theoretically establish metallic transition metal oxides (TMOs) as intriguing novel electrocatalysts for H2 generation. Such TMOs with OVs might be promising candidates for other energy storage and conversion applications.

  9. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    PubMed

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  10. Extracting metals directly from metal oxides

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

    1997-01-01

    A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones, halogenated .beta.-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process.

  11. Extracting metals directly from metal oxides

    DOEpatents

    Wai, C.M.; Smart, N.G.; Phelps, C.

    1997-02-25

    A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of {beta}-diketones, halogenated {beta}-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs.

  12. Ferroelectric BiFeO3 as an Oxide Dye in Highly Tunable Mesoporous All-Oxide Photovoltaic Heterojunctions.

    PubMed

    Wang, Lingfei; Ma, He; Chang, Lei; Ma, Chun; Yuan, Guoliang; Wang, Junling; Wu, Tom

    2017-01-01

    As potential photovoltaic materials, transition-metal oxides such as BiFeO3 (BFO) are capable of absorbing a substantial portion of solar light and incorporating ferroic orders into solar cells with enhanced performance. But the photovoltaic application of BFO has been hindered by low energy-conversion efficiency due to poor carrier transport and collection. In this work, a new approach of utilizing BFO as a light-absorbing sensitizer is developed to interface with charge-transporting TiO2 nanoparticles. This mesoporous all-oxide architecture, similar to that of dye-sensitized solar cells, can effectively facilitate the extraction of photocarriers. Under the standard AM1.5 (100 mW cm(-2) ) irradiation, the optimized cell shows an open-circuit voltage of 0.67 V, which can be enhanced to 1.0 V by tailoring the bias history. A fill factor of 55% is achieved, which is much higher than those in previous reports on BFO-based photovoltaic devices. The results provide here a new viable approach toward developing highly tunable and stable photovoltaic devices based on ferroelectric transition-metal oxides.

  13. Preparation, characterization, and electrochemical application of mesoporous copper oxide

    SciTech Connect

    Cheng, Liang; Shao, Mingwang; Chen, Dayan; Zhang, Yuzhong

    2010-02-15

    Mesoporous CuO was successfully synthesized via thermal decomposition of CuC{sub 2}O{sub 4} precursors. These products had ring-like morphology, which was made up of nanoparticles with the average diameter of 40 nm. The electrochemical experiments showed that the mesoporous CuO decreased the overvoltage of the electrode and increased electron transference in the measurement of dopamine.

  14. Synthesis and characterization of a mesoporous hydrous zirconium oxide used for arsenic removal from drinking water

    SciTech Connect

    Bortun, Anatoly; Bortun, Mila; Pardini, James; Khainakov, Sergei A.; Garcia, Jose R.

    2010-02-15

    Powder (20-50 {mu}m) mesoporous hydrous zirconium oxide was prepared from a zirconium salt granular precursor. The effect of some process parameters on product morphology, porous structure and adsorption performance has been studied. The use of hydrous zirconium oxide for selective arsenic removal from drinking water is discussed.

  15. High-activity mesoporous Pt/Ru catalysts for methanol oxidation.

    PubMed

    Franceschini, Esteban A; Bruno, Mariano M; Williams, Federico J; Viva, Federico A; Corti, Horacio R

    2013-11-13

    High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores.

  16. Synthesis and characterization of novel mesocomposites Co3O4 and CuO@OMS (ordered mesoporous silica) as active catalysts for hydrocarbon oxidation

    NASA Astrophysics Data System (ADS)

    Comănescu, Cezar

    2014-03-01

    Novel metal nanoporous transition metal oxides M x O y (Co3O4, CuO) have been synthesized by thermal decomposition of inorganic salts precursors (acetates, nitrates) impregnated into hexagonal mesoporous silica (OMS, ordered mesoporous silica) of SBA-15 type (prepared in-house) at different precursor loadings, the mesocomposites thus obtained being monitored after each impregnation-calcination step by small and wide angle powder XRD. The pore size for the ordered silica host range from 5.08 to 7.06 nm. Retention of the hexagonal silica framework has been observed in spite of the temperatures up to 500 °C. Mesoporous Co3O4 has been obtained by leaching the silica through overnight HF dissolution, which partially preserved the small-range ordering found in the parent Co3O4@OMS composite prior to leaching. Both Co3O4 ( meso) and Co3O4@SBA-15 have been tested in methane oxidation and were found to be superior to the bulk Co3O4 performance, with mesoporous Co3O4 being able to fully oxidize methane to CO2 and H2O at 350 °C, while Co3O4@OMS exhibits a lower activity with 20 % conversion at 350 °C. CuO@OMS shows the lowest activity, with only 13 % conversion at 500 °C.

  17. Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO

    NASA Astrophysics Data System (ADS)

    Liu, Changxiang; Gong, Lei; Dai, Runying; Lu, Meijuan; Sun, Tingting; Liu, Qian; Huang, Xigen; Huang, Zhong

    2017-09-01

    Mesoporous Mn-doped Co3O4 catalysts were successfully prepared via a dry soft reactive grinding method based on solid state reaction, and their catalytic performances on CO oxidation were evaluated at a high space velocity of 49,500 mL g-1 h-1. A significant promoted effect was observed once the atomic ratios of Mn/(Co+Mn) were lower than 10%, for instance, the temperature for 50% conversion decreased to about -60 °C, showing superior catalytic performance compared to the single metal oxide. Especially, the Mn-promoted Co3O4 catalyst with a Mn/(Co+Mn) molar ratio of 10% could convert 100% CO after 3000 min of time-on-steam without any deactivation at room temperature. As prepared catalysts were characterized by XRD, N2-adsorption/desorption, TEM, H2-TPR, O2-TPD and CO-titration analysis. The significant enhancement of performance for oxidation of CO over Mn-Co-O mixed oxides was associated with the high active oxygen species concentrations formed during the pretreatment in O2 atmosphere.

  18. Structural and morphological properties of mesoporous carbon coated molybdenum oxide films

    SciTech Connect

    Dayal, Saurabh Kumar, C. Sasi

    2016-05-06

    In the present study, we report the structural and morphological properties of mesoporous carbon coated molybdenum oxide films. The deposition of films was carried out in a two-step process, the first step involves deposition of molybdenum and carbon bilayer thin films using DC magnetron sputtering. In the second step the sample was ex-situ annealed in a muffle furnace at different temperatures (400°C to 600°C) and air cooled in the ambient atmosphere. The formation of the meso-porous carbon clusters on molybdenum oxide during the cooling step was investigated using FESEM and AFM techniques. The structural details were explored using XRD. The meso-porous carbon were found growing over molybdenum oxide layer as a result of segregation phenomena.

  19. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    DOE PAGES

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

    2015-10-15

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganesemore » doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

  20. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    PubMed Central

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

    2015-01-01

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface. PMID:26469151

  1. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

    2015-10-01

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C-H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100-120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140-160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C-H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.

  2. Synthesis of novel thiol-functionalized mesoporous silica nanorods and their sorbent properties on heavy metals

    NASA Astrophysics Data System (ADS)

    Chen, Xi; Cai, Qiang; Sun, Lin-Hao; Zhang, Wei; Jiang, Xing-Yu

    2012-09-01

    Novel thiol-functionalized mesoporous silica nanorods (MSNRs) were synthesized through a base co-condensation method, in which two organoalkoxysilanes, tetraethoxylsilane (TEOS) and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT), were used as silica precursors simultaneously. TESPT was firstly used for both morphology control and inner surface functionalization of mesoporous silica hybrid materials. The microstructures as well as porous character of the MSNRs were characterized by means of SEM, XRD, TEM and N2 sorption measurements. Infrared spectrum analysis and heavy metal ions (Ag+ and Cd2+) adsorption measurements were carried out to confirm the functionalized framework of MSNRs.

  3. Copper benzene tricarboxylate metal-organic framework with wide permanent mesopores stabilized by Keggin polyoxometallate ions.

    PubMed

    Wee, Lik H; Wiktor, Christian; Turner, Stuart; Vanderlinden, Willem; Janssens, Nikki; Bajpe, Sneha R; Houthoofd, Kristof; Van Tendeloo, Gustaaf; De Feyter, Steven; Kirschhock, Christine E A; Martens, Johan A

    2012-07-04

    Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal-organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu(3)(BTC)(2) (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores.

  4. Proton conductivity of naphthalene sulfonate formaldehyde resin-doped mesoporous niobium and tantalum oxide composites.

    PubMed

    Turley, Jonathan P; Romer, Frederik; Trudeau, Michel L; Dias, Marcos L; Smith, Mark E; Hanna, John V; Antonelli, David M

    2015-01-01

    Proton conductivity in a series of mesoporous niobium and tantalum metal oxide (mX2 O5 ) composites of naphthalene sulfonic acid formaldehyde resin (NSF) that are resistant to moisture loss at temperatures greater than 50 °C is reported. The investigation focuses on the effect to proton conductivity by changing pore size and metal in the mesostructure of the mX2 O5 system and thus, a series of mX2 O5 -NSF composites were synthesized with C6 , C12 , and C18 templates. These were characterized by XRD, thermogravimetric analysis, nitrogen adsorption, and scanning TEM and then studied using impedance spectroscopy to establish proton conductivity values at various temperatures ranging from 25 to 150 °C. The most promising sample displayed a conductivity of 21.96 mS cm(-1) at 100 °C, surpassing the literature value for Nafion 117 (ca. 8 mS cm(-1) ). (1) H and (13) C solid state NMR studies the mX2 O5 -NSF composites demonstrate that the oligomeric nature of the NSF is preserved while in contact with the mX2 O5 surface, thus facilitating conductivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

    PubMed Central

    Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

    2016-01-01

    Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g−1), a high mass activity (398 mA mg−1) and specific activity (0.98 mA cm−2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst. PMID:27550737

  6. Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

    2016-08-01

    Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

  7. Inhibition of a protein tyrosine phosphatase using mesoporous oxides.

    PubMed

    Kapoor, S; Girish, T S; Mandal, S S; Gopal, B; Bhattacharyya, A J

    2010-03-11

    The feasibility of utilizing mesoporous matrices of alumina and silica for the inhibition of enzymatic activity is presented here. These studies were performed on a protein tyrosine phosphatase by the name chick retinal tyrosine phosphotase-2 (CRYP-2), a protein that is identical in sequence to the human glomerular epithelial protein-1 and involved in hepatic carcinoma. The inhibition of CRYP-2 is of tremendous therapeutic importance. Inhibition of catalytic activity was examined using the sustained delivery of p-nitrocatechol sulfate (pNCS) from bare and amine functionalized mesoporous silica (MCM-48) and mesoporous alumina (Al(2)O(3)). Among the various mesoporous matrices employed, amine functionalized MCM-48 exhibited the best release of pNCS and also inhibition of CRYP-2. The maximum speed of reaction v(max) (=160 +/- 10 micromol/mnt/mg) and inhibition constant K(i) (=85.0 +/- 5.0 micromol) estimated using a competitive inhibition model were found to be very similar to inhibition activities of protein tyrosine phosphatases using other methods.

  8. Novel Photocatalytic Metal Oxides

    SciTech Connect

    Smith, Robert W.; Mei, Wai-Ning; Sabirianov, Renat; Wang, Lu

    2012-08-31

    The principal short-term objective is to develop improved solid-state photocatalysts for the decomposition of water into hydrogen gas using ultraviolet and visible solar radiation. We will pursue our objective by modeling candidate metal oxides through computer simulations followed by synthesis of promising candidates. We will characterize samples through standard experimental techniques. The long-term objective is to provide a more efficient source of hydrogen gas for fixed-site hydrogen fuel cells, particularly for energy users in remote locations.

  9. Metallic cobalt nanoparticles imbedded into ordered mesoporous carbon: A non-precious metal catalyst with excellent hydrogenation performance.

    PubMed

    Liu, Jiangyong; Wang, Zihao; Yan, Xiaodong; Jian, Panming

    2017-11-01

    Ordered mesoporous carbon (OMC)-metal composites have attracted great attention owing to their combination of high surface area, controlled pore size distribution and physicochemical properties of metals. Herein, we report the cobalt nanoparticles/ordered mesoporous carbon (CoNPs@OMC) composite prepared by a one-step carbonization/reduction process assisted by a hydrothermal pre-reaction. The CoNPs@OMC composite presents a high specific surface area of 544m(2)g(-1), and the CoNPs are uniformly imbedded or confined in the ordered mesoporous carbon matrix. When used as a non-precious metal-containing catalyst for hydrogenation reduction of p-nitrophenol and nitrobenzene, it demonstrates high efficiency and good cycling stability. Furthermore, the CoNPs@OMC composite can be directly used to catalyze the Fischer-Tropsch synthesis for the high-pressure CO hydrogenation, and presents a good catalytic selectivity for C5(+) hydrocarbons. The excellent catalytic performance of the CoNPs@OMC composite can be ascribed to synergistic effect between the high specific surface area, mesoporous structure and well-imbedded CoNPs in the carbon matrix. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Mesoporous titanium zirconium oxide nanospheres with potential for drug delivery applications.

    PubMed

    Wang, Xiaojian; Chen, Dehong; Cao, Lu; Li, Yuncang; Boyd, Ben J; Caruso, Rachel A

    2013-11-13

    Mesoporous titanium zirconium (TiZr) oxide nanospheres with variable Ti to Zr ratios were synthesized using sol-gel chemistry followed by solvothermal treatment. These oxide nanospheres exhibited similar diameters (~360 nm), high surface areas (from 237 ± 2 to 419 ± 4 m(2) g(-1)), and uniform pore diameters (~3.7 nm). Three drugs, ibuprofen, dexamethasone, and erythromycin, were loaded into the TiZr oxide nanospheres. The TiZr oxide nanospheres exhibited a high loading capacity, up to 719 mg g(-1), and sustained release profiles in phosphate buffered saline (PBS) at pH 7.4. The mesoporous TiZr oxide nanospheres also exhibited hydrolytic stability, as evidenced by the retention of the integrity of the mesostructures after drug release in PBS for 21 days.

  11. Graphene oxide wrapping on squaraine-loaded mesoporous silica nanoparticles for bioimaging.

    PubMed

    Sreejith, Sivaramapanicker; Ma, Xing; Zhao, Yanli

    2012-10-24

    Squaraine dyes were loaded inside mesoporous silica nanoparticles, and the nanoparticle surfaces were then wrapped with ultrathin graphene oxide sheets, leading to the formation of a novel hybrid material. The hybrid exhibits remarkable stability and can efficiently protect the loaded dye from nucleophilic attack. The biocompatible hybrid is noncytotoxic and presents significant potential for application in fluorescence imaging in vitro.

  12. Synthesis and catalytic properties of mesoporous, bifunctional, gallium-niobium mixed oxides.

    PubMed

    Deshmane, Chinmay A; Jasinski, Jacek B; Ratnasamy, Paul; Carreon, Moises A

    2010-09-14

    Thermally stable mesoporous Ga-Nb mixed oxides, active in both acid-catalysed and redox reactions have been synthesized via self-assembly hydrothermal assisted approach. Methyl oleate, a major component of biodiesels, undergoes double bond and skeletal isomerisation as well as dehydrogenation over these novel mesophases.

  13. Mesoporous carbon nitride-tungsten oxide composites for enhanced photocatalytic hydrogen evolution.

    PubMed

    Kailasam, Kamalakannan; Fischer, Anna; Zhang, Guigang; Zhang, Jinshui; Schwarze, Michael; Schröder, Marc; Wang, Xinchen; Schomäcker, Reinhard; Thomas, Arne

    2015-04-24

    Composites of mesoporous polymeric carbon nitride and tungsten(VI) oxide show very high photocatalytic activity for the evolution of hydrogen from water under visible light and in the presence of sacrificial electron donors. Already addition of very small amounts of WO3 yields up to a twofold increase in the efficiency when compared to bulk carbon nitrides and their composites and more notably even to the best reported mesoporous carbon nitride-based photocatalytic materials. The higher activity can be attributed to the high surface area and synergetic effect of the carbon nitrides and the WO3 resulting in improved charge separation through a photocatalytic solid-state Z-scheme mechanism.

  14. One-pot synthesis of platinum-based nanoparticles incorporated into mesoporous niobium oxide-carbon composites for fuel cell electrodes.

    PubMed

    Orilall, M Christopher; Matsumoto, Futoshi; Zhou, Qin; Sai, Hiroaki; Abruña, Héctor D; DiSalvo, Francis J; Wiesner, Ulrich

    2009-07-08

    Catalyst-electrode design is crucial for the commercialization and widespread use of polymer electrolyte membrane fuel cells. There are considerable challenges in making less expensive, more durable, and more active catalysts. Herein, we report the one-pot synthesis of Pt and Pt-Pb nanoparticles incorporated into the pores of mesoporous niobium oxide-carbon composites. The self-assembly of block copolymers with niobium oxide and metal precursors results in an ordered mesostructured hybrid. Appropriate heat treatment of this hybrid produces highly crystalline, well-ordered mesoporous niobium oxide-carbon composites with Pt (or Pt-Pb) nanoparticles incorporated into the mesopores. The in situ-generated graphitic-like carbon material prevents the collapse of the mesostructure, while the metal oxide crystallizes at high temperatures and enhances the electrical conductivity of the final material. Formic acid electrooxidation with this novel material shows 4 times higher mass activities (3.3 mA/microg) and somewhat lower onset potentials (-0.24 V vs Ag/AgCl) than the best previously reported values employing Pt-Pb intermetallic nanoparticles supported on conducting carbon (0.85 mA/microg and -0.18 V, respectively).

  15. Synthesis, characterization, and catalytic application of ordered mesoporous carbon–niobium oxide composites

    SciTech Connect

    Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling; Liu, Zhao-Tie; Dong, Wen-Sheng

    2014-11-15

    Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride as precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.

  16. Fabrication of ordered mesoporous carbon film supporting vanadium oxides for electrochemical supercapacitor

    NASA Astrophysics Data System (ADS)

    Zhao, Chunxia; Li, Junshen; Cao, Jinqiao; Chen, Wen

    2015-11-01

    Ordered mesoporous carbon film supporting vanadium oxide nanoparticles has been synthesized via ultrasound-assistant impregnation method with ordered mesoporous carbon C-FDU15 film as the host and V2O5 sol as the guest precursor. The hybrids exhibit type IV sorption isotherms with H2 hysteresis loop, indicating the well-retained characteristics of ordered mesoporous structure. The capacitance of the materials is enhanced with V2O5 loading. Particularly, the hybrids with 32.26 wt.% V2O5 loading yield an important capacitance of 128 F/g in 1 mol/L KNO3 electrolyte under a potential range from -0.6 V to 0.6 V. The improved specific capacitance of the hybrids is proposed to be the combination of the double-layer capacitance of ordered porous structure and the pseudocapacitance derived from V2O5.

  17. Mesoporous tin oxide nanospheres for a NO x in air sensor

    NASA Astrophysics Data System (ADS)

    Zhang, Haonan; Zhuo, Ming; Luo, Yazi; Chen, Yuejiao

    2017-02-01

    Mesoporous tin oxide (SnO2) with a high surface area of 147.5 m2/g has been successfully synthesized via self-assembly process, combining the driven forces of water-evaporation and molecular interactions. Scanning electron microscope, X-ray diffraction, transmission electron micrograph, Fourier transform infrared and Brunauer-Emmett-Teller were employed to analyze the morphology and crystal structure of the as-synthesized mesoporous materials. As a gas sensor, mesoporous SnO2 shows impressive performances towards NO x gas with high selectivity and stability as well as ultra high sensitivity about 94.3 to 10 ppm NO x gas at 300 °C. The best response time of the sample S-500 is about 3.4 s to 10 ppm NO x at 450°C. Project supported by the Hunan Provincial Innovation Foundation for Postgraduates (No. CX2014B133).

  18. Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

    PubMed Central

    von Graberg, Till; Hartmann, Pascal; Rein, Alexander; Gross, Silvia; Seelandt, Britta; Röger, Cornelia; Zieba, Roman; Traut, Alexander; Wark, Michael; Janek, Jürgen; Smarsly, Bernd M

    2011-01-01

    We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material. PMID:27877387

  19. Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

    NASA Astrophysics Data System (ADS)

    von Graberg, Till; Hartmann, Pascal; Rein, Alexander; Gross, Silvia; Seelandt, Britta; Röger, Cornelia; Zieba, Roman; Traut, Alexander; Wark, Michael; Janek, Jürgen; Smarsly, Bernd M.

    2011-03-01

    We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20-25 and 35-45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.

  20. Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation

    PubMed Central

    Serrà, Albert; Montiel, Manuel; Gómez, Elvira; Vallés, Elisa

    2014-01-01

    A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane’s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

  1. Synergistic removal of Pb(II), Cd(II) and humic acid by Fe3O4@mesoporous silica-graphene oxide composites.

    PubMed

    Wang, Yilong; Liang, Song; Chen, Bingdi; Guo, Fangfang; Yu, Shuili; Tang, Yulin

    2013-01-01

    The synergistic adsorption of heavy metal ions and humic acid can be very challenging. This is largely because of their competitive adsorption onto most adsorbent materials. Hierarchically structured composites containing polyethylenimine-modified magnetic mesoporous silica and graphene oxide (MMSP-GO) were here prepared to address this. Magnetic mesoporous silica microspheres were synthesized and functionalized with PEI molecules, providing many amine groups for chemical conjugation with the carboxyl groups on GO sheets and enhanced the affinity between the pollutants and the mesoporous silica. The features of the composites were characterized using TEM, SEM, TGA, DLS, and VSM measurements. Series adsorption results proved that this system was suitable for simultaneous and efficient removal of heavy metal ions and humic acid using MMSP-GO composites as adsorbents. The maximum adsorption capacities of MMSP-GO for Pb(II) and Cd (II) were 333 and 167 mg g(-1) caculated by Langmuir model, respectively. HA enhances adsorption of heavy metals by MMSP-GO composites due to their interactions in aqueous solutions. The underlying mechanism of synergistic adsorption of heavy metal ions and humic acid were discussed. MMSP-GO composites have shown promise for use as adsorbents in the simultaneous removal of heavy metals and humic acid in wastewater treatment processes.

  2. Synergistic Removal of Pb(II), Cd(II) and Humic Acid by Fe3O4@Mesoporous Silica-Graphene Oxide Composites

    PubMed Central

    Wang, Yilong; Liang, Song; Chen, Bingdi; Guo, Fangfang; Yu, Shuili; Tang, Yulin

    2013-01-01

    The synergistic adsorption of heavy metal ions and humic acid can be very challenging. This is largely because of their competitive adsorption onto most adsorbent materials. Hierarchically structured composites containing polyethylenimine-modified magnetic mesoporous silica and graphene oxide (MMSP-GO) were here prepared to address this. Magnetic mesoporous silica microspheres were synthesized and functionalized with PEI molecules, providing many amine groups for chemical conjugation with the carboxyl groups on GO sheets and enhanced the affinity between the pollutants and the mesoporous silica. The features of the composites were characterized using TEM, SEM, TGA, DLS, and VSM measurements. Series adsorption results proved that this system was suitable for simultaneous and efficient removal of heavy metal ions and humic acid using MMSP-GO composites as adsorbents. The maximum adsorption capacities of MMSP-GO for Pb(II) and Cd (II) were 333 and 167 mg g−1 caculated by Langmuir model, respectively. HA enhances adsorption of heavy metals by MMSP-GO composites due to their interactions in aqueous solutions. The underlying mechanism of synergistic adsorption of heavy metal ions and humic acid were discussed. MMSP-GO composites have shown promise for use as adsorbents in the simultaneous removal of heavy metals and humic acid in wastewater treatment processes. PMID:23776514

  3. Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors.

    PubMed

    Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F; Su, Wu

    2015-01-14

    Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m(2) g(-1)). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.

  4. Mesoporous SnO2-coated metal nanoparticles with enhanced catalytic efficiency.

    PubMed

    Zhou, Na; Polavarapu, Lakshminarayana; Wang, Qing; Xu, Qing-Hua

    2015-03-04

    Aggregation of plasmonic nanoparticles under harsh conditions has been one of the major obstacles to their potential applications. Here we present the preparation of uniform mesoporous SnO2 shell coated Au nanospheres, Au nanorods and Au/Ag core-shell nanorods and their applications in molecular sensing and catalysis. In these nanostructures, the mesoporous SnO2 shell stabilizes the metal nanoparticle and allows the metal core to be exposed to the surrounding environment for various applications at the same time. These nanostructures display high refractive index sensitivity, which makes them promising materials for LSPR based molecular sensing. Applications of these materials as catalysts for reduction of 4-nitrophenol by NaBH4 have also been demonstrated. Both uncoated and SnO2-coated anisotropic Au and Au/Ag nanorods were found to display significantly better catalytic efficiency compared to the corresponding spherical Au nanoparticles. Catalytic activities of different metal nanoparticles were significantly enhanced by 4-6 times upon coating with the mesoporous SnO2 shell. The enhanced catalytic activity of metal nanoparticles upon SnO2 coating was attributed to charge-redistribution between noble metal and SnO2 that disperses the electrons to a large area and prolonged electron lifetime in SnO2-coated metal nanoparticles. The charge transfer mechanism of enhanced catalytic efficiency for SnO2-coated metal nanoparticles has been further demonstrated by photochemical reduction of silver ions on the outer surface of these NPs. These metal/semiconductor core-shell nanomaterials are potentially useful for various applications such as molecular sensing and catalysis.

  5. Fabrication of Co3O4 mesoporous thin films by using cobalt/chitosan precursor on fluorine-doped tin oxide glass

    NASA Astrophysics Data System (ADS)

    Yang, Hui-Chia; Tsai, Jung-Che

    2017-06-01

    For the development of high-performance and low-cost electrode materials, many alternative materials have been fabricated by various groups. Among these materials, Co3O4 has been demonstrated to be a promising candidate for pseudocapacitors because of its low potential environmental pollution, low cost, and extremely high theoretical specific capacitance. Chitosan, a linear polysaccharide produced by the deacetylation of chitin, is a nontoxic, tissue-compatible polymeric biomaterial. It is usually used to eliminate or filter the heavy metals in wastewater. That is, chitosan can act as a deliverer of metal ions and a nanostructure constructer of metals (or metal oxides). In this study, a facile approach is developed to synthesize mesoporous cobalt oxide thin films on fluorine-doped tin oxide (FTO)-coated glass with environmentally friendly chitosan, which chelates cobalt ions.

  6. Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors

    NASA Astrophysics Data System (ADS)

    Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F.; Su, Wu

    2014-12-01

    Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi

  7. Method of producing homogeneous mixed metal oxides and metal-metal oxide mixtures

    DOEpatents

    Quinby, Thomas C.

    1978-01-01

    Metal powders, metal oxide powders, and mixtures thereof of controlled particle size are provided by reacting an aqueous solution containing dissolved metal values with excess urea. Upon heating, urea reacts with water from the solution leaving a molten urea solution containing the metal values. The molten urea solution is heated to above about 180.degree. C. whereupon metal values precipitate homogeneously as a powder. The powder is reduced to metal or calcined to form oxide particles. One or more metal oxides in a mixture can be selectively reduced to produce metal particles or a mixture of metal and metal oxide particles.

  8. Transparent metal oxide nanowire transistors

    NASA Astrophysics Data System (ADS)

    Chen, Di; Liu, Zhe; Liang, Bo; Wang, Xianfu; Shen, Guozhen

    2012-05-01

    With the features of high mobility, a high electric on/off ratio and excellent transparency, metal oxide nanowires are excellent candidates for transparent thin-film transistors, which is one of the key technologies to realize transparent electronics. This article provides a comprehensive review of the state-of-the-art research activities that focus on transparent metal oxide nanowire transistors. It begins with the brief introduction to the synthetic methods for high quality metal oxide nanowires, and the typical nanowire transfer and printing techniques with emphasis on the simple contact printing methodology. High performance transparent transistors built on both single nanowires and nanowire thin films are then highlighted. The final section deals with the applications of transparent metal oxide nanowire transistors in the field of transparent displays and concludes with an outlook on the current perspectives and future directions of transparent metal oxide nanowire transistors.

  9. Transparent metal oxide nanowire transistors.

    PubMed

    Chen, Di; Liu, Zhe; Liang, Bo; Wang, Xianfu; Shen, Guozhen

    2012-05-21

    With the features of high mobility, a high electric on/off ratio and excellent transparency, metal oxide nanowires are excellent candidates for transparent thin-film transistors, which is one of the key technologies to realize transparent electronics. This article provides a comprehensive review of the state-of-the-art research activities that focus on transparent metal oxide nanowire transistors. It begins with the brief introduction to the synthetic methods for high quality metal oxide nanowires, and the typical nanowire transfer and printing techniques with emphasis on the simple contact printing methodology. High performance transparent transistors built on both single nanowires and nanowire thin films are then highlighted. The final section deals with the applications of transparent metal oxide nanowire transistors in the field of transparent displays and concludes with an outlook on the current perspectives and future directions of transparent metal oxide nanowire transistors.

  10. Excellent performance of Pt-C/TiO2 for methanol oxidation: Contribution of mesopores and partially coated carbon

    NASA Astrophysics Data System (ADS)

    Wu, Xinbing; Zhuang, Wei; Lu, Linghong; Li, Licheng; Zhu, Jiahua; Mu, Liwen; Li, Wei; Zhu, Yudan; Lu, Xiaohua

    2017-12-01

    Partial deposition of carbon onto mesoporous TiO2 (C/TiO2) were prepared as supporting substrate for Pt catalyst development. Carbon deposition is achieved by in-situ carbonization of furfuryl alcohol. The hybrid catalysts were characterized by XRD, Raman, SEM and TEM and exhibited outstanding catalytic activity and stability in methanol oxidation reaction. The heterogeneous carbon coated on mesoporous TiO2 fibers provided excellent electrical conductivity and strong interfacial interaction between TiO2 support and Pt metal nanoparticles. Methanol oxidation reaction results showed that the activity of Pt-C/TiO2 is 3.0 and 1.5 times higher than that of Pt-TiO2 and Pt-C, respectively. In addition, the Pt-C/TiO2 exhibited a 6.7 times enhanced stability compared with Pt-C after 2000 cycles. The synergistic effect of C/TiO2 is responsible for the enhanced activity of Pt-C/TiO2, and its excellent durability could be ascribed to the strong interfacial interaction between Pt nanoparticles and C/TiO2 support.

  11. Mesoporous cerium oxide nanospheres for the visible-light driven photocatalytic degradation of dyes

    PubMed Central

    Chen, Shi; Ng, Chin Fan; Huan, Cheng Hon Alfred

    2014-01-01

    Summary A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species. PMID:24991486

  12. Effect of Mesoporous Nano Water Reservoir on MR Relaxivity.

    PubMed

    Sharmiladevi, Palani; Haribabu, Viswanathan; Girigoswami, Koyeli; Sulaiman Farook, Abubacker; Girigoswami, Agnishwar

    2017-09-11

    In the present work, an attempt was made to engineer a mesoporous silica coated magnetic nanoparticles (MNF@mSiO2) for twin mode contrast in magnetic resonance imaging (MRI) with reduced toxicity. Superparamagnetic manganese ferrite nanoparticles were synthesized with variable mesoporous silica shell thickness to control the water molecules interacting with metal oxide core. 178 nm was the optimum hydrodynamic diameter of mesoporous ferrite core-shell nanoparticles that showed maximum longitudinal relaxation time (T1) and transverse relaxation time (T2) in MRI due to the storage of water molecules in mesoporous silica coating. Besides the major role of mesoporous silica in controlling relaxivity, mesoporous silica shell also reduces the toxicity and enhances the bioavailability of superparamagnetic manganese ferrite nanoparticles. The in vitro toxicity assessment using HepG2 liver carcinoma cells shows that the mesoporous silica coating over ferrite nanoparticles could exert less toxicity compared to the uncoated particle.

  13. Selective adsorption of arsenate and the reversible structure transformation of the mesoporous metal-organic framework MIL-100(Fe).

    PubMed

    Cai, Jianhua; Wang, Xueyun; Zhou, Yue; Jiang, Li; Wang, Chunru

    2016-04-28

    Here we describe a highly porous metal-organic framework MIL-100(Fe), which is initially used as an arsenate adsorbent in water. An appropriate mesoporous size allows AsO4(3-) to enter unrestrained and then be captured successfully, furthermore resulting in the damage of long-range order of uniform mesopores. Moreover, the porous framework could also make AsO4(3-) be reversibly desorbed without structural changes and the long-range order of mesopores be recovered again.

  14. 3-D periodic mesoporous nickel oxide for nonenzymatic uric acid sensors with improved sensitivity

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Cao, Yang; Chen, Yong; Zhou, Yang; Huang, Qingyou

    2015-12-01

    3-D periodic mesoporous nickel oxide (NiO) particles with crystalline walls have been synthesized through the microwave-assisted hard template route toward the KIT-6 silica. It was investigated as a nonenzymatic amperometric sensor for the detection of uric acid. 3-D periodic nickel oxide matrix has been obtained by the hard template route from the KIT-6 silica template. The crystalline nickel oxide belonged to the Ia3d space group, and its structure was characterized by X-ray diffraction (XRD), N2 adsorption-desorption, and transmission electron microscopy (TEM). The analysis results showed that the microwave-assisted mesoporous NiO materials were more appropriate to be electrochemical sensors than the traditional mesoporous NiO. Cyclic voltammetry (CV) revealed that 3-D periodic NiO exhibited a direct electrocatalytic activity for the oxidation of uric acid in sodium hydroxide solution. The enzyme-less amperometric sensor used in the detection of uric acid with detection limit of 0.005 μM (S/N = 3) over wide linear detection ranges up to 0.374 mM and with a high sensitivity of 756.26 μA mM-1 cm-2, and a possible mechanism was also given in the paper.

  15. Thin film hydrous metal oxide catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  16. A red metallic oxide photocatalyst

    NASA Astrophysics Data System (ADS)

    Xu, Xiaoxiang; Randorn, Chamnan; Efstathiou, Paraskevi; Irvine, John T. S.

    2012-07-01

    Light absorption across the bandgap in semiconductors is exploited in many important applications such as photovoltaics, light emitting diodes and photocatalytic conversion. Metals differ from semiconductors in that there is no energy gap separating occupied and unoccupied levels; however, it is still possible to excite electrons between bands. This is evidenced by materials with metallic properties that are also strongly coloured. An important question is whether such coloured metals could be used in light harvesting or similar applications. The high conductivity of a metal would preclude sufficient electric field being available to separate photocarriers; however, the high carrier mobility in a metal might also facilitate kinetic charge separation. Here we clearly demonstrate for the first time the use of a red metallic oxide, Sr1-xNbO3 as an effective photocatalyst. The material has been used under visible light to photocatalyse the oxidation of methylene blue and both the oxidation and reduction of water assisted by appropriate sacrificial elements.

  17. Ionic liquid-mediated synthesis of meso-scale porous lanthanum-transition-metal perovskites with high CO oxidation performance

    SciTech Connect

    Lu, Hanfeng; Zhang, Pengfei; Qiao, Zhen-An; Zhang, Jinshui; Zhu, Huiyuan; Chen, Jihua; Chen, Yinfei; Dai, Sheng

    2015-01-01

    Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO3) are synthesized through use of ionic liquids. The resultant samples demonstrate a rather high activity for CO oxidation, by taking advantage of unique nanostructure-derived benefits. This synthesis strategy opens up a new opportunity for preparing functional mesoporous complex oxides of various compositions.

  18. Ionic liquid-mediated synthesis of meso-scale porous lanthanum-transition-metal perovskites with high CO oxidation performance

    DOE PAGES

    Lu, Hanfeng; Zhang, Pengfei; Qiao, Zhen-An; ...

    2015-01-01

    Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO3) are synthesized through use of ionic liquids. The resultant samples demonstrate a rather high activity for CO oxidation, by taking advantage of unique nanostructure-derived benefits. This synthesis strategy opens up a new opportunity for preparing functional mesoporous complex oxides of various compositions.

  19. Mesoporous Nb and Ta Oxides: Synthesis, Characterization and Applications in Heterogeneous Acid Catalysis

    NASA Astrophysics Data System (ADS)

    Rao, Yuxiang Tony

    In this work, a series of mesoporous Niobium and Tantalum oxides with different pore sizes (C6, C12, C18 , ranging from 12A to 30 A) were synthesized using the ligand-assisted templating approach and investigated for their activities in a wide range of catalytic applications including benzylation, alkylation and isomerization. The as-synthesized mesoporous materials were characterized by nitrogen adsorption, powder X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), and solid-state Nuclear magnetic resonance (NMR) techniques. In order to probe into the structural and coordination geometry of mesoporous Nb oxide and in efforts to make meaningful comparisons of mesoporous niobia prepared by the amine-templating method with the corresponding bulk sol-gel prepared Nb2O5 phase, 17O magic-angle-spinning solid-state NMR studies were conducted. The results showed a very high local order in the mesoporous sample. The oxygen atoms are coordinated only as ONb 2 in contrast with bulk phases in which the oxygen atoms are always present in a mixture of ONb2 and ONb3 coordination environments. To enhance their surface acidities and thus improve their performance as solid acid catalysts in the acid-catalyzed reactions mentioned above, pure mesoporous Nb and Ta oxides were further treated with 1M sulfuric acid or phosphoric acid. Their surface acidities before and after acid treatment were measured by Fourier transform infraRed (FT IR), amine titration and temperature programmed desorption of ammonia (NH3-TPD). Results obtained in this study showed that sulfated mesoporous Nb and Ta oxides materials possess relative high surface areas (up to 612 m 2/g) and amorphous wormhole structure. These mesoporous structures are thus quite stable to acid treatment. It was also found that Bronsted (1540 cm-1) and Lewis (1450 cm-1) acid sites coexist in a roughly 50:50 mixture

  20. Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Chen, Yun; Gerdes, Kirk; Song, Xueyan

    2016-09-01

    Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1‑xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C.

  1. Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

    PubMed Central

    Chen, Yun; Gerdes, Kirk; Song, Xueyan

    2016-01-01

    Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1−xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C. PMID:27605121

  2. Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells.

    PubMed

    Chen, Yun; Gerdes, Kirk; Song, Xueyan

    2016-09-08

    Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1-xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650-800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5-1.7 operated at 0.8 V at 750 °C.

  3. Metal Atom Oxidation Laser

    DTIC Science & Technology

    1976-09-01

    mixtures of dusts of rare earth fluorides and oxides administered intratracheally and by inhalation. Some of the test animals (guinea pigs) died of...neodymium and cerium oxides were also made. These dusts were administered intratracheally to white rats. The investigation showed that these oxides...but milder. Cerium oxide was the least damaging of the three. With regard to the" aerosols of the oxides of yttrium, neodymium and other rare earth

  4. Catalytically active Au-O(OH)x- species stabilized by alkali ions on zeolites and mesoporous oxides

    SciTech Connect

    Yang, Ming; Li, Sha; Wang, Yuan; Herron, Jeffrey A.; Xu, Ye; Allard, Lawrence F.; Lee, Sungsik; Huang, Jun; Mavrikakis, Manos; Flytzani-Stephanopoulos, Maria

    2014-11-27

    Here we report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (<200°C) water-gas shift (WGS) reaction. Unexpectedly, gold is thus similar to platinum in creating –O linkages with more than eight alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold active site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.

  5. Catalytically active Au-O(OH)x- species stabilized by alkali ions on zeolites and mesoporous oxides

    DOE PAGES

    Yang, Ming; Li, Sha; Wang, Yuan; ...

    2014-11-27

    Here we report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (<200°C) water-gas shift (WGS) reaction. Unexpectedly, gold is thus similar to platinum in creating –O linkages with more than eight alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold active site.more » This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.« less

  6. Catalytically active Au-O(OH)x- species stabilized by alkali ions on zeolites and mesoporous oxides

    SciTech Connect

    Lee, Sungsik

    2014-12-19

    We report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (< 200°C) water-gas shift (WGS) reaction. Unexpectedly, gold is thus similar to platinum in creating –O and –OH linkages with more than eight alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports; apparently all sharing a common, similarly structured gold active site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel processing reactions.

  7. Mesoporous magnetic secondary nanostructures as versatile adsorbent for efficient scavenging of heavy metals

    PubMed Central

    Bhattacharya, Kakoli; Parasar, Devaborniny; Mondal, Bholanath; Deb, Pritam

    2015-01-01

    Porous magnetic secondary nanostructures exhibit high surface area because of the presence of plentiful interparticle spaces or pores. Mesoporous Fe3O4 secondary nanostructures (MFSNs) have been studied here as versatile adsorbent for heavy metal scavenging. The porosity combined with magnetic functionality of the secondary nanostructures has facilitated efficient heavy metal (As, Cu and Cd) remediation from water solution within a short period of contact time. It is because of the larger surface area of MFSNs due to the porous network in addition to primary nanostructures which provides abundant adsorption sites facilitating high adsorption of the heavy metal ions. The brilliance of adsorption property of MFSNs has been realized through comprehensive adsorption studies and detailed kinetics. Due to their larger dimension, MFSNs help in overcoming the Brownian motion which facilitates easy separation of the metal ion sorbed secondary nanostructures and also do not get drained out during filtration, thus providing pure water. PMID:26602613

  8. Mesoporous magnetic secondary nanostructures as versatile adsorbent for efficient scavenging of heavy metals

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Kakoli; Parasar, Devaborniny; Mondal, Bholanath; Deb, Pritam

    2015-11-01

    Porous magnetic secondary nanostructures exhibit high surface area because of the presence of plentiful interparticle spaces or pores. Mesoporous Fe3O4 secondary nanostructures (MFSNs) have been studied here as versatile adsorbent for heavy metal scavenging. The porosity combined with magnetic functionality of the secondary nanostructures has facilitated efficient heavy metal (As, Cu and Cd) remediation from water solution within a short period of contact time. It is because of the larger surface area of MFSNs due to the porous network in addition to primary nanostructures which provides abundant adsorption sites facilitating high adsorption of the heavy metal ions. The brilliance of adsorption property of MFSNs has been realized through comprehensive adsorption studies and detailed kinetics. Due to their larger dimension, MFSNs help in overcoming the Brownian motion which facilitates easy separation of the metal ion sorbed secondary nanostructures and also do not get drained out during filtration, thus providing pure water.

  9. Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline

    SciTech Connect

    Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon; Grudzien, Rafal M.; Fryxell, Glen E.

    2009-11-01

    Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30Å, and contained as much as 8.2 weight percent N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl4-2 and H2VO4-1. 1,10-phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to a pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion exchange resin or activated carbon.

  10. Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline☆

    PubMed Central

    Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon; Grudzien, Rafal M.; Fryxell, Glen E.

    2012-01-01

    Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30 Å, and contained as much as 8.2 wt% N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl42- and H2VO41-. 1,10-Phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to a pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion-exchange resin or activated carbon. PMID:23762013

  11. Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework.

    PubMed

    Baldwin, Luke A; Crowe, Jonathan W; Pyles, David A; McGrier, Psaras L

    2016-11-23

    Constructing metalated three-dimensional (3D) covalent organic frameworks is a challenging synthetic task. Herein, we report the synthesis and characterization of a highly porous (SABET = 5083 m(2) g(-1)) 3D COF with a record low density (0.13 g cm(-3)) containing π-electron conjugated dehydrobenzoannulene (DBA) units. Metalation of DBA-3D-COF 1 with Ni to produce Ni-DBA-3D-COF results in a minimal reduction in the surface area (SABET = 4763 m(2) g(-1)) of the material due to the incorporation of the metal within the cavity of the DBA units, and retention of crystallinity. Both 3D DBA-COFs also display great uptake capacities for ethane and ethylene gas.

  12. Metal-silicate catalysts: Single site, mesoporous systems without templates

    SciTech Connect

    Barnes, Craig E.; Sharp, Katherine; Albert, Austin A; Abbott, Joshua; Peretich, Michael E; Fulvio, Pasquale; Ciesielski, Peter N.; Donohoe, Bryon S.

    2015-06-01

    The textural properties of a family of silicate and mixed metal-silicate materials prepared by a nonaqueous sol-gel reaction involving the cubic silicate Si8O20(SnMe3)8 and metal chlorides MCl4 (M = Si, Ti, Zr) cross-linking reagents are described. Nitrogen adsorption isotherm data is presented and surface area and pore size distribution analyses for several examples of these materials are developed and correlated with the ratio of cross-linking reagent and the cubic silicate building block at the time of synthesis. Significant surface area and pore size distributions that shift to higher pore diameters are observed as the ratio of cross-linking reagent-to-cubic building block increases. A simple strategy for simultaneously controlling the porosity of these matrices while homogeneously dispersing identical metal centers on their surfaces for next generation catalysts is described.

  13. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

  14. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  15. Metal oxide nanostructures with hierarchical morphology

    DOEpatents

    Ren, Zhifeng; Lao, Jing Yu; Banerjee, Debasish

    2007-11-13

    The present invention relates generally to metal oxide materials with varied symmetrical nanostructure morphologies. In particular, the present invention provides metal oxide materials comprising one or more metallic oxides with three-dimensionally ordered nanostructural morphologies, including hierarchical morphologies. The present invention also provides methods for producing such metal oxide materials.

  16. Photoionization of oxidized metal clusters

    SciTech Connect

    Dao, P.D.; Peterson, K.I.; Castleman, A.W. Jr.

    1984-01-01

    Oxidized metal clusters (Na/sub x/O and K/sub x/O for 2< or =x< or =4) were formed in a gas phase reaction between metal clusters and an oxidizing gas using a double expansion technique. Their appearance potentials were measured using a molecular beam-photoionization mass spectrometer system. These first photoionization data for oxidized clusters provide information on trends of ionization potentials as a function of the degree of aggregation. The ionization potentials do not differ greatly from the analogous metallic species, but in the case of the sodium tetramer the value does fall below that of the bare metal cluster. This finding is in accord with what has been observed as an influence of impurities on the work function of the bulk sodium. The results are also of interest concerning questions of octet rule violations and hypervalency.

  17. METAL OXIDE NANOPARTICLES

    SciTech Connect

    FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

    2007-10-01

    This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

  18. Single-step preparation of mesoporous, anatase-based titanium-vanadium oxide and its application.

    PubMed

    Shyue, Jing-Jong; De Guire, Mark R

    2005-09-14

    Mesoporous solid solutions of anatase-based titanium-vanadium oxides were synthesized from aqueous solutions. The V/Ti ratio was determined by the composition of the deposition solution, while the morphology and nanoscale porosity were controlled using micelles of the surfactants cetyltrimethylammonium bromide (CTAB), or hexadecylamine (HDA). The use of CTAB resulted in mesoporous powders, whereas HDA yielded clusters of nanotubes. As compared to materials of the same composition made without the use of a surfactant, the catalyst made with CTAB had 50% higher catalytic activity, and that made with HDA had 70% higher activity. As compared to titania-supported vanadia catalysts with equivalent vanadium loading and synthesized using wet impregnation, the co-deposited materials exhibited significantly higher (up to 3.8x) catalytic activity.

  19. Nitrogen and fluorine dual-doped mesoporous graphene: a high-performance metal-free ORR electrocatalyst with a super-low HO2(-) yield.

    PubMed

    Jiang, Shu; Sun, Yujing; Dai, Haichao; Hu, Jingting; Ni, Pengjuan; Wang, Yilin; Li, Zhen; Li, Zhuang

    2015-06-28

    In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells.

  20. A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores.

    SciTech Connect

    Feng, Dawei; Wang, Kecheng; Su, Jie; Liu, Tian-Fu; Park, Jihye; Wei, Zhangwen; Bosch, Mathieu; Yakovenko, Andrey; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-02

    Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8nm and the highest pore volume of 2.8cm(3)g(-1) among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization

  1. Process for fabrication of metal oxide films

    SciTech Connect

    Tracy, C.E.; Benson, D.; Svensson, S.

    1990-07-17

    This invention is comprised of a method of fabricating metal oxide films from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of metal oxides, e.g. electro-optically active transition metal oxides, at a high deposition rate. The presence of hydrogen during the plasma reaction enhances the deposition rate of the metal oxide. Various types of metal oxide films can be produced.

  2. Synthesis, characterization and catalytic application of nanoscale metal and metal oxide heterogeneous catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Xue

    Nanoscale metals or metal oxides with high surface area to volume ratios have been widely used as catalysts for various chemical reactions. A major challenge to utilize metal nanocatalysts commercially is their tendency to sinter under working reaction conditions. To overcome this, much research is being done to anchor metal nanocatalysts on various supports to prevent their agglomeration. Mesoporous silica, SBA-15 is an attractive support material candidate because of its high surface area, stable structure and chemical inertness. Scientists have anchored metal nanocatalysts onto the pore of SBA-15 and observed some improvement in the stability. However, the interactions between the nanocatalysts and SBA-15 are relatively weak and sintering still occurs resulting in a loss of activity. In order to impart enhanced robustness, a new type of stable metal/SBA-15 nanocomposite has been prepared by intercalating metal nanoparticles into the walls of mesoporous silica SBA-15 by a unique synthetic strategy using metal coordinating agents such as bis[3-(triethoxysilyl) propyl]-tetrasulfide (TESPTS). In this dissertation, systemic research on the preparation parameters and extension to other metals will be presented. The structure changes caused by addition of TESPTS to the preparation of mesoporous silica were investigated. The relationship between increasing amounts of TESPTS and the structural change was obtained. Afterwards, a new type of PdMS catalyst with Pd intercalated in the walls of SBA-15 was synthesized for the first time using a modified preparation pathway. These materials were characterized by N2 physisorption, X-ray diffraction, transmission electron microscopy and inductively coupled plasma. The PdMS system was utilized as an active and robust catalyst for Heck reactions. Notably, after the catalytic reaction, the PdMS catalysts maintained its reactivity and size without undergoing any agglomeration due to the stable nanocomposite structure. Carbon

  3. SINTERING METAL OXIDES

    DOEpatents

    Roake, W.E.

    1960-09-13

    A process is given for producing uranium dioxide material of great density by preparing a compacted mixture of uranium dioxide and from 1 to 3 wt.% of calcium hydride, heating the mixture to at least 675 deg C for decomposition of the hydride and then for sintering, preferably in a vacuum, at from 1550 to 2000 deg C. Calcium metal is formed, some uranium is reduced by the calcium to the metal and a product of high density is obtained.

  4. Methods for synthesizing metal oxide nanowires

    DOEpatents

    Sunkara, Mahendra Kumar; Kumar, Vivekanand; Kim, Jeong H.; Clark, Ezra Lee

    2016-08-09

    A method of synthesizing a metal oxide nanowire includes the steps of: combining an amount of a transition metal or a transition metal oxide with an amount of an alkali metal compound to produce a mixture; activating a plasma discharge reactor to create a plasma discharge; exposing the mixture to the plasma discharge for a first predetermined time period such that transition metal oxide nanowires are formed; contacting the transition metal oxide nanowires with an acid solution such that an alkali metal ion is exchanged for a hydrogen ion on each of the transition metal oxide nanowires; and exposing the transition metal oxide nanowires to the plasma discharge for a second predetermined time period to thermally anneal the transition metal oxide nanowires. Transition metal oxide nanowires produced using the synthesis methods described herein are also provided.

  5. A General Method for Constructing Two-Dimensional Layered Mesoporous Mono- and Binary-Transition-Metal Nitride/Graphene as an Ultra-Efficient Support to Enhance Its Catalytic Activity and Durability for Electrocatalytic Application.

    PubMed

    Liu, Baocang; Huo, Lili; Si, Rui; Liu, Jian; Zhang, Jun

    2016-07-27

    We constructed a series of two-dimensional (2D) layered mesoporous mono- and binary-transition-metal nitride/graphene nanocomposites (TMN/G, TM = Ti, Cr, W, Mo, TiCr, TiW, and TiMo) via an efficient and versatile nanocasting strategy for the first time. The 2D layered mesoporous TMN/G is constituted of small TMN nanoparticles composited with graphene nanosheets and has a large surface area with high porosity. Through decoration with well-dispersed Pt nanoparticles, 2D layered mesoporous Pt/TMN/G catalysts can be obtained that display excellent catalytic activity and stability for methanol electro-oxidation reactions (MOR) and oxygen reduction reactions (ORR) in both acidic and alkaline media. The 2D layered mesoporous binary-Pt/TMN/G catalysts possess catalytic activity superior to that of mono-Pt/TMN/G, graphene free Pt/TMN, Pt/G, and Pt/C catalysts. Encouragingly, the 2D layered mesoporous Pt/Ti0.5Cr0.5N/G catalyst exhibits the best electrocatalytic performance for both MOR and ORR. The outstanding electrocatalytic performance of the Pt/Ti0.5Cr0.5N/G catalyst is rooted in its large surface area, high porosity, strong interaction among Pt, Ti0.5Cr0.5N, and graphene, an excellent electron transfer property facilitated by N-doped graphene, and the small size of Pt and Ti0.5Cr0.5N nanocrystals. The outstanding catalytic performance provides the 2D layered mesoporous Pt/Ti0.5Cr0.5N/G catalyst with a wide range of application prospects in direct methanol fuel cells in both acidic and alkaline media. The synthetic method may be available for constructing other 2D layered mesoporous metal nitrides, carbides, and phosphides.

  6. Generation of metal, metal oxide and metal-metal oxide powders by spray pyrolysis for microelectronic thick film applications

    NASA Astrophysics Data System (ADS)

    Majumdar, Diptarka

    Materials in powdered form have wide ranging applications. In thick film microelectronics, powders are dispersed in organic liquids to form pastes which are screen printed on ceramic substrates and fired to fabricate active and passive electronic devices. The functional phase is a metal powder in conductive pastes, a metal or conductive metal oxide powder in resistive pastes and a ceramic powder in dielectric pastes. Particulate additives such as glasses and metal oxides in pastes promote adhesion of conductor lines to the substrate, minimize shrinkage mismatch during cofiring of conductors and dielectrics and facilitate densification of the functional phase during firing. This dissertation focuses on the generation of metal, metal oxide and metal-metal oxide powders by spray pyrolysis for microelectronic applications. The important results of this work are outlined below. (1) This work has demonstrated the ability to synthesize phase-pure, micron-sized, spherical, unagglomerated metal (gold) and metal oxide (copper (I) oxide) particles by spray pyrolysis. (2) It has extended the versatility of spray pyrolysis as a powdermaking technique to include the synthesis of metal-metal oxide composite particles. Such particles have been generated for both wetting (silver-copper (II) oxide) and poorly wetting (silver-silica) metal-metal oxide pairs. (3) The sintering of thick films of the metal-metal oxide particles has indicated the possibility of retarding the sintering kinetics of silver by using composite particles of the metal with relatively refractory metal oxides.

  7. Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

    PubMed

    Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

    2000-12-01

    Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active

  8. Lithium metal reduction of plutonium oxide to produce plutonium metal

    DOEpatents

    Coops, Melvin S.

    1992-01-01

    A method is described for the chemical reduction of plutonium oxides to plutonium metal by the use of pure lithium metal. Lithium metal is used to reduce plutonium oxide to alpha plutonium metal (alpha-Pu). The lithium oxide by-product is reclaimed by sublimation and converted to the chloride salt, and after electrolysis, is removed as lithium metal. Zinc may be used as a solvent metal to improve thermodynamics of the reduction reaction at lower temperatures. Lithium metal reduction enables plutonium oxide reduction without the production of huge quantities of CaO--CaCl.sub.2 residues normally produced in conventional direct oxide reduction processes.

  9. Platinum/mesoporous WO3 as a carbon-free electrocatalyst with enhanced electrochemical activity for methanol oxidation.

    PubMed

    Cui, Xiangzhi; Shi, Jianlin; Chen, Hangrong; Zhang, Lingxia; Guo, Limin; Gao, Jianhua; Li, Jingbo

    2008-09-25

    A new type of carbon-free electrode catalyst, Pt/mesoporous WO3 composite, has been prepared and its electrochemical activity for methanol oxidation has been investigated. The mesoporous tungsten trioxide support was synthesized by a replicating route and the mesoporous composties with Pt loaded were characterized by using X-ray diffraction (XRD), nitrogen sorption, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) techniques. Cyclic voltammetry (CV), line scan voltammetry (LSV) and chronoamperometry (CA) were adopted to characterize the electrochemical activities of the composites. The mesoporous WO3 showed high surface area, ordered pore structure, and nanosized wall thickness of about 6-7 nm. When a certain amount of Pt nanoparticles were dispersed in the pore structure of mesoporous WO3, the resultant mesostructured Pt/WO3 composites exhibit high electro-catalytic activity toward methanol oxidation. The overall electro-catalytic activities of 20 wt % Pt/WO3 composites are significantly higher than that of commercial 20 wt % Pt/C catalyst and are comparable to the 20 wt % PtRu/C catalyst in the potential region of 0.5-0.7 V. The enhanced electro-catalytic activity is attributed to be resulted from the assistant catalytic effect and the mesoporous structure of WO3 supports.

  10. Synthesis and characterization of hierarchically porous metal, metal oxide, and carbon monoliths with highly ordered nanostructure

    NASA Astrophysics Data System (ADS)

    Grano, Amy Janine

    Hierarchically porous materials are of great interest in such applications as catalysis, separations, fuel cells, and advanced batteries. One such way of producing these materials is through the process of nanocasting, in which a sacrificial template is replicated and then removed to form a monolithic replica. This replica consists of mesopores, which can be ordered or disordered, and bicontinuous macropores, which allow flow throughout the length of the monolith. Hierarchically porous metal oxide and carbon monoliths with an ordered mesopores system are synthesized for the first time via nanocasting. These replicas were used as supports for the deposition of silver particles and the catalytic efficiency was evaluated. The ordered silica template used in producing these monoliths was also used for an in-situ TEM study involving metal nanocasting, and an observation of the destruction of the silica template during nanocasting made. Two new methods of removing the silica template were developed and applied to the synthesis of copper, nickel oxide, and zinc oxide monoliths. Finally, hollow fiber membrane monoliths were examined via x-ray tomography in an attempt to establish the presence of this structure throughout the monolith.

  11. Mesoporous NiO-samaria doped ceria for low-temperature solid oxide fuel cells.

    PubMed

    Kim, Jin-Yeop; Kim, Ji Hyeon; Choi, Hyung Wook; Kim, Kyung Hwan; Park, Sang Joon

    2014-08-01

    In order to prepare anode material for low-temperature solid oxide fuel cells (SOFCs), the mesoporous NiO-SDC was synthesized using a cationic surfactant (cetyltrimethyl-ammonium bromide; CTAB) for obtaining wide triple-phase boundary (TPB). In addition, Ni-SDC anode-supported SOFC single cells with YSZ electrolyte and LSM cathode were fabricated and the performance of single cells was evaluated at 600 °C. The microstructure of NiO-SDC was characterized by XRD, EDX, SEM, and BET, and the results showed that the mesoporous NiO-SDC with 10 nm pores could be obtained. It was found that the surface area and the electrical performance were strongly influenced by the Ni content in Ni-SDC cermets. After calcined at 600 °C, the surface area of NiO-SDC was between 90-117 m2/g at 35-45 Ni wt%, which was sufficiently high for providing large TPB in SOFC anode. The optimum Ni content for cell performance was around 45 wt% and the corresponding MPD was 0.36 W/cm2. Indeed, the mesoporous NiO-SDC cermet may be of interest for use as an anode for low-temperature SOFCs.

  12. Surface-functionalized mesoporous carbon materials

    DOEpatents

    Dai, Sheng; Gorka, Joanna; Mayes, Richard T.

    2016-02-02

    A functionalized mesoporous carbon composition comprising a mesoporous carbon scaffold having mesopores in which polyvinyl polymer grafts are covalently attached, wherein said mesopores have a size of at least 2 nm and up to 50 nm. Also described is a method for producing the functionalized mesoporous composition, wherein a reaction medium comprising a precursor mesoporous carbon, vinyl monomer, initiator, and solvent is subjected to sonication of sufficient power to result in grafting and polymerization of the vinyl monomer into mesopores of the precursor mesoporous carbon. Also described are methods for using the functionalized mesoporous carbon, particularly in extracting metal ions from metal-containing solutions.

  13. Method for plating with metal oxides

    SciTech Connect

    Silver, Gary L.; Martin, Frank S.

    1994-08-23

    A method of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate.

  14. Method for plating with metal oxides

    SciTech Connect

    Silver, G.L.; Martin, F.S.

    1994-08-23

    A method is disclosed of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate. 1 fig.

  15. Method for plating with metal oxides

    DOEpatents

    Silver, G.L.; Martin, F.S.

    1994-08-23

    A method is disclosed of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate. 1 fig.

  16. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

    SciTech Connect

    Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

    2015-10-15

    The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.

  17. Sol-gel derived mesoporous cobalt silica catalyst: Synthesis, characterization and its activity in the oxidation of phenol

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2014-10-01

    Highly mesoporous cobalt silica rice husk catalysts with (5-15 wt.%) Co2+ loading were prepared via a simple sol-gel technique at room temperature. The successful insertion of cobalt ions into silica matrix was evidenced from FT-IR, NMR, XPS and AAS analyses. Preservation of the mesoporosity nature of silica upon incorporating Co2+ was confirmed from the N2-sorption studies. The topography and morphology viewed by TEM analysis differs as the cobalt concentration varies from 5 to 15 wt.%. Parallel pore channels and spherical nanoparticles of 9.44 nm were achieved for cobalt silica catalysts with 10 and 15 wt.% respectively. Cobalt catalysts were active in the liquid-phase oxidation of phenol with H2O2 as an oxygen source. The performances of the catalysts were greatly influenced by various parameters such as reaction temperature, catalyst amount, molar ratio of substrate to oxidant, nature of solvent, metal loading and homogeneous precursor salt. Water served as the best reaction medium for this oxidation system. The regeneration studies confirmed cobalt catalyst could be reused for five cycles without experiencing large loss in the conversion. Both leaching and reusability studies testified that the catalysts were truly heterogeneous.

  18. Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys

    DOEpatents

    Woodfield, Brian F.; Liu, Shengfeng; Boerio-Goates, Juliana; Liu, Qingyuan; Smith, Stacey Janel

    2012-07-03

    In preferred embodiments, metal nanoparticles, mixed-metal (alloy) nanoparticles, metal oxide nanoparticles and mixed-metal oxide nanoparticles are provided. According to embodiments, the nanoparticles may possess narrow size distributions and high purities. In certain preferred embodiments, methods of preparing metal nanoparticles, mixed-metal nanoparticles, metal oxide nanoparticles and mixed-metal nanoparticles are provided. These methods may provide tight control of particle size, size distribution, and oxidation state. Other preferred embodiments relate to a precursor material that may be used to form nanoparticles. In addition, products prepared from such nanoparticles are disclosed.

  19. Dual template effect of supercritical CO2 in ionic liquid to fabricate a highly mesoporous cobalt metal-organic framework.

    PubMed

    Yu, Huanan; Xu, Dongdong; Xu, Qun

    2015-08-28

    A hierarchical meso- and microporous metal-organic framework (MOF) was facilely fabricated in an ionic liquid (IL)/supercritical CO2 (SC CO2)/surfactant emulsion system. Notably, CO2 exerts a dual effect during the synthesis; that is, CO2 droplets act as a template for the cores of nanospheres while CO2-swollen micelles induce mesopores on nanospheres.

  20. Single-crystal-like nanoporous spinel oxides: a strategy for synthesis of nanoporous metal oxides utilizing metal-cyanide hybrid coordination polymers.

    PubMed

    Zakaria, Mohamed B; Hu, Ming; Imura, Masataka; Salunkhe, Rahul R; Umezawa, Naoto; Hamoudi, Hicham; Belik, Alexei A; Yamauchi, Yusuke

    2014-12-22

    Development of a new method to synthesize nanoporous metal oxides with highly crystallized frameworks is of great interest because of their wide use in practical applications. Here we demonstrate a thermal decomposition of metal-cyanide hybrid coordination polymers (CPs) to prepare nanoporous metal oxides. During the thermal treatment, the organic units (carbon and nitrogen) are completely removed, and only metal contents are retained to prepare nanoporous metal oxides. The original nanocube shapes are well-retained even after the thermal treatment. When both Fe and Co atoms are contained in the precursors, nanoporous Fe-Co oxide with a highly oriented crystalline framework is obtained. On the other hand, when nanoporous Co oxide and Fe oxide are obtained from Co- and Fe-contacting precursors, their frameworks are amorphous and/or poorly crystallized. Single-crystal-like nanoporous Fe-Co oxide shows a stable magnetic property at room temperature compared to poly-crystalline metal oxides. We further extend this concept to prepare nanoporous metal oxides with hollow interiors. Core-shell heterostructures consisting of different metal-cyanide hybrid CPs are prepared first. Then the cores are dissolved by chemical etching using a hydrochloric acid solution (i.e., the cores are used as sacrificial templates), leading to the formation of hollow interiors in the nanocubes. These hollow nanocubes are also successfully converted to nanoporous metal oxides with hollow interiors by thermal treatment. The present approach is entirely different from the surfactant-templating approaches that traditionally have been utilized for the preparation of mesoporous metal oxides. We believe the present work proves a new way to synthesize nanoporous metal oxides with controlled crystalline frameworks and architectures. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Breakthrough and future: nanoscale controls of compositions, morphologies, and mesochannel orientations toward advanced mesoporous materials.

    PubMed

    Yamauchi, Yusuke; Suzuki, Norihiro; Radhakrishnan, Logudurai; Wang, Liang

    2009-01-01

    Currently, ordered mesoporous materials prepared through the self-assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic-based materials, for example, transition-metal oxides, carbons, inorganic-organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant-based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation-mediated direct templating (EDIT), spray-dried techniques, and collaboration with hard-templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic-scale controls of mesochannels are important for innovative applications such as molecular-scale devices and electrodes with enhanced diffusions of guest species. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  2. Nitrogen and fluorine dual-doped mesoporous graphene: a high-performance metal-free ORR electrocatalyst with a super-low HO2- yield

    NASA Astrophysics Data System (ADS)

    Jiang, Shu; Sun, Yujing; Dai, Haichao; Hu, Jingting; Ni, Pengjuan; Wang, Yilin; Li, Zhen; Li, Zhuang

    2015-06-01

    In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells.In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells. Electronic supplementary information (ESI) available: Experimental details (Scheme S1), optimization and morphology of NF-MGs catalysts (Fig. S1-S2), Fig. S3-S9, and Tables S1-S2. See DOI: 10.1039/c5nr01793a

  3. Nano-Engineered Electrochemical Sensors for Monitoring of Toxic Metals in Groundwater: Development of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled Monolayers on Mesoporous Supports

    DTIC Science & Technology

    2007-03-15

    in Groundwater Development Of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled Monolayers On Mesoporous Supports...Sensors for Monitoring of Toxic Metals in Groundwater Development Of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled... Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled onolayers On Mesoporous Supports SI-1267 95440Zemanian, Thomas S., and Lin

  4. Synthesis and photocatalytic applications of nano-sized zinc-doped mesoporous titanium oxide

    SciTech Connect

    Sánchez-Muñoz, Sergio; Pérez-Quintanilla, Damián

    2013-02-15

    Graphical abstract: Nano-sized mesoporous titanium oxide (T0) and zinc-doped nano-sized mesoporous titanium oxides (TA–TD) were synthesized by a simple method and characterized by different techniques. All materials have been studied in the photocatalytic degradation of methylene blue under UV light, observing that the decrease in the band gap of the materials seems to have a positive influence in the photocatalytic activity. Display Omitted Highlights: ► Nano-sized mesoporous TiO{sub 2} and Zn-doped TiO{sub 2} have been synthesized and characterized. ► Band gap of the Zn-doped TiO{sub 2} decreases when the Zn amount increases. ► Materials consist of porous particles (10–20 nm). ► The photocatalytic degradation of MB has been studied for these materials. ► A decrease in the band gap of the materials enhances the photocatalytic activity. -- Abstract: The synthesis of nano-sized mesoporous titanium oxide (T0) is described by an easy synthetic method which consists of the reaction of titanium tetraisopropoxide and a solution of HNO{sub 3} in water (pH 2.0) and the subsequent elimination of the volatiles by simple distillation. On the other hand, zinc-doped mesoporous titanium oxides (TA–TD) were synthesized using the same method but adding increasing amounts of Zn(NO{sub 3}){sub 2} to give materials which contain between 0.12 and 6.17 wt.% Zn. Upon the calcinations of all the obtained materials, characterization has been carried out by using N{sub 2} adsorption–desorption isotherms, powder X-ray diffraction, X-ray fluorescence, UV–vis spectrometry, solid state {sup 47,49}Ti NMR spectroscopy and transmission electronic microscopy (TEM). The results show that all these materials are mesoporous, with BET surfaces between 54 and 121 m{sup 2}/g and similar pore diameters between 6.4 and 9.1 nm. XRD studies show that these materials mainly consist of anatase and very small amounts of brookite. TEM technique shows the small particle sizes of the

  5. Metallic nanocrystallites-incorporated ordered mesoporous carbon as labels for a sensitive simultaneous multianalyte electrochemical immunoassay.

    PubMed

    Fang, Yishan; Huang, Xinjian; Zeng, Qiang; Wang, Lishi

    2015-11-15

    This work reports on a facile, novel multianalyte electrochemical immunoassay for simultaneous detection of a-fetoprotein (AFP) and human epidermal growth factor receptor type-2 (HER-2) using metal-containing nanomaterials confined in the ordered mesoporous carbon matrix (OMC-M) as labels. Well-dispersed uniform metallic nanocrystallites incorporated OMC materials were fabricated through a simple, economical, and green preparative strategy toward phenolic resol as a carbon source and metal nitrate as metal sources. The large amount of metallic nanocrystallites loading on the OMC nanomaterials, greatly amplified the detection signals, and the good biocompatibility of carbon nanotubes-chitosan retained excellent stability for the sandwich-type immunoassay. Under optimal experimental conditions, the proposed immunoassay exhibited high sensitivity and selectivity for the detection of analytes, providing a better linear response range from 0.001 to 150 ng/mL for AFP and for HER-2, with a lower limit of detectionof 0.6p g/mL and 0.35 pg/mL (S/N=3), respectively. The immunosensor exhibited convenience, low cost, rapidity, good specificity, acceptable stability and reproducibility. Moreover, satisfactory results were obtained for the determination of AFP and HER-2 in real human serum samples, indicating that the developed immunoassay has the potential to find application in clinical detection of AFP and HER-2 and other tumor markers as an alternative approach.

  6. High sensitive mesoporous TiO2-coated love wave device for heavy metal detection.

    PubMed

    Gammoudi, I; Blanc, L; Moroté, F; Grauby-Heywang, C; Boissière, C; Kalfat, R; Rebière, D; Cohen-Bouhacina, T; Dejous, C

    2014-07-15

    This work deals with the design of a highly sensitive whole cell-based biosensor for heavy metal detection in liquid medium. The biosensor is constituted of a Love wave sensor coated with a polyelectrolyte multilayer (PEM). Escherichia coli bacteria are used as bioreceptors as their viscoelastic properties are influenced by toxic heavy metals. The acoustic sensor is constituted of a quartz substrate with interdigitated transducers and a SiO2 guiding layer. However, SiO2 shows some degradation when used in a saline medium. Mesoporous TiO2 presents good mechanical and chemical stability and offers a high active surface area. Then, the addition of a thin titania layer dip-coated onto the acoustic path of the sensor is proposed to overcome the silica degradation and to improve the mass effect sensitivity of the acoustic device. PEM and bacteria deposition, and heavy metal influence, are real time monitored through the resonance frequency variations of the acoustic device. The first polyelectrolyte layer is inserted through the titania mesoporosity, favouring rigid link of the PEM on the sensor and improving the device sensitivity. Also, the mesoporosity of surface increases the specific surface area which can be occupied and favors the formation of homogeneous PEM. It was found a frequency shift near -20±1 kHz for bacteria immobilization with titania film instead of -7±3 kHz with bare silica surface. The sensitivity is highlighted towards cadmium detection. Moreover, in this paper, particular attention is given to the immobilization of bacteria and to biosensor lifetime. Atomic Force Microscopy characterizations of the biosurface have been done for several weeks. They showed significant morphological differences depending on the bacterial life time. We noticed that the lifetime of the biosensor is longer in the case of using a mesoporous TiO2 layer. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Synthesis of morphology-controllable mesoporous Co{sub 3}O{sub 4} and CeO{sub 2}

    SciTech Connect

    Wang Yangang; Wang Yanqin; Ren Jiawen; Mi Yan; Zhang Fengyuan; Li Changlin; Liu Xiaohui; Guo Yun; Guo Yanglong; Lu Guanzhong

    2010-02-15

    Recently, extensive works have been devoted to the morphology control of mesoporous materials with respect to their use in various applications. In this paper, we used two kinds of mesoporous silica, SBA-15 rods and spheres as hard templates to synthesize morphology-controllable mesoporous metal oxides. By carefully controlling the loading of metal precursors in the mesopores of the hard template, mesoporous Co{sub 3}O{sub 4} and CeO{sub 2} with different morphologies, such as micrometer-sized rod, hollow sphere, saucer-like sphere, and solid sphere were conveniently obtained. The structural properties of these materials were characterized by XRD, BET, SEM and TEM. In addition, it is found that the differences observed in the textural properties of the two mesoporous metal oxides nanocasted from the same template can be attributed to the properties of metal precursors and the interaction between metal oxide and SiO{sub 2}. Thus-obtained mesoporous metal oxides with such special morphologies may have a potential application in the field of environmental catalytic oxidation. - Graphical Abstract: Mesoporous Co{sub 3}O{sub 4} and CeO{sub 2} with different morphologies, such as micrometer-sized rod, hollow sphere, saucer-like sphere, and solid sphere were synthesized by nanocasting.

  8. Molecular Level Coating of Metal Oxide Particles

    NASA Technical Reports Server (NTRS)

    McDaniel, Patricia R. (Inventor); St.Clair, Terry L. (Inventor)

    2002-01-01

    Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar osmotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing, synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper. making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

  9. Molecular Level Coating for Metal Oxide Particles

    NASA Technical Reports Server (NTRS)

    McDaniel, Patricia R. (Inventor); Saint Clair, Terry L. (Inventor)

    2000-01-01

    Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar aprotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper, making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

  10. Molecular Level Coating of Metal Oxide Particles

    NASA Technical Reports Server (NTRS)

    McDaniel, Patricia R. (Inventor); St.Clair, Terry L. (Inventor)

    2002-01-01

    Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar osmotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing, synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper. making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

  11. Easy and General Synthesis of Large-Sized Mesoporous Rare-Earth Oxide Thin Films by 'Micelle Assembly'.

    PubMed

    Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Dai, Pengcheng; Yamauchi, Yusuke

    2015-12-01

    Large-sized (ca. 40 nm) mesoporous Er2O3 thin films are synthesized by using a triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er(3+) is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare-earth oxide (Sm2O3, Dy2O3, Tb2O3, Ho2O3, Yb2O3, and Lu2O3) thin films with potential uses in electronics and optical devices.

  12. Hydrogen Oxidation-Mediated Current Discharge in Mesoporous Pt/TiO2 Nanocomposite.

    PubMed

    Ray, Nathan J; Karpov, Eduard G

    2016-11-23

    Here we report on direct evidence of a correlation between hydrogen-to-water oxidation on mesoporous Pt/TiO2 nanocomposites at room temperature and the conversion of surface-released chemical energy into a stationary electrical current. The Pt phase of this heterojunction device is an electrically continuous 15 nm thick mesh deposited onto a mesoporous TiO2 substrate fabricated with a plasma electrolytic oxidation process. The H2O turnover frequency approaches an asymptotic value associated with the saturation of the Pt/TiO2 interface as the concentration of hydrogen gas is increased. In situ measurements of the reaction-induced current concurrently with mass spectrometry measurements illuminate the polarity switch of the reaction current (from thermionic emission to a reverse steady-state flow) simultaneously with the production of water. Furthermore, a concentration-dependent value of 5 min is measured as the time constant for the adsorption of the initial addition of H2 and H2O formation and desorption.

  13. Ultrafine ferroferric oxide nanoparticles embedded into mesoporous carbon nanotubes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Gao, Guo; Zhang, Qiang; Cheng, Xin-Bing; Shapter, Joseph G.; Yin, Ting; Sun, Rongjin; Cui, Daxiang

    2015-12-01

    An effective one-pot hydrothermal method for in situ filling of multi-wall carbon nanotubes (CNT, diameter of 20-40 nm, length of 30-100 μm) with ultrafine ferroferric oxide (Fe3O4) nanoparticles (8-10 nm) has been demonstrated. The synthesized Fe3O4@CNT exhibited a mesoporous texture with a specific surface area of 109.4 m2 g-1. The loading of CNT, in terms of the weight ratio of Fe3O4 nanoparticles, can reach as high as 66.5 wt%. Compared to the conventional method of using a Al2O3 membrane as template to fill CNT with iron oxides nanoparticles, our strategy is facile, effective, low cost and easy to scale up to large scale production (~1.42 g per one-pot). When evaluated for lithium storage at 1.0 C (1 C = 928 mA g-1), the mesoporous Fe3O4@CNT can retain at 358.9 mAh g-1 after 60 cycles. Even when cycled at high rate of 20 C, high capacity of 275.2 mAh g-1 could still be achieved. At high rate (10 C) and long life cycling (500 cycles), the cells still exhibit a good capacity of 137.5 mAhg-1.

  14. Mesoporous Silica Coated Polydopamine Functionalized Reduced Graphene Oxide for Synergistic Targeted Chemo-Photothermal Therapy.

    PubMed

    Shao, Leihou; Zhang, Ruirui; Lu, Jianqing; Zhao, Caiyan; Deng, Xiongwei; Wu, Yan

    2017-01-18

    The integration of different therapies into a single nanoplatform has shown great promise for synergistic tumor treatment. Herein, mesoporous silica (MS) coated polydopamine functionalized reduced graphene oxide (pRGO) further modified with hyaluronic acid (HA) (pRGO@MS-HA) has been utilized as a versatile nanoplatform for synergistic targeted chemo-photothermal therapy against cancer. A facile and green chemical method is adopted for the simultaneous reduction and noncovalent functionalization of graphene oxide (GO) by using mussel inspired dopamine (DA) to enhance biocompatibility and the photothermal effect. Then, it was coated with mesoporous silica (MS) (pRGO@MS) to enhance doxorubicin (DOX) loading and be further modified with the targeting moieties hyaluronic acid (HA). The pH-dependent and near-infrared (NIR) laser irradiation-triggered DOX release from pRGO@MS(DOX)-HA is observed, which could enhance the chemo-photothermal therapy effect. In vitro experimental results confirm that pRGO@MS(DOX)-HA exhibits good dispersibility, excellent photothermal property, remarkable tumor cell killing efficiency, and specificity to target tumor cells. In vivo antitumor experiments further demonstrated that pRGO@MS(DOX)-HA could exhibit an excellent synergistic antitumor efficacy, which is much more distinct than any monotherapy. This work presents a novel nanoplatform which could load chemotherapy drugs with high efficiency and be used as light-mediated photothermal cancer therapy agent.

  15. Novel mesoporous FeAl bimetal oxides for As(III) removal: Performance and mechanism.

    PubMed

    Ding, Zecong; Fu, Fenglian; Cheng, Zihang; Lu, Jianwei; Tang, Bing

    2017-02-01

    In this study, novel mesoporous FeAl bimetal oxides were successfully synthesized, characterized, and employed for As(III) removal. Batch experiments were conducted to investigate the effects of Fe/Al molar ratio, dosage, and initial solution pH values on As(III) removal. The results showed that the FeAl bimetal oxide with Fe/Al molar ratio 4:1 (shorten as FeAl-4) can quickly remove As(III) from aqueous solution in a wide pH range. The FeAl-4 before and after reaction with As(III) was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED), Brunauer-Emmett-Teller (BET) surface area measurement, and X-ray photoelectron spectroscopy (XPS). The BET results showed that the original FeAl-4 with a high surface area of 223.9 m(2)/g was a mesoporous material. XPS analysis indicated that the surface of FeAl-4 possessed a high concentration of M-OH (where M represents Fe and Al), which was beneficial to the immobility of As(III). The excellent performance of FeAl-4 makes it a potentially attractive material for As(III) removal from aqueous solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Metals, toxicity and oxidative stress.

    PubMed

    Valko, M; Morris, H; Cronin, M T D

    2005-01-01

    Metal-induced toxicity and carcinogenicity, with an emphasis on the generation and role of reactive oxygen and nitrogen species, is reviewed. Metal-mediated formation of free radicals causes various modifications to DNA bases, enhanced lipid peroxidation, and altered calcium and sulfhydryl homeostasis. Lipid peroxides, formed by the attack of radicals on polyunsaturated fatty acid residues of phospholipids, can further react with redox metals finally producing mutagenic and carcinogenic malondialdehyde, 4-hydroxynonenal and other exocyclic DNA adducts (etheno and/or propano adducts). Whilst iron (Fe), copper (Cu), chromium (Cr), vanadium (V) and cobalt (Co) undergo redox-cycling reactions, for a second group of metals, mercury (Hg), cadmium (Cd) and nickel (Ni), the primary route for their toxicity is depletion of glutathione and bonding to sulfhydryl groups of proteins. Arsenic (As) is thought to bind directly to critical thiols, however, other mechanisms, involving formation of hydrogen peroxide under physiological conditions, have been proposed. The unifying factor in determining toxicity and carcinogenicity for all these metals is the generation of reactive oxygen and nitrogen species. Common mechanisms involving the Fenton reaction, generation of the superoxide radical and the hydroxyl radical appear to be involved for iron, copper, chromium, vanadium and cobalt primarily associated with mitochondria, microsomes and peroxisomes. However, a recent discovery that the upper limit of "free pools" of copper is far less than a single atom per cell casts serious doubt on the in vivo role of copper in Fenton-like generation of free radicals. Nitric oxide (NO) seems to be involved in arsenite-induced DNA damage and pyrimidine excision inhibition. Various studies have confirmed that metals activate signalling pathways and the carcinogenic effect of metals has been related to activation of mainly redox-sensitive transcription factors, involving NF-kappaB, AP-1 and p53

  17. Method for preparing hollow metal oxide microsphere

    DOEpatents

    Schmitt, C.R.

    1974-02-12

    Hollow refractory metal oxide microspheres are prepared by impregnating resinous microspheres with a metallic compound, drying the impregnated microspheres, heating the microspheres slowly to carbonize the resin, and igniting the microspheres to remove the carbon and to produce the metal oxide. Zirconium oxide is given as an example. (Official Gazette)

  18. A synthetic route to ultralight hierarchically micro/mesoporous Al(III)-carboxylate metal-organic aerogels

    PubMed Central

    Li, Lei; Xiang, Shenglin; Cao, Shuqi; Zhang, Jianyong; Ouyang, Gangfeng; Chen, Liuping; Su, Cheng-Yong

    2013-01-01

    Developing a synthetic methodology for the fabrication of hierarchically porous metal-organic monoliths that feature high surface area, low density and tunable porosity is imperative for mass transfer applications, including bulky molecule capture, heterogeneous catalysis and drug delivery. Here we report a versatile and facile synthetic route towards ultralight micro/mesoporous metal-organic aerogels based on the two-step gelation of metal-organic framework nanoparticles. Heating represents a key factor in the control of gelation versus crystallization of Al(III)-multicarboxylate systems. The porosity of the resulting metal-organic aerogels can be readily tuned, leading to the formation of well-ordered intraparticle micropores and aerogel-specific interparticle mesopores, thereby integrating the merits of both crystalline metal-organic frameworks and light aerogels. The hierarchical micro/mesoporosity of the Al-metal-organic aerogels is thoroughly evaluated by N2 sorption. The good accessibility of the micro/mesopores is verified by vapour/dye uptake, and their potential for utilization as effective fibre-coating absorbents is tested in solid-phase microextraction analyses. PMID:23653186

  19. Directly Patterned Mesoporous Carbon and Metal-Doped Carbon Films Prepared using Block Copolymer Templates in Supercritical CO2

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Gaurav; Watkins, James

    2006-03-01

    Porous carbon and metal-doped porous carbon films have wide applications in separations, sensors, catalysis and magnetic storage applications. Conventionally prepared carbon films have micropores in the size range of 2 nm. Recent techniques for the synthesize of mesoporous carbon with 10-50 nm pores using sacrificial silica templates have limitations with respect to pore connectivity and the preparation of patterned and metal-doped carbon films. Here we report supercritical fluid-assisted infusion and phase selective reaction within pre-organized block copolymer and block copolymer/homopolymer templates to synthesize mesoporous carbon and metal doped carbon films. Well-defined mesoporous carbon films patterned at the device level with good mechanical properties and metal doped carbon films by pre-infusion of block copolymer templates with metal precursors in supercritical carbon dioxide were synthesized. Platinum doped carbon films for applications in fuel cells having good electrochemical response were produced. The preparation of cobalt containing carbon films with potential use in magnetic storage applications demonstrates the general applicability of supercritical infusion technique to produce metal cluster containing films.

  20. Gelatin-templated mesoporous titania for photocatalytic air treatment and application in metal chalcogenide nanoparticle-sensitized solar cells.

    PubMed

    Stroyuk, Oleksandr L; Rayevska, Oleksandra Ye; Shvalagin, Vitaly V; Kuchmiy, Stepan Ya; Bavykin, Dmitry V; Streltsov, Eugene A; Poznyak, Sergey K

    2013-04-01

    Mesoporous titania as powders and thin films on ITO were prepared using gelatin as an available and non-expensive pore-forming agent. The mesoporous TiO2 manifested a much higher photocatalytic activity in the gas-phase air oxidation of ethanol and acetaldehyde than the commercial nanocrystalline TiO2 P25 (Degussa Corp.). The mesoporous ITO/TiO2 films exhibited 12-14% efficiency of photocurrent generation in aqueous Na2S electrolyte when illuminated by UV light. Deposition of CdS and PbS nanoparticles onto the surface of ITO/TiO2 further increases the photocurrent yields and expands the light sensitivity range of the films to 500-520 nm (CdS) and to 650-700 nm (PbS).

  1. Graphene-supported metal oxide monolith

    DOEpatents

    Worsley, Marcus A.; Baumann, Theodore F.; Biener, Juergen; Biener, Monika A.; Wang, Yinmin; Ye, Jianchao; Tylski, Elijah

    2017-01-10

    A composition comprising at least one graphene-supported metal oxide monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds, wherein the graphene sheets are coated by at least one metal oxide such as iron oxide or titanium oxide. Also provided is an electrode comprising the aforementioned graphene-supported metal oxide monolith, wherein the electrode can be substantially free of any carbon-black and substantially free of any binder.

  2. Oxidation-triggered release of fluorescent molecules or drugs from mesoporous Si microparticles

    PubMed Central

    Wu, Elizabeth C.; Park, Ji-Ho; Park, Jennifer; Segal, Ester; Cunin, Frédérique; Sailor, Michael J.

    2009-01-01

    The fluorescent dye Alexa Fluor 488 or the anti-cancer drug doxorubicin is attached to the surface and inner pore walls of mesoporous Si particles by covalent attachment, and the oxidation-induced release of each molecule is studied. The molecules are bound to the Si matrix using a 10-undecenoic acid linker, which is attached by thermal hydrosilylation. Loading capacity of the microparticles using this method is ∼ 0.5 and 45 mg/g of porous Si microparticle for Alexa Fluor 488 and doxorubicin, respectively. The Si-C-bound assembly is initially stable in aqueous solution, although oxidation of the underlying Si matrix results in conversion to silicon oxide and slow release of the linker-molecule complex by hydrolysis of the Si-O attachment points. When the attached molecule is a fluorophore (Alexa Fluor 488 or doxorubicin), its fluorescence is effectively quenched by the semiconducting silicon matrix. As the particle oxidizes in water, the fluorescence intensity of the attached dye increases due to growth of the insulating silicon oxide layer and, ultimately, dye release from the surface. The recovery of fluorescence in the microparticle and the release of the molecule into solution are monitored in real-time by fluorescence microscopy. Both processes are accelerated by introduction of the oxidizing species peroxynitrite to the aqueous solution. The oxidation-triggered release of the anti-cancer drug doxorubicin to HeLa cells is demonstrated. PMID:19206408

  3. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000

    DOE PAGES

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; ...

    2015-12-17

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitablemore » for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg–2.5 g of NU-1000. Lastly, the entire synthesis is performed without purification by column chromatography and can be completed within 10 d.« less

  4. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000

    SciTech Connect

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; Martinson, Alex B. F.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.

    2015-12-17

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg–2.5 g of NU-1000. Lastly, the entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  5. A scalable synthesis of a mesoporous metal-organic framework called NU-1000.

    SciTech Connect

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; Martinson, Alex B. F.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.

    2016-01-01

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably and is suitable for the production of 50 grams of the requisite organic linker and ?? grams of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 days.

  6. Metal-Free Nitrogen-Doped Mesoporous Carbon for Electroreduction of CO2 to Ethanol.

    PubMed

    Song, Yanfang; Chen, Wei; Zhao, Chengcheng; Li, Shenggang; Wei, Wei; Sun, Yuhan

    2017-08-28

    CO2 electroreduction is a promising technique for satisfying both renewable energy storage and a negative carbon cycle. However, it remains a challenge to convert CO2 into C2 products with high efficiency and selectivity. Herein, we report a nitrogen-doped ordered cylindrical mesoporous carbon as a robust metal-free catalyst for CO2 electroreduction, enabling the efficient production of ethanol with nearly 100 % selectivity and high faradaic efficiency of 77 % at -0.56 V versus the reversible hydrogen electrode. Experiments and density functional theory calculations demonstrate that the synergetic effect of the nitrogen heteroatoms and the cylindrical channel configurations facilitate the dimerization of key CO* intermediates and the subsequent proton-electron transfers, resulting in superior electrocatalytic performance for synthesizing ethanol from CO2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. pH-Responsive Dual Cargo Delivery from Mesoporous Silica Nanoparticles with a Metal-latched Nanogate

    PubMed Central

    Tarn, Derrick; Xue, Min; Zink, Jeffrey I.

    2013-01-01

    A nanogate composed of two iminodiacetic acid (IDA) and a metal ion latch was designed, synthesized and assembled on mesoporous silica nanoparticles. This gating mechanism is capable of storing and releasing metal ions and molecules trapped in the pores. Pore openings derivatized with IDA can be latched shut by forming a bis-IDA chelate complex with a metal ion. This system was tested by loading with Hoechst 33342 as the probe cargo molecule, and latching with cobalt, nickel or calcium metal ions. No cargo release was observed in a neutral aqueous environment, but both cargoes were delivered after acid stimulation and/or the addition of a competitively binding ligand. PMID:23391170

  8. Multifunctional organized mesoporous tin oxide films templated by graft copolymers for dye-sensitized solar cells.

    PubMed

    Park, Jung Tae; Ahn, Sung Hoon; Roh, Dong Kyu; Lee, Chang Soo; Kim, Jong Hak

    2014-07-01

    The synthesis of organized mesoporous SnO2 films with high porosity, larger pores, and good interconnectivity, obtained by sol-gel templating with an amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), is reported. An improved performance of dye-sensitized solar cells (DSSCs) is demonstrated by the introduction of a 400 nm thick organized mesoporous SnO2 interfacial (om-SnO2 IF) layer between nanocrystalline TiO2 (nc-TiO2 ) and a fluorine-doped tin oxide substrate. To elucidate the improved efficiency, the structural, optical, and electrochemical properties of the devices were characterized by SEM, UV/Vis spectroscopy, noncontact 3D surface profilometry, intensity-modulated photocurrent/voltage spectroscopy, incident photon-to-electron conversion efficiency, and electrochemical impedance spectroscopy measurements. The energy-conversion efficiency of the solid polymerized ionic liquid based DSSC fabricated with the om-SnO2 IF/nc-TiO2 photoanode reached 5.9% at 100 mW cm(-2) ; this is higher than those of neat nc-TiO2 (3.5%) and organized mesoporous TiO2 interfacial/nc-TiO2 layer (5.4%) photoanodes. The improved efficiency is attributed to the antireflective property, cascadal energy band gap, good interconnectivity, and high electrical conductivity of the om-SnO2 IF layer, which results in enhanced light harvesting, increased electron transport, reduced charge recombination, and decreased interfacial/internal resistance.

  9. The grain growth behavior of NiO in thermally-stable mesoporous gadolinium-doped ceria network for intermediate-temperature solid oxide fuel cell anode materials.

    PubMed

    Ahn, Seunghyun; Koo, Hyun; Bae, Sung-Hwan; Chang, Ikwhang; Cha, Sukwon; Yoo, Young-Sung; Park, Chan

    2014-10-01

    The grain growth behavior of NiO nano grains in mesoporous gadolinium-doped ceria (GDC) network was investigated for anode materials of intermediate-temperature solid oxide fuel cell (SOFC). Both mesoporous GDC and NiO-GDC powders were synthesized using tri-block copolymer, Pluronic F127 as a structure-directing agent, and then X-ray diffraction, N2 adsorption/desorption isotherms, thermo gravimetric analysis, field-emission scanning electron microscopy and transmission electron microscopy were used for characterization of the mesoporous structure. Mesoporous GDC synthesized using pluronic F127 triblock copolymer had ordered double mesoporous structure with an average pore size of 9.68 nm and was thermally stable up to 700 degrees C. NiO grains in the mesoporous GDC network grew to have an octahedral shape with truncated-edges, but massive NiO agglomeration occurred as the calcination temperature increases up to 850 degrees C.

  10. Surface patterning of mesoporous niobium oxide films for solar energy conversion.

    PubMed

    Ok, Myoung-Ryul; Ghosh, Rudresh; Brennaman, M Kyle; Lopez, Rene; Meyer, Thomas J; Samulski, Edward T

    2013-04-24

    An array of periodic surface features were patterned on mesoporous niobium oxide films by a soft-lithographic technique with the goal of constructing a photonic crystal (PC) structure on the back side of the oxide. The oxide films, fabricated by mixing sol-gel derived niobium oxide nanoparticles and hydroxypropyl cellulose, were employed as photoelectrodes in dye-sensitized solar cells (DSSCs), and their performance evaluated against their flat counterparts. The surface patterns were imprinted using a photocurable perfluoropolyether (PFPE) soft-replica of a silicon master with a two-dimensional array of cylindrical posts (200 nm (D) × 200 nm (H)) in hexagonal geometry. The PC on the niobium oxide surface caused large changes in optical measurements, particularly in the blue wavelengths. To evaluate the optical effect on solar energy conversion, the incident photon-to-current conversion efficiency (IPCE) was measured in the patterned devices and the control group. The IPCE of patterned niobium oxide anodes exhibited a relative enhancement in photocurrent generation over the wavelength range corresponding to the higher absorption in optical measurements.

  11. Structure of assemblies of metal nanowires in mesoporous alumina membranes studied by EXAFS, XANES, X-ray diffraction and SAXS.

    PubMed

    Benfield, Robert E; Grandjean, Didier; Dore, John C; Esfahanian, Hamid; Wu, Zhonghua; Kröll, Michael; Geerkens, Marcus; Schmid, Günter

    2004-01-01

    Mesoporous alumina membranes ("anodic aluminium oxide", or "AAO") are made by anodic oxidation of aluminium metal. These membranes contain hexagonal arrays of parallel non-intersecting cylindrical pores perpendicular to the membrane surface. By varying the anodisation voltage, the pore diameters are controllable within the range 5-250 nm. We have used AAO membranes as templates for the electrochemical deposition of metals within the pores to produce nanowires. These represent assemblies of one-dimensional quantum wires with prospective applications in electronic, optoelectronic and magnetic devices. Detailed characterisation of the structures of these nanowire assemblies on a variety of length scales is essential to understand their physical properties and evaluate their possible applications. We have used EXAFS, XANES, WAXS, high energy X-ray diffraction and SAXS to study their structure and bonding. In this paper we report the results of our studies of four different nanowire systems supported in AAO membranes. These are the ferromagnetic metals iron and cobalt, the superconducting metal tin, and the semiconductor gallium nitride. Iron nanowires in pores of diameter over the range 12 nm-72 nm are structurally very similar to bcc bulk iron. They have a strong preferred orientation within the alumina pores. Their XANES shows significant differences from that of bulk iron, showing that the electronic structure of the iron nanowires depends systematically on their diameter. Cobalt nanowires are composed of a mixture of hcp and fcc phases, but the ratio of the two phases does not depend in a simple way on the pore diameter or preparation conditions. In bulk cobalt, the fcc beta-phase is normally stable only at high temperatures. Strong preferred orientation of the c-axis in the pores was found. Tin nanowires in alumina membranes with pores diameters between 12 nm and 72 nm have a tetragonal beta-structure at ambient temperature and also at 80 K. Magnetic

  12. Method of recovering volatile metals from material containing metal oxides

    SciTech Connect

    Santen, S.

    1984-12-18

    A method of reducing and recovering volatile metal from metal oxides comprising the steps of injecting metal oxide-containing material into a shaft reactor, simultaneously injecting reducing agent into said reactor, continuously maintaining said reactor substantially filled with coke, supplying thermal energy to the reactor, preferably by means of a plasma burner, such that at least some of the metal oxides are reduced to metal and melted or volatilized depending upon whether the metal is volatile. The melted metal is removed from the bottom of the reactor while the volatilized metal is permitted to flow upwardly through the shaft reactor in the form of metal vapor together with a gas flow. The coke in the shaft reactor through which the volatilized metal passes is maintained at a temperature in excess of 1000/sup 0/ C., thus screening the upper portion of the shaft reactor and the reactor top by means of the coke so as to prevent condensation of the volatilized metal.

  13. Carbon nanofiber mesoporous films: efficient platforms for bio-hydrogen oxidation in biofuel cells.

    PubMed

    de Poulpiquet, Anne; Marques-Knopf, Helena; Wernert, Véronique; Giudici-Orticoni, Marie Thérèse; Gadiou, Roger; Lojou, Elisabeth

    2014-01-28

    The discovery of oxygen and carbon monoxide tolerant [NiFe] hydrogenases was the first necessary step toward the definition of a novel generation of hydrogen fed biofuel cells. The next important milestone is now to identify and overcome bottlenecks limiting the current densities, hence the power densities. In the present work we report for the first time a comprehensive study of herringbone carbon nanofiber mesoporous films as platforms for enhanced biooxidation of hydrogen. The 3D network allows mediatorless hydrogen oxidation by the membrane-bound hydrogenase from the hyperthermophilic bacterium Aquifex aeolicus. We investigate the key physico-chemical parameters that enhance the catalytic efficiency, including surface chemistry and hierarchical porosity of the biohybrid film. We also emphasize that the catalytic current is limited by mass transport inside the mesoporous carbon nanofiber film. Provided hydrogen is supplied inside the carbon film, the combination of the hierarchical porosity of the carbon nanofiber film with the hydrophobicity of the treated carbon material results in very high efficiency of the bioelectrode. By optimization of the whole procedure, current densities as high as 4.5 mA cm(-2) are reached with a turnover frequency of 48 s(-1). This current density is almost 100 times higher than when hydrogenase is simply adsorbed at a bare graphite electrode, and more than 5 times higher than the average of the previous reported current densities at carbon nanotube modified electrodes, suggesting that carbon nanofibers can be efficiently used in future sustainable H2/O2 biofuel cells.

  14. Photothermal combined gene therapy achieved by polyethyleneimine-grafted oxidized mesoporous carbon nanospheres.

    PubMed

    Meng, Ying; Wang, Shanshan; Li, Chengyi; Qian, Min; Yan, Xueying; Yao, Shuangchao; Peng, Xiyue; Wang, Yi; Huang, Rongqin

    2016-09-01

    Combining controllable photothermal therapy and efficacious gene therapy in a single platform holds great promise in cancer therapy due to the enhanced combined therapeutic effects. Herein, polyethyleneimine-grafted oxidized mesoporous carbon nanospheres (OP) were developed for combined photothermal combined gene therapy in vitro and in vivo. The synthesized OP was characterized to have three dimensional spherical structure with uniformed diameter, ordered mesopores with graphitic domains, high water dispersion with zeta potential of +22 mV, and good biocompatibility. Consequently, OP was exploited as the photothermal convertor with strong NIR absorption and the gene vector via electrostatic interaction, which therefore cannot only deliver the therapeutic gene (pING4) to tumors for gene therapy, but also can eliminate the tumors by photothermal ablation. Moreover, the improved gene therapy accompanied by the NIR photothermally enhanced gene release was also well achieved based on OP. The excellent combined therapeutic effects demonstrated in vitro and in vivo suggested the OP's potential for cancer therapy.

  15. Mesoporous graphene-like nanobowls as Pt electrocatalyst support for highly active and stable methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; He, Guoqiang; Jiang, Zhifeng; Wei, Wei; Gao, Lina; Xie, Jimin

    2015-06-01

    Mesoporous graphene-like nanobowls (GLBs) with high surface area of 1091 m2 g-1, high pore volume of 2.7 cm3 g-1 and average pore diameter of 9.8 nm are synthesized through template method. The GLBs with inherent excellent electrical conductivity and chemical inertia show the properties of well mass transfer, poison resistance and stable loading of smaller Pt particles. Therefore, the Pt/GLB catalyst shows much higher activity and stability than that of commercial Pt/C (TKK) for methanol oxidation reaction (MOR). Therein, the peak current density on Pt/GLB (2075 mA mgPt-1) for MOR is 2.87 times that of commercial Pt/C (723 mA mgPt-1); and the onset potential for the MOR on the former is negatively shifted about 160 mV compared with that on the latter. The catalytic performances of the Pt/GLB are also better than those of the Pt loading on mesoporous amorphous carbon nanobowls (Pt/BLC), indicating promotion effect of graphite on Pt catalytic performance.

  16. Sustained Release of a Monoclonal Antibody from Electrochemically Prepared Mesoporous Silicon Oxide

    PubMed Central

    Andrew, Jennifer S.; Anglin, Emily J.; Wu, Elizabeth C.; Chen, Michelle Y.; Cheng, Lingyun; Freeman, William R.; Sailor, Michael J.

    2011-01-01

    Nanostructured mesoporous silica (SiO2) films are used to load and release the monoclonal antibody bevacizumab (Avastin) in vitro. A biocompatible and biodegradable form of mesoporous SiO2 is prepared by electrochemical etching of single crystalline Si, followed by thermal oxidation in air at 800 °C. Porous SiO2 exhibits a negative surface charge at physiological pH (7.4), allowing it to spontaneously adsorb the positively charged antibody from an aqueous phosphate buffered saline solution. This electrostatic adsorption allows bevacizumab to be concentrated by >100× (300 mg bevacziumab per gram of porous SiO2 when loaded from a 1 mg mL−1 solution of bevacziumab). Drug loading is monitored by optical interferometric measurements of the thin porous film. A two-component Bruggeman effective medium model is employed to calculate percent porosity and film thickness, and is further used to determine the extent of drug loading into the porous SiO2 film. In vitro drug release profiles are characterized by an enzyme-linked immunosorbent assay (ELISA), which confirms that the antibody is released in its active, VEGF-binding form. The nanostructured delivery system described here provides a sustained release of the monoclonal antibody where approximately 98% of drug is released over a period of one month. PMID:21274422

  17. A Deep Reduction and Partial Oxidation Strategy for Fabrication of Mesoporous Si Anode for Lithium Ion Batteries.

    PubMed

    Liang, Jianwen; Li, Xiaona; Hou, Zhiguo; Zhang, Wanqun; Zhu, Yongchun; Qian, Yitai

    2016-02-23

    A deep reduction and partial oxidation strategy to convert low-cost SiO2 into mesoporous Si anode with the yield higher than 90% is provided. This strategy has advantage in efficient mesoporous silicon production and in situ formation of several nanometers SiO2 layer on the surface of silicon particles. Thus, the resulted silicon anode provides extremely high reversible capacity of 1772 mAh g(-1), superior cycling stability with more than 873 mAh g(-1) at 1.8 A g(-1) after 1400 cycles (corresponding to the capacity decay rate of 0.035% per cycle), and good rate capability (∼710 mAh g(-1) at 18A g(-1)). These promising results suggest that such strategy for mesoporous Si anode can be potentially commercialized for high energy Li-ion batteries.

  18. Making A Noble-Metal-On-Metal-Oxide Catalyst

    NASA Technical Reports Server (NTRS)

    Miller, Irvin M.; Davis, Patricia P.; Upchurch, Billy T.

    1989-01-01

    Catalyst exhibits superior performance in oxidation of CO in CO2 lasers. Two-step process developed for preparing platinum- or palladium-on-tin-oxide catalyst for recombination of CO and O2, decomposition products that occur in high-voltage discharge region of closed-cycle CO2 laser. Process also applicable to other noble-metal/metal-oxide combinations.

  19. Ferromagnetism in Metal Oxide Nanowires

    NASA Astrophysics Data System (ADS)

    Maloney, Francis Scott

    Maloney, Francis S., Ferromagnetism in Metal Oxide Nanowires, Ph.D, Department of. Physics and Astronomy, Dec. 2016. Metal-oxide nanowires (NWs) are versatile, 1-dimensional semiconducting structures. with unique properties and great potential for device applications. One particularly. interesting feature of these structures is that they often show ferromagnetic behavior. where their bulk counterparts do not. Their ferromagnetism may offer a new medium for. sub-micron scale spintronic devices. In this work, two different metal oxide NW systems. are studied; Mn-doped ZnO and Sn-doped In2O3 (ITO). Mn-ZnO and ITO NWs were. fabricated by a vapor-liquid-solid transport (VLS) mechanism within a chemical-vapor. deposition (CVD) process. The optical and magnetic properties of Mn-doped ZnO NWs were examined before. and after semiconducting CdSe quantum dots (QDs) were deposited on the NW surface. Both undoped and Mn-doped QDs were examined. Bare Mn-doped ZnO NWs were. found to be ferromagnetic at room temperature. Their total saturation magnetization. increased after the deposition of QDs. The origin of the ferromagnetism is believed to be. due to the contributions of both zinc vacancies (VZn’s) and exchange coupling between. Mn ions. Mn-ZnO NWs were then utilized in quantum dot sensitized solar cells. (QDSSCs), where Mn-doping in both the NW and QD were found to improve the overall. performance of the cell. Ferromagnetism was also observed in ITO NWs. The oxidation state of the Sn ions. was examined using x-ray photoelectron spectroscopy (XPS). It was found that Sn2+ was. the dominant ionic species in samples over 6% (atomic percentage) Sn. Their saturation. magnetization increased with increasing Sn concentration, which could be associated. with the spin-splitting of a defect band that was encouraged by the imbalance of Sn2+ to. Sn4+ species at high Sn concentrations.

  20. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides

    NASA Astrophysics Data System (ADS)

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-01

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co3O4, ZnO, Mn2O3, MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N2, whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N2. Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N2 and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H2 and CO2 adsorption properties depending on the environment used for the thermolysis of MOFs.Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co3O4, ZnO, Mn2O3, MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N2, whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N2. Another point of interest is the fact that we have

  1. Preparing oxidizer coated metal fuel particles

    NASA Technical Reports Server (NTRS)

    Shafer, J. I.; Simmons, G. M. (Inventor)

    1974-01-01

    A solid propellant composition of improved efficiency is described which includes an oxidizer containing ammonium perchlorate, and a powered metal fuel, preferably aluminum or beryllium, in the form of a composite. The metal fuel is contained in the crystalline lattice framework of the oxidizer, as well as within the oxidizer particles, and is disposed in the interstices between the oxidizer particles of the composition. The propellant composition is produced by a process comprising the crystallization of ammonium perchlorate in water, in the presence of finely divided aluminum or beryllium. A suitable binder is incorporated in the propellant composition to bind the individual particles of metal with the particles of oxidizer containing occluded metal.

  2. Ammonia release method for depositing metal oxides

    DOEpatents

    Silver, G.L.; Martin, F.S.

    1994-12-13

    A method is described for depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates. 1 figure.

  3. Ammonia release method for depositing metal oxides

    DOEpatents

    Silver, Gary L.; Martin, Frank S.

    1994-12-13

    A method of depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates.

  4. Method for producing metal oxide nanoparticles

    DOEpatents

    Phillips, Jonathan; Mendoza, Daniel; Chen, Chun-Ku

    2008-04-15

    Method for producing metal oxide nanoparticles. The method includes generating an aerosol of solid metallic microparticles, generating plasma with a plasma hot zone at a temperature sufficiently high to vaporize the microparticles into metal vapor, and directing the aerosol into the hot zone of the plasma. The microparticles vaporize in the hot zone into metal vapor. The metal vapor is directed away from the hot zone and into the cooler plasma afterglow where it oxidizes, cools and condenses to form solid metal oxide nanoparticles.

  5. Reduced Graphene Oxide/Mesoporous TiO2 Nanocomposite Based Perovskite Solar Cells.

    PubMed

    Han, Gill Sang; Song, Young Hyun; Jin, Young Un; Lee, Jin-Wook; Park, Nam-Gyu; Kang, Bong Kyun; Lee, Jung-Kun; Cho, In Sun; Yoon, Dae Ho; Jung, Hyun Suk

    2015-10-28

    We report on reduced graphene oxide (rGO)/mesoporous (mp)-TiO2 nanocomposite based mesostructured perovskite solar cells that show an improved electron transport property owing to the reduced interfacial resistance. The amount of rGO added to the TiO2 nanoparticles electron transport layer was optimized, and their impacts on film resistivity, electron diffusion, recombination time, and photovoltaic performance were investigated. The rGO/mp-TiO2 nanocomposite film reduces interfacial resistance when compared to the mp-TiO2 film, and hence, it improves charge collection efficiency. This effect significantly increases the short circuit current density and open circuit voltage. The rGO/mp-TiO2 nanocomposite film with an optimal rGO content of 0.4 vol % shows 18% higher photon conversion efficiency compared with the TiO2 nanoparticles based perovskite solar cells.

  6. Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

    PubMed

    Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

    2016-05-20

    Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. One-pot synthesis of intermetallic electrocatalysts in ordered, large-pore mesoporous carbon/silica toward formic acid oxidation.

    PubMed

    Shim, Jongmin; Lee, Jaehyuk; Ye, Youngjin; Hwang, Jongkook; Kim, Soo-Kil; Lim, Tae-Hoon; Wiesner, Ulrich; Lee, Jinwoo

    2012-08-28

    This study describes the one-pot synthesis and single-cell characterization of ordered, large-pore (>30 nm) mesoporous carbon/silica (OMCS) composites with well-dispersed intermetallic PtPb nanoparticles on pore wall surfaces as anode catalysts for direct formic acid fuel cells (DFAFCs). Lab-synthesized amphiphilic diblock copolymers coassemble hydrophobic metal precursors as well as hydrophilic carbon and silica precursors. The final materials have a two-dimensional hexagonal-type structure. Uniform and large pores, in which intermetallic PtPb nanocrystals are significantly smaller than the pore size and highly dispersed, enable pore backfilling with ionomers and formation of the desired triple-phase boundary in single cells. The materials show more than 10 times higher mass activity and significantly lower onset potential for formic acid oxidation as compared with commercial Pt/C, as well as high stability due to better resistivity toward CO poisoning. In single cells, the maximum power density was higher than that of commercial Pt/C, and the stability highly improved, compared with commercial Pd/C. The results suggest that PtPb-based catalysts on large-pore OMCSs may be practically applied as real fuel cell catalysts for DFAFC.

  8. Nanostructured transition metal oxides useful for water oxidation catalysis

    DOEpatents

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  9. Heterogeneous oxidative desulfurization of diesel fuel catalyzed by mesoporous polyoxometallate-based polymeric hybrid.

    PubMed

    Yang, Huawei; Jiang, Bin; Sun, Yongli; Zhang, Luhong; Huang, Zhaohe; Sun, Zhaoning; Yang, Na

    2017-03-10

    In this work, the simple preparation of novel polymer supported polyoxometallates (POMs) catalysts has been reported. Soluble task-specific cross-linked poly (ionic liquid) (PIL) was prepared with N,​N-​dimethyl-​dodecyl-​(4-​vinylbenzyl) ammonium chloride and divinylbenzene as co-monomers. The as-prepared cationic PILs were assembled with different commercial POMs to form the interlinked mesoporous catalysts, and the formation mechanism was provided. The catalytic oxidation activities of the catalysts were closely related to the formation pathway of their corresponding peroxide active species. The catalyst with H2W12O42(10-) as counterion, which exhibited the best activity in the oxidation of benzothiophene (BT) and dibenzothiophene (DBT) to sulfones in model oil with hydrogen peroxide (H2O2, 30wt%) as oxidant, was characterized by different techniques and systematically studied for its sulfur removal performance. As for the oxidative desulfurization of a real diesel, it was observed that almost all of the original sulfur compounds could be completely converted, and the catalyst could be reused for at least eight cycles without noticeable changes in both catalytic activity and chemical structure. In the end, a catalytic mechanism was put forward with the assistant of Raman analysis.

  10. Mesoporous silica/ionic liquid quasi-solid-state electrolytes and their application in lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Yin, Kun; Yang, Li; Tachibana, Kazuhiro; Hirano, Shin-ichi

    2015-03-01

    In this work, the ordered mesoporous silica, SBA-15, is chosen as the matrix for the first time to prepare quasi-solid-state electrolytes (QSSEs) with an ionic liquid, LiTFSI salt and PVdF-HFP. The as-obtained QSSEs are evaluated by electrochemical methods. Lithium metal batteries containing these QSSEs exhibit high discharge capacity and good cycle performance at room temperature, indicating successful battery operation.

  11. Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

    SciTech Connect

    Yu, Xiaofang; Zou, Yongcun; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-06-15

    Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

  12. Ultrafine ferroferric oxide nanoparticles embedded into mesoporous carbon nanotubes for lithium ion batteries

    PubMed Central

    Gao, Guo; Zhang, Qiang; Cheng, Xin-Bing; Shapter, Joseph G.; Yin, Ting; Sun, Rongjin; Cui, Daxiang

    2015-01-01

    An effective one-pot hydrothermal method for in situ filling of multi-wall carbon nanotubes (CNT, diameter of 20–40 nm, length of 30–100 μm) with ultrafine ferroferric oxide (Fe3O4) nanoparticles (8–10 nm) has been demonstrated. The synthesized Fe3O4@CNT exhibited a mesoporous texture with a specific surface area of 109.4 m2 g−1. The loading of CNT, in terms of the weight ratio of Fe3O4 nanoparticles, can reach as high as 66.5 wt%. Compared to the conventional method of using a Al2O3 membrane as template to fill CNT with iron oxides nanoparticles, our strategy is facile, effective, low cost and easy to scale up to large scale production (~1.42 g per one-pot). When evaluated for lithium storage at 1.0 C (1 C = 928 mA g−1), the mesoporous Fe3O4@CNT can retain at 358.9 mAh g−1 after 60 cycles. Even when cycled at high rate of 20 C, high capacity of 275.2 mAh g−1 could still be achieved. At high rate (10 C) and long life cycling (500 cycles), the cells still exhibit a good capacity of 137.5 mAhg−1. PMID:26631536

  13. Metal oxide-based transparent conducting oxides

    NASA Astrophysics Data System (ADS)

    Gillispie, Meagen Anne

    Transparent conducting oxides (TCOs) are important materials widely used for transparent contacts in flat panel displays, light emitting diodes, and solar cells. While Sn-doped In2O3 (ITO) continues to be the TCO of choice, the increasing cost of raw In has resulted in an increasing interest in developing In-free alternatives to ITO. In this work, two metal oxide systems were investigated for their viability as In-free TCO materials. First, Nb- or Ta-doped anatase TiO2 was selected due to the recent reports of high conductivity in pulse laser deposited (PLD) films. Thin films doped with either 15 mol% Nb or 20 mol% Ta were deposited on glass and SrTiO3 (STO) substrates using RF magnetron sputtering techniques. In all cases, maximum conductivity was achieved when the films crystallized in the anatase structure of TiO2. Films sputtered on STO possessed similar electrical and optical properties as PLD films on STO, yet at a much lower deposition temperature while films deposited on glass had much lower conductivity, due to dramatically reduced mobility. Two-dimensional x-ray diffraction analysis showed that doped TiO2 films sputter deposited on STO were biaxially textured along the (004) direction. This texturing was not observed in films deposited on glass, which were composed of randomly-oriented crystalline anatase. Biaxial texturing in the film helps to reduce grain boundary resistance, thereby increasing carrier mobility and further enhancing conductivity. The Cu-based delafossite system (CuBO2, B is a 3+ metal cation) was selected as the second TCO material system due to its natural p-type conductivity, a rarity among existing TCOs. Study of this system was two-pronged: (1) application of codoping techniques to achieve bipolar conductivity; and (2) investigate stability of mixed B cation delafossites. CuAlO2 and CuGaO2 were both codoped with varying ratios of donors and acceptors in an attempt to achieve bipolar conductivity. Very little change in the electrical

  14. Biodegradable Magnetic Silica@Iron Oxide Nanovectors with Ultra-Large Mesopores for High Protein Loading, Magnetothermal Release, and Delivery.

    PubMed

    Omar, Haneen; Croissant, Jonas G; Alamoudi, Kholod; Alsaiari, Shahad; Alradwan, Ibrahim; Majrashi, Majed A; Anjum, Dalaver H; Martins, Patricia; Moosa, Basem; Almalik, Abdulaziz; Khashab, Niveen M

    2016-11-29

    The delivery of large cargos of diameter above 15nm for biomedical applications has proved challenging since it requires biocompatible, stably-loaded, and biodegradable nanomaterials. In this study, we describe the design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells. The mesopores of the nanomaterials spanned from 20 to 60nm in diameter and post-functionalization allowed the electrostatic immobilization of large proteins (e.g. mTFP-Ferritin, ~534kDa). Half of the content of the nanovectors was based with iron oxide nanophases which allowed the rapid biodegradation of the carrier in fetal bovine serum and a magnetic responsiveness. The nanovectors released large protein cargos in aqueous solution under acidic pH or magnetic stimuli. The delivery of large proteins was then autonomously achieved in cancer cells via the silica-iron oxide nanovectors, which is thus a promising for biomedical applications.

  15. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides.

    PubMed

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-21

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co(3)O(4), ZnO, Mn(2)O(3), MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N(2), whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N(2). Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N(2) and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H(2) and CO(2) adsorption properties depending on the environment used for the thermolysis of MOFs.

  16. Fabrication of Meso-Porous Sintered Metal Thin Films by Selective Etching of Silica Based Sacrificial Template

    PubMed Central

    Dumée, Ludovic F.; She, Fenghua; Duke, Mikel; Gray, Stephen; Hodgson, Peter; Kong, Lingxue

    2014-01-01

    Meso-porous metal materials have enhanced surface energies offering unique surface properties with potential applications in chemical catalysis, molecular sensing and selective separation. In this paper, commercial 20 nm diameter metal nano-particles, including silver and copper were blended with 7 nm silica nano-particles by shear mixing. The resulted powders were cold-sintered to form dense, hybrid thin films. The sacrificial silica template was then removed by selective etching in 12 wt% hydrofluoric acid solutions for 15 min to reveal a purely metallic meso-porous thin film material. The impact of the initial silica nano-particle diameter (7–20 nm) as well as the sintering pressure (5–20 ton·m−2) and etching conditions on the morphology and properties of the final nano-porous thin films were investigated by porometry, pyknometery, gas and liquid permeation and electron microscopy. Furthermore, the morphology of the pores and particle aggregation during shear mixing were assessed through cross-sectioning by focus ion beam milling. It is demonstrated that meso-pores ranging between 50 and 320 nm in average diameter and porosities up to 47% can be successfully formed for the range of materials tested.

  17. Polydopamine-graphene oxide derived mesoporous carbon nanosheets for enhanced oxygen reduction

    NASA Astrophysics Data System (ADS)

    Qu, Konggang; Zheng, Yao; Dai, Sheng; Qiao, Shi Zhang

    2015-07-01

    Composite materials combining nitrogen-doped carbon (NC) with active species represent a paramount breakthrough as alternative catalysts to Pt for the oxygen reduction reaction (ORR) due to their competitive activity, low cost and excellent stability. In this paper, a simple strategy is presented to construct graphene oxide-polydopamine (GD) based carbon nanosheets. This approach does not need to modify graphene and use any catalyst for polymerization under ambient conditions, and the obtained carbon nanosheets possess adjustable thicknesses and uniform mesoporous structures without using any template. The thickness of GD hybrids and the carbonization temperature are found to play crucial roles in adjusting the microstructure of the resulting carbon nanosheets and, accordingly their ORR catalytic activity. The optimized carbon nanosheet generated by a GD hybrid of 5 nm thickness after 900 °C carbonization exhibits superior ORR activity with an onset potential of -0.07 V and a kinetic current density of 13.7 mA cm-2 at -0.6 V. The unique mesoporous structure, high surface areas, abundant defects and favorable nitrogen species are believed to significantly benefit the ORR catalytic process. Furthermore, it also shows remarkable durability and excellent methanol tolerance outperforming those of commercial Pt/C. In view of the physicochemical versatility and structural tunability of polydopamine (PDA) materials, our work would shed new light on the understanding and further development of PDA-based carbon materials for highly efficient electrocatalysts.Composite materials combining nitrogen-doped carbon (NC) with active species represent a paramount breakthrough as alternative catalysts to Pt for the oxygen reduction reaction (ORR) due to their competitive activity, low cost and excellent stability. In this paper, a simple strategy is presented to construct graphene oxide-polydopamine (GD) based carbon nanosheets. This approach does not need to modify graphene and use

  18. Effects of Mesoporous Silica Coating and Post-Synthetic Treatment on the Transverse Relaxivity of Iron Oxide Nanoparticles

    PubMed Central

    Hurley, Katie R.; Lin, Yu-Shen; Zhang, Jinjin; Egger, Sam M.; Haynes, Christy L.

    2013-01-01

    Mesoporous silica nanoparticles have the capacity to load and deliver therapeutic cargo and incorporate imaging modalities, making them prominent candidates for theranostic devices. One of the most widespread imaging agents utilized in this and other theranostic platforms is nanoscale superparamagnetic iron oxide. Although several core-shell magnetic mesoporous silica nanoparticles presented in the literature have provided high T2 contrast in vitro and in vivo, there is ambiguity surrounding which parameters lead to enhanced contrast. Additionally, there is a need to understand the behavior of these imaging agents over time in biologically relevant environments. Herein, we present a systematic analysis of how the transverse relaxivity (r2) of magnetic mesoporous silica nanoparticles is influenced by nanoparticle diameter, iron oxide nanoparticle core synthesis, and the use of a hydrothermal treatment. This work demonstrates that samples which did not undergo a hydrothermal treatment experienced a drop in r2 (75% of original r2 within 8 days of water storage), while samples with hydrothermal treatment maintained roughly the same r2 for over 30 days in water. Our results suggest that iron oxide oxidation is the cause of the r2 loss, and this oxidation can be prevented both during synthesis and storage by the use of deoxygenated conditions during nanoparticle synthesis. The hydrothermal treatment also provides colloidal stability, even in acidic and highly salted solutions, and a resistance against acid degradation of the iron oxide nanoparticle core. The results of this study show the promise of multifunctional mesoporous silica nanoparticles but will also likely inspire further investigation into multiples types of theranostic devices, taking into consideration their behavior over time and in relevant biological environments. PMID:23814377

  19. Metal oxide composite dosimeter method and material

    DOEpatents

    Miller, Steven D.

    1998-01-01

    The present invention is a method of measuring a radiation dose wherein a radiation responsive material consisting essentially of metal oxide is first exposed to ionizing radiation. The metal oxide is then stimulating with light thereby causing the radiation responsive material to photoluminesce. Photons emitted from the metal oxide as a result of photoluminescence may be counted to provide a measure of the ionizing radiation.

  20. Incongruent sputtering in metal oxides

    NASA Astrophysics Data System (ADS)

    Langell, M. A.

    1987-11-01

    Preferential sputtering has been observed for NiO(100) and CoO(100) under low fluxes of 2 keV Ar +, with oxygen/metal sputtering yields a strong function of substrate temperature. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to follow the chemical and compositional nature of the surface for substrates prepared and characterized under UHV. Using O/M AES ratios as a measure of oxygen content, congruent sputtering was found for the oxides at 300 K for fluences of up to 10 17 Ar +/cm 2 and threshold temperatures for sputter reduction were observed at 350 K and 500 K for NiO and CoO, respectively. The relatively close thresholds for NiO and CoO sputter reduction argue against current thermal sputtering theory which predicts incongruent sputtering through oxygen vaporization. The temperature dependence of the O/M sputtering yields indicates that metal oxide sputtering is far more complex than current theory is able to describe. XPS data show evidence that adsorbed oxygen species, distinct from lattice oxygen, have formed on surfaces which have undergone sputter reduction and these species are postulated to play a role in the sputtering mechanism. MnO(100) crystals show no evidence for preferential sputtering for substrate temperature of up to 1000 K.

  1. Controllable Synthesis of Mesoporous Iron Oxide Nanoparticle Assemblies for Chemoselective Catalytic Reduction of Nitroarenes.

    PubMed

    Papadas, Ioannis T; Fountoulaki, Stella; Lykakis, Ioannis N; Armatas, Gerasimos S

    2016-03-18

    Iron(III) oxide is a low-cost material with applications ranging from electronics to magnetism, and catalysis. Recent efforts have targeted new nanostructured forms of Fe2O3 with high surface area-to-volume ratio and large pore volume. Herein, the synthesis of 3D mesoporous networks consisting of 4-5 nm γ-Fe2O3 nanoparticles by a polymer-assisted aggregating self-assembly method is reported. Iron oxide assemblies obtained from the hybrid networks after heat treatment have an open-pore structure with high surface area (up to 167 m(2)g(-1)) and uniform pores (ca. 6.3 nm). The constituent iron oxide nanocrystals can undergo controllable phase transition from γ-Fe2O3 to α-Fe2O3 and to Fe3O4 under different annealing conditions while maintaining the 3D structure and open porosity. These new ensemble structures exhibit high catalytic activity and stability for the selective reduction of aryl and alkyl nitro compounds to the corresponding aryl amines and oximes, even in large-scale synthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enhanced visible-light absorption of mesoporous TiO2 by co-doping with transition-metal/nitrogen ions

    SciTech Connect

    Mathis, John; Bi, Zhonghe; Bridges, Craig A; Kidder, Michelle; Paranthaman, Mariappan Parans

    2013-01-01

    Titanium (IV) oxide, TiO2, has been the object of intense scrutiny for energy applications. TiO2 is inexpensive, non-toxic, and has excellent corrosion resistance when exposed to electrolytes. A major drawback preventing the widespread use TiO2 for photolysis is its relatively large band gap of ~3eV. Only light with wavelengths shorter than 400 nm, which is in the ultraviolet portion of the spectrum, has sufficient energy to be absorbed. Less than 14 percent of the solar irradiation reaching the earth s surface has energy exceeding this band gap. Adding dopants such as transition metals has long been used to reduce the gap and increase photocatalytic activity by accessing the visible part of the solar spectrum. The degree to which the band gap is reduced using transition metals depends in part on the overlap of the d-orbitals of the transition metals with the oxygen p-orbitals. Therefore, doping with anions such as nitrogen to modify the cation-anion orbital overlap is another approach to reduce the gap. Recent studies suggest that using a combination of transition metals and nitrogen as dopants is more effective at introducing intermediate states within the band gap, effectively narrowing it. Here we report the synthesis of mesoporous TiO2 spheres, co-doped with transition metals and nitrogen that exhibit a nearly flat absorbance response across the visible spectrum extending into the near infrared.

  3. The oxidation of metals and alloys

    NASA Technical Reports Server (NTRS)

    Scheil, Erich

    1952-01-01

    This paper reviews the various types of oxidation processes occurring with pure metals and gives explanations for the varying time-temperature-oxidation rate relations that exist for copper, tungsten, zinc, cadmium, and tantalum. The effect of shape and crystal structure on oxidation is discussed. Principles derived are applied to the oxidation of alloys.

  4. Reduction of Metal Oxide to Metal using Ionic Liquids

    SciTech Connect

    Dr. Ramana Reddy

    2012-04-12

    A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode

  5. Metal oxides for optoelectronic applications.

    PubMed

    Yu, Xinge; Marks, Tobin J; Facchetti, Antonio

    2016-04-01

    Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

  6. Metal oxides for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Yu, Xinge; Marks, Tobin J.; Facchetti, Antonio

    2016-04-01

    Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

  7. Highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on reduced graphene oxide as an oxygen reduction electrocatalyst.

    PubMed

    Huang, Liang; Han, Yujie; Dong, Shaojun

    2016-07-05

    Herein, we develop a one-pot, two surfactant-assisted synthesis of highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on rGO with superior electrochemical performance for the ORR. Similarly to the interaction between Pluronic F127 and hexadecylpyridinium chloride (HDPC), this method may be extended to other nonionic/ionic surfactants to synthesize all-metal branched porous nanoparticles, and shows promising applications in electrochemistry and catalysis.

  8. Gold nanoparticles supported on mesoporous silica: origin of high activity and role of Au NPs in selective oxidation of cyclohexane

    PubMed Central

    Wu, Pingping; Bai, Peng; Yan, Zifeng; Zhao, George X. S.

    2016-01-01

    Homogeneous immobilization of gold nanoparticles (Au NPs) on mesoporous silica has been achieved by using a one-pot synthesis method in the presence of organosilane mercapto-propyl-trimethoxysilane (MPTMS). The resultant Au NPs exhibited an excellent catalytic activity in the solvent-free selective oxidation of cyclohexane using molecular oxygen. By establishing the structure-performance relationship, the origin of the high activity of mesoporous supported Au catalyst was identified to be due to the presence of low-coordinated Au (0) sites with high dispersion. Au NPs were confirmed to play a critical role in the catalytic oxidation of cyclohexane by promoting the activation of O2 molecules and accelerating the formation of surface-active oxygen species. PMID:26729288

  9. Mesoporous amorphous binary Ru–Ti oxides as bifunctional catalysts for non-aqueous Li–O2 batteries

    NASA Astrophysics Data System (ADS)

    Kim, Jisu; Jo, HeeGoo; Wu, Mihye; Yoon, Dae-Ho; Kang, Yongku; Jung, Ha-Kyun

    2017-04-01

    Mesoporous amorphous binary Ru–Ti oxides were prepared as bifunctional catalysts for non-aqueous Li–O2 batteries, and their electrochemical performance was investigated for the first time. A Li–O2 battery with mesoporous amorphous binary Ru–Ti oxides exhibited a remarkably high capacity of 27100 mAh g‑1 as well as a reduced overpotential. A GITT analysis suggested that the introduction of amorphous TiO2 to amorphous RuO2 was responsible for the enhanced kinetics toward both the oxygen reduction reaction and oxygen evolution reaction. Excellent cyclic stability up to 230 cycles was achieved, confirming the applicability of the new bifunctional catalyst in non-aqueous Li–O2 batteries.

  10. Mesoporous amorphous binary Ru-Ti oxides as bifunctional catalysts for non-aqueous Li-O2 batteries.

    PubMed

    Kim, Jisu; Jo, HeeGoo; Wu, Mihye; Yoon, Dae-Ho; Kang, Yongku; Jung, Ha-Kyun

    2017-04-07

    Mesoporous amorphous binary Ru-Ti oxides were prepared as bifunctional catalysts for non-aqueous Li-O2 batteries, and their electrochemical performance was investigated for the first time. A Li-O2 battery with mesoporous amorphous binary Ru-Ti oxides exhibited a remarkably high capacity of 27100 mAh g(-1) as well as a reduced overpotential. A GITT analysis suggested that the introduction of amorphous TiO2 to amorphous RuO2 was responsible for the enhanced kinetics toward both the oxygen reduction reaction and oxygen evolution reaction. Excellent cyclic stability up to 230 cycles was achieved, confirming the applicability of the new bifunctional catalyst in non-aqueous Li-O2 batteries.

  11. Ni-functionalized submicron mesoporous silica particles as a sorbent for metal affinity chromatography.

    PubMed

    Kurdyukov, Dmitry A; Chernova, Ekaterina N; Russkikh, Yana V; Eurov, Daniil A; Sokolov, Vasily V; Bykova, Anna A; Shilovskikh, Vladimir V; Keltsieva, Olga A; Ubyivovk, Eugenii V; Anufrikov, Yuri A; Fedorova, Anna V; Selyutin, Artem A; Sukhodolov, Nicolay G; Podolskaya, Ekaterina P; Golubev, Valery G

    2017-09-01

    In this research, a novel IMAC sorbent with high specificity for chlorine-containing compounds was developed. Ni-functionalized monodisperse spherical mesoporous silica particles of 500±25nm diameter were synthesized and their metal affinity properties were studied with the use of diclofenac as the model substance. The particles were aggregatively stable in the pH range of 3-12. The sorbent demonstrated a high adsorption capacity (0.60±0.06μg of DCF per 1mg of the sorbent) and high adsorption/desorption rate (20 and 5min was enough for the sorbent saturation and desorption of DCF, correspondingly). A mixture of eluents with addition of PFOS providing the almost complete recovery (98%) of diclofenac was first proposed. The monodispersity and the high sedimentation and aggregative stability of the particles provide the formation of a stable hydrosol even under ultrasound treatment which makes the mSiO2/Ni particles suitable for batch chromatography. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Ligand Symmetry Modulation for Designing a Mesoporous Metal-Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization.

    PubMed

    Du, Miao; Wang, Xi; Chen, Min; Li, Cheng-Peng; Tian, Jia-Yue; Wang, Zhuo-Wei; Liu, Chun-Sen

    2015-06-26

    A promising alternative strategy for designing mesoporous metal-organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn8(ad)4] (ad = adeninate) clusters and C3-symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8 nm) and hexagonal mesoporous (ca., 3.0 nm) 1D channels. Moreover, the resulting 446-MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of Co(II) or Ni(II) on the Zn(II) centers in 446-MOF can enhance the sorption capacities of CO2 and CH4 (16-21%), whereas the impregnation of Eu(III) and Tb(III) in the channels of 446-MOF will result in adjustable light-emitting behaviors.

  13. High temperature, oxidation resistant noble metal-Al alloy thermocouple

    NASA Technical Reports Server (NTRS)

    Smialek, James L. (Inventor); Gedwill, Michael G. (Inventor)

    1994-01-01

    A thermocouple is disclosed. The thermocouple is comprised of an electropositive leg formed of a noble metal-Al alloy and an electronegative leg electrically joined to form a thermocouple junction. The thermocouple provides for accurate and reproducible measurement of high temperatures (600 - 1300 C) in inert, oxidizing or reducing environments, gases, or vacuum. Furthermore, the thermocouple circumvents the need for expensive, strategic precious metals such as rhodium as a constituent component. Selective oxidation of rhodium is also thereby precluded.

  14. Sonochemical preparation and characterization of nanoporous transition metal oxides for environmental catalysis

    NASA Astrophysics Data System (ADS)

    Zhang, Lizhi

    A series of single and multi-component nanoporous transition metal oxides were prepared by sonochemical processing. This is based on a new idea that the controlled condensation and agglomeration of monodispersed sol particles would form a nanoporous structure with a narrow pore size distribution under ultrasound irradiation. Therefore, nanoporous transition metal oxides may be obtained without using surfactant templates. X-ray diffraction (XRD), nitrogen adsorption, UV-vis diffuse reflectance spectrometry, transmission electron microscopy (TEM), infrared (IR) spectrometry, thermalgravimetric analysis (TGA) and differential thermal analysis (DTA) were used to characterize the resulting materials. Compared with conventional surfactant-templated approaches, sonochemical method can avoid the collapse of the framework of nanoporous materials and the pollution arising from the removal of surfactant templates. The first part of the thesis describes the preparation of thermally stable mesoporous TiO2 under high intensity ultrasound irradiation. The photocatalytic activities of the resulting mesoporous TiO2 materials were evaluated by the degradation of volatile organic compounds. These sonochemically prepared mesoporous TiO2 showed better activities than the commercial photocatalyst P25. The reasons of the high activities of the mesoporous TiO 2 were discussed based on the characterization results in the thesis. Nanoporous ceria-zirconia solid solutions with high surface area were also prepared. It was found that the sonochemically prepared solid solutions possessed higher thermal stability than that synthesized by other conventional methods. XPS analysis showed that the molar ratios of Ce to Zr in solid solutions were quite close to that in the starting solutions. This study also confirmed that the addition of zirconia to ceria could enhance the thermal resistance of ceria. Nanoporous composites of amorphous titanium oxide and size-tunable strontium titanate nanocrystals

  15. Catalytic ozonation of selected pharmaceuticals over mesoporous alumina-supported manganese oxide.

    PubMed

    Yang, Li; Hu, Chun; Nie, Yulun; Qu, Jiuhui

    2009-04-01

    Catalytic ozonation of five pharmaceutical compounds (PhACs)-phenazone, ibuprofen, diphenhydramine, phenytoin, and diclofenac sodium in alumina-supported manganese oxide (MnOx) suspension was carried out with a semicontinuous laboratory reactor. MnOx supported by mesoporous alumina (MnOx/MA) was highly effective in mineralizing the PhACs in aqueous solution. Fourier transform infrared (FTIR) spectroscopy and in situ attenuated total reflection FTIR (ATR-FTIR) spectroscopy were used to examine the interaction of ozone with different catalysts undervarious conditions. The crucial active sites, surface oxide species at 1380 cm(-1), were formed by the interaction of ozone with Lewis acid sites on the alumina surface. New surface hydroxyl groups at 2915 and 2845 cm(-1) were produced by the interaction of the catalyst and ozone in aqueous suspension and became active sites in the presence of MnOx. The introduction of MnOx enhanced the formation and activation of surface hydroxyl groups, causing higher catalytic reactivity. On the basis of these findings, a reaction mechanism is proposed for the catalytic ozonation of PhACs in MnOx/MA suspension.

  16. Intrinsic catalytic role of mesoporous silica in preferential oxidation of carbon monoxide in excess hydrogen.

    PubMed

    Huang, Shengjun; Hara, Kenji; Fukuoka, Atsushi

    2012-04-10

    We have studied the intrinsic catalytic role of MCM-41 mesoporous silica in preferential oxidation of CO in excess H(2) (PROX). Two types of MCM-41 supports (MCM-41A and MCM-41B) were obtained from the same pristine as-synthesized materials by using different procedures for surfactant removal: one-step calcination or two-step extraction-calcination. Although two kinds of Pt catalysts prepared from the MCM-41 supports exhibit high similarity in apparent physicochemical parameters such as Pt morphology, particle-size distribution, electronic states, support architecture, and pore-size distribution, they show a dramatic difference in catalytic activity (ca. 100 % versus 10 % CO conversions at 298 K). This feature motivated us to investigate the catalytic role of MCM-41 in the PROX reaction. By means of infrared experiments with the isotope tracer technique, it was revealed that the reactive microenvironment at the interface between Pt and the MCM-41A support is the origin of the high activity. On the highly active Pt/MCM-41A catalyst, interfacial silanols play a decisive role in the ignition of CO oxidation, and gaseous O(2) and H(2) are dissociated on CO-free Pt sites created by the interfacial reaction. The dissociated oxygen and hydrogen are proposed to sustain the catalytic cycle in the form of regenerated silanols on the support, which is catalyzed by the Pt surface in the presence of H(2).

  17. Mesoporous Zirconium Titanium Oxides. Part 2: Synthesis, Porosity, and Adsorption Properties of Beads

    SciTech Connect

    Sizgek, G. Devlet; Sizgek, Erden; Griffith, Christopher S.; Luca, Vittorio

    2009-01-15

    Mesoporous zirconium titanium mixed-oxide beads having disordered wormhole textures and mole fractions of Zr (x) ranging from x = 0.25 to 0.67 have been prepared. The bead preparation method combined the forced hydrolysis of mixtures of zirconium-titanium alkoxides in the presence of long-chain carboxylates with external gelation. Uniformly sized beads could be produced in the size range 0.5--1.1 mm by varying the droplet size and viscosity of the mixed-oxide sol, thus making them suitable for large-scale column chromatographic applications. The beads exhibited narrow pore size distributions with similar mean pore diameters of around 3.7 nm. The specific surface areas of the beads were linked to the Zr mole fraction in the precursor solution and were generally greater than 350 m{sup 2}/g for x = 0.5. A combination of scanning transmission electron microscopy and X-ray absorption fine structure analysis indicated that the pore walls of the beads were composed of atomically dispersed Zr and Ti to form a continuous network of Zr-O-Ti bonds. Mass transport in the beads was evaluated by monitoring the kinetics of vanadate and vanadyl adsorption at pH 10.5 and 0.87, respectively.

  18. Fabrication of Ordered Mesoporous Silica with Encapsulated Iron Oxide Particles using Ferritin-Doped Block Copolymer Templates

    NASA Astrophysics Data System (ADS)

    Hess, D.; Watkins, J.; Naik, R.

    2006-03-01

    Recently, two-dimensional arrays of iron oxide clusters were fabricated by dip-coating a silica substrate into an aqueous solution. Here we report the encapsulation of ferritin in 3D mesoporous silica structures by the replication of block copolymer templates in supercritical CO2. In our approach, preparation of the highly ordered, doped template via spincasting and microphase separation and silica network formation occur in discreet steps. A solution of an amphiphilic PEO-PPO-PEO triblock copolymer (Pluronic) template, horse spleen ferritin and a low concentration of PTSA acid was prepared and spin-coated onto a Si wafer. Upon drying the block copolymer microphase separates resulting in partitioning of the acid catalyst and ferritin to the hydrophilic domain. The polymer template was then exposed to a solution of supercritical carbon dioxide and tetraethyl orthosilicate (TEOS) at 125 bar and 40^oC. Equilibrium limited CO2 sorption in the block copolymer template resulted in modest dialation of the microphase segregated structure. Under these conditions, the precursor was readily infused into the copolymer and reacted within the hydrophilic domain containing the acid catalyst. The resultant film was calcined in air at 400^oC for 6 hours producing a well-ordered iron oxide-doped mesoporous silica film. TEM and XRD revealed crystalline iron oxide structures within the mesoporous silica supports. Magnetic properties were analyzed using a superconducting quantum intereference device (SQUID).

  19. Facile synthesis of mesoporous Ce-Fe bimetal oxide and its enhanced adsorption of arsenate from aqueous solutions.

    PubMed

    Chen, Bo; Zhu, Zhiliang; Guo, Yanwei; Qiu, Yanling; Zhao, Jianfu

    2013-05-15

    The mesoporous Ce-Fe bimetal oxide (MCFO) was synthesized through a soft-template method and first applied in the adsorption of arsenate in aqueous solutions. The synthesized MCFO was characterized with BET surface area, X-ray diffraction (XRD), zeta potential, scanning electron microscope (SEM), and Fourier transform infrared (FTIR) analysis. The mesoporous structure of the MCFO was determined according to the characterization result. The adsorption efficiency of arsenate ions on the MCFO was studied as a function of initial As(V) concentration, contact time, pH, and coexistent anions. It was found that the adsorption isotherms could be well described by Langmuir model, and the calculated maximum adsorption capacity of MCFO-1 for As(V) was 91.74 mg g(-1), which was significantly greater than that of ordinary Ce-Fe bimetal oxide (CFO). The results showed that the adsorption kinetic data obeyed the pseudo-second order model. Lower pH was favorable for As(V) adsorption on the MCFO. Coexistent phosphate ions exhibited an obvious interference on As(V) adsorption, followed by silicate and fluoride ions. The analysis of BET and FTIR indicated that the high efficiency of As(V) adsorption on this Ce-Fe bimetal oxide (MCFO) was closely related to its uniform mesoporous structure and abundant surface hydroxyl groups. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Synthesis and characterization of magnetic iron oxide/calcium silicate mesoporous nanocomposites as a promising vehicle for drug delivery.

    PubMed

    Lu, Bing-Qiang; Zhu, Ying-Jie; Ao, Hai-Yong; Qi, Chao; Chen, Feng

    2012-12-01

    The synthesis of the mesoporous nanocomposites consisting of magnetic iron oxide nanoparticles and calcium silicate with uniform size has been a challenge, although they are the ideal potential agent for medical diagnosis and therapy. In this work, the core/shell structured mesoporous nanocomposites consisting of magnetic iron oxide nanoparticles as the core and calcium silicate as the shell have been successfully synthesized using a two liquid phase system by ultrasound irradiation, in which the hydrophobic phase is composed of hydrophobic Fe(3)O(4) nanoparticles and tetraethyl orthosilicate (TEOS), and the water phase consists of Ca(NO(3))(2), NaOH, and water. The hollow mesoporous nanocomposites consisting of magnetic iron oxide nanoparticles and calcium silicate are obtained by adding a certain amount of the inert hydrophobic solvent isooctane in the reaction system before ultrasound irradiation. The nanocomposites have a superparamagnetic behavior, high Brunauer-Emmett-Teller (BET) specific surface area (474 m(2) g(-1)), and high Barrett-Joyner-Halenda (BJH) pore volume (2.75 cm(3) g(-1)). The nanocomposites have high drug loading capacities for bovine hemoglobin, docetaxel, and ibuprofen. The docetaxel-loaded nanocomposites have the anticancer ability and, thus, are promising for applications in biomedical fields.

  1. Nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A.; Choi, Daiwon; Wang, Donghai; Yang, Zhenguo

    2013-10-15

    Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10 C.

  2. Photodegradation of chlorofluorocarbon alternatives on metal oxide

    SciTech Connect

    Tanaka, K.; Hisanaga, T. )

    1994-05-01

    HCFC and HFC were photodegraded on metal oxides. Degradation rate on several metal oxides was in the order: TiO[sub 2] > ZnO > Fe[sub 2]O[sub 3] > kaolin [ge] SiO[sub 2] [ge] Al[sub 2]O[sub 3]. Principal degradation products were CO[sub 2], Cl[sup [minus

  3. Nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A.; Choi, Daiwon; Wang, Donghai; Yang, Zhenguo

    2012-09-04

    Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10C.

  4. Nanocomposite of graphene and metal oxide materials

    DOEpatents

    Liu, Jun; Aksay, Ilhan A.; Choi, Daiwon; Wang, Donghai; Yang, Zhenguo

    2015-06-30

    Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10 C.

  5. Thermal conductivity studies of novel nanofluids based on metallic silver decorated mesoporous silica nanoparticles

    SciTech Connect

    Tadjarodi, Azadeh; Zabihi, Fatemeh

    2013-10-15

    Graphical abstract: - Highlights: • Metallic silver was decorated in mSiO{sub 2} with grafted hemiaminal functional groups. • Synthesized nanoparticles were used for preparation of glycerol based nanofluids. • The effect of temperature, weight fraction of mSiO{sub 2} and concentration of silver nanoparticles on thermal conductivity of nanofluids was investigated. - Abstract: In the present study, the mesoporous structure of silica (mSiO{sub 2}) nanoparticles as well as hemiaminal grafted mSiO{sub 2} decorated by metallic silver (Ag/mSiO{sub 2}) has been used for the preparation of glycerol based nanofluids. Structural and morphological characterization of the synthesized products have been carried out using Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray diffraction (XRD), UV–vis spectroscopy, inductively coupled plasma (ICP) and N{sub 2} adsorption–desorption isotherms. The thermal conductivity and viscosity of the nanofluids have been measured as a function of temperature for various weight fractions and silver concentrations of mSiO{sub 2} and Ag/mSiO{sub 2} nanoparticles, respectively. The results show that the thermal conductivity of the nanofluids increase up to 9.24% as the weight fraction of mSiO{sub 2} increases up to 4 wt%. Also, increasing the percent of the silver decorated mSiO{sub 2} (Ag/mSiO{sub 2}) up to 2.98% caused an enhancement in the thermal conductivity of the base fluid up to 10.95%. Furthermore, the results show that the nanofluids have Newtonian behavior in the tested temperature range for various concentrations of nanoparticles.

  6. Investigating the Heavy Metal Adsorption of Mesoporous Silica Materials Prepared by Microwave Synthesis

    NASA Astrophysics Data System (ADS)

    Zhu, Wenjie; Wang, Jingxuan; Wu, Di; Li, Xitong; Luo, Yongming; Han, Caiyun; Ma, Wenhui; He, Sufang

    2017-05-01

    Mesoporous silica materials (MSMs) of the MCM-41 type were rapidly synthesized by microwave heating using silica fume as silica source and evaluated as adsorbents for the removal of Cu2+, Pb2+, and Cd2+ from aqueous solutions. The effects of microwave heating times on the pore structure of the resulting MSMs were investigated as well as the effects of different acids which were employed to adjust the solution pH during the synthesis. The obtained MCM-41 samples were characterized by nitrogen adsorption-desorption analyses, X-ray powder diffraction, and transmission electron microscopy. The results indicated that microwave heating method can significantly reduce the synthesis time of MCM-41 to 40 min. The MCM-41 prepared using citric acid (c-MCM-41(40)) possessed more ordered hexagonal mesostructure, higher pore volume, and pore diameter. We also explored the ability of c-MCM-41(40) for removing heavy metal ions (Cu2+, Pb2+, and Cd2+) from aqueous solution and evaluated the influence of pH on its adsorption capacity. In addition, the adsorption isotherms were fitted by Langmuir and Freundlich models, and the adsorption kinetics were assessed using pseudo-first-order and pseudo-second-order models. The intraparticle diffusion model was studied to understand the adsorption process and mechanism. The results confirmed that the as-synthesized adsorbent could efficiently remove the heavy metal ions from aqueous solution at pH range of 5-7. The adsorption isotherms obeyed the Langmuir model, and the maximum adsorption capacities of the adsorbent for Cu2+, Pb2+, and Cd2+ were 36.3, 58.5, and 32.3 mg/g, respectively. The kinetic data were well fitted to the pseudo-second-order model, and the results of intraparticle diffusion model showed complex chemical reaction might be involved during adsorption process.

  7. Immobilization of chloroperoxidase on mesoporous materials for the oxidation of 4,6-dimethyldibenzothiophene, a recalcitrant organic sulfur compound present in petroleum fractions.

    PubMed

    Terrés, Eduardo; Montiel, Mayra; Le Borgne, Sylvie; Torres, Eduardo

    2008-01-01

    The catalytic potential of chloroperoxidase (CPO) immobilized on mesoporous materials was evaluated for the oxidation of 4,6-dimethyldibenzothiophene in water/acetonitrile mixtures. Two different types of materials were used for the immobilization: a metal containing Al-MCM-41 material with a pore size of 26 A and SBA-16 materials with three different pore sizes: 40, 90 and 117 A. The SBA-16 40 A did not retain any CPO. The nature and the pore size of the material affected the catalytic activity of the enzyme as well as its stability. Compared to the free enzyme, the thermal stability of CPO at 45 degrees C was two and three times higher than when immobilized on Al-MCM-41 and SBA-16 90 A, respectively.

  8. Surface protected lithium-metal-oxide electrodes

    DOEpatents

    Thackeray, Michael M.; Kang, Sun-Ho

    2016-04-05

    A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

  9. Methods of producing adsorption media including a metal oxide

    DOEpatents

    Mann, Nicholas R; Tranter, Troy J

    2014-03-04

    Methods of producing a metal oxide are disclosed. The method comprises dissolving a metal salt in a reaction solvent to form a metal salt/reaction solvent solution. The metal salt is converted to a metal oxide and a caustic solution is added to the metal oxide/reaction solvent solution to adjust the pH of the metal oxide/reaction solvent solution to less than approximately 7.0. The metal oxide is precipitated and recovered. A method of producing adsorption media including the metal oxide is also disclosed, as is a precursor of an active component including particles of a metal oxide.

  10. Three-electrode metal oxide reduction cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2008-08-12

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  11. Method for making monolithic metal oxide aerogels

    DOEpatents

    Droege, M.W.; Coronado, P.R.; Hair, L.M.

    1995-03-07

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels. 6 figs.

  12. Method for making monolithic metal oxide aerogels

    DOEpatents

    Droege, Michael W.; Coronado, Paul R.; Hair, Lucy M.

    1995-01-01

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels.

  13. Three-Electrode Metal Oxide Reduction Cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2005-06-28

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  14. Direct electrochemical reduction of metal-oxides

    DOEpatents

    Redey, Laszlo I.; Gourishankar, Karthick

    2003-01-01

    A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

  15. Synthesis of metal oxide nanoparticles via a robust ``solvent-deficient'' method

    NASA Astrophysics Data System (ADS)

    Smith, Stacey J.; Huang, Baiyu; Liu, Shengfeng; Liu, Qingyuan; Olsen, Rebecca E.; Boerio-Goates, Juliana; Woodfield, Brian F.

    2014-11-01

    We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2-3 simple steps; a hydrated metal salt (usually a nitrate or chloride salt) is ground with bicarbonate (usually NH4HCO3) for 10-30 minutes to form a precursor that is then either untreated or rinsed before being calcined at relatively low temperatures (220-550 °C) for 1-3 hours. The method is thus similar to surfactant-free aqueous methods such as co-precipitation but is unique in that no solvents are added. The resulting ``solvent-deficient'' environment has interesting and unique consequences, including increased crystallinity of the products over other aqueous methods and a mesoporous nature in the inevitable agglomerates. The products are chemically pure and phase pure with crystallites generally 3-30 nm in average size that aggregate into high surface area, mesoporous agglomerates 50-300 nm in size that would be useful for catalyst and gas sensing applications. The versatility of products and efficiency of the method lend its unique potential for improving the industrial viability of a broad family of useful metal oxide nanomaterials. In this paper, we outline the methodology of the solvent-deficient method using our understanding of its mechanism, and we describe the range and quality of nanomaterials it has produced thus far.We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2

  16. Metal Oxide Solubility and Molten Salt Corrosion.

    DTIC Science & Technology

    1982-03-29

    METAL OXIDE SOLUBILITY AND MOLTEN SALT CORROSION.(U) MAR 82 K H STERN UNCLASSI E DL R L-4772NL EL .2. MICROCOPY RESOLUTION TEST CHART NATIONAL BURALU...METAL OXIDE SOLUBILITY AND MOLTEN SALT Interim report on a continuing CORROSION NRL problem. S. PERFORMING a4. REPORT NUMlER 7. AuTtwORr) S. CONTRACT OR...EQUILIBRIA AND OXIDE SOLUTION RELATIONS IN MOLTEN SALTS ............................................. 2 IV. METHODS FOR DETERMINING SOLUBILITIES

  17. Metal Oxide Reduction Linked to Anaerobic Methane Oxidation.

    PubMed

    Oni, Oluwatobi E; Friedrich, Michael W

    2017-02-01

    Microbial methanotrophy is important in mitigating methane emissions to the atmosphere. Geochemical evidence suggests the occurrence of anaerobic methane oxidation with metal oxides in natural environments. A study has now identified, for the first time, novel freshwater archaea of the order Methanosarcinales that can oxidize methane with Fe(III) and Mn(IV) minerals as electron acceptors.

  18. Effect of iron oxide loading on the phase transformation and physicochemical properties of nanosized mesoporous ZrO{sub 2}

    SciTech Connect

    Basahel, S.N.; Ali, Tarek T.; Narasimharao, K.; Bagabas, A.A.; Mokhtar, M.

    2012-11-15

    Highlights: ► Modified preparation method for nanosized iron oxide supported ZrO{sub 2} catalysts. ► Systematic study of effect of high iron oxide loading over ZrO{sub 2}. ► Influence of iron oxide on the stabilization of tetragonal ZrO{sub 2} phase. ► A mesoporous nature of zirconia changed upon changing iron oxide loading. ► Surface to bulk migration of iron oxide evidenced by XPS technique. -- Abstract: Mesoporous ZrO{sub 2}-supported iron oxide materials were prepared with nominal loadings of iron oxide of 5, 10, 15 and 20 wt.% using a modified co-precipitation method. The physicochemical properties of the catalysts were characterized by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy, N{sub 2} adsorption, X-ray photoelectron spectroscopy and infrared spectroscopy methods. A delay in the ZrO{sub 2} phase transformation as a result of the incorporation of iron was determined using TG/DSC measurements. XRD, Raman spectroscopy and HRTEM results revealed that an increase of iron oxide loading from 5 to 15 wt.% enhanced the transformation of the monoclinic to tetragonal phase. Unexpectedly, 20 wt.% iron oxide loading was required for complete tetragonal structure stabilization due to the mesoporosity of the ZrO{sub 2} support. Iron oxide loadings from 5 to 15 wt.% showed an increase in the BET-surface area due to the presence of amorphous iron oxide on the surface. XPS and FTIR results indicated that increasing the iron oxide content to 20 wt.% resulted in stabilization of the tetragonal zirconia phase as a result of surface-to-bulk migration and incorporation of Fe{sup 3+} ions in the ZrO{sub 2} lattice.

  19. Magnetic mesoporous material for the sequestration of algae

    DOEpatents

    Trewyn, Brian G.; Kandel, Kapil; Slowing, Igor Ivan; Lee, Show-Ling

    2014-09-09

    The present invention provides a magnetic mesoporous nanoparticle that includes a mesoporous silicate nanoparticle and iron oxide. The present invention also provides a method of using magnetic mesoporous nanoparticles to sequester microorganisms from a media.

  20. Mesoporous iron oxide nanoparticles prepared by polyacrylic acid etching and their application in gene delivery to mesenchymal stem cells.

    PubMed

    Cao, Binrui; Qiu, Penghe; Mao, Chuanbin

    2013-09-01

    Novel monodisperse mesoporous iron oxide nanoparticles (m-IONPs) were synthesized by a postsynthesis etching approach and characterized by electron microscopy. In this approach, solid iron oxide nanoparticles (s-IONPs) were first prepared following a solvothermal method, and then etched anisotropically by polyacrylic acid to form the mesoporous nanostructures. MTT cytotoxicity assay demonstrated that the m-IONPs have good biocompatibility with mesenchymal stem cells (MSCs). Owing to their mesoporous structure and good biocompatibility, these monodisperse m-IONPs were used as a nonviral vector for the delivery of a gene of vascular endothelial growth factor (VEGF) tagged with a green fluorescence protein (GFP) into the hard-to-transfect stem cells. Successful gene delivery and transfection were verified by detecting the GFP fluorescence from MSCs using fluorescence microscopy. Our results illustrated that the m-IONPs synthesized in this work can serve as a potential nonviral carrier in gene therapy where stem cells should be first transfected and then implanted into disease sites for disease treatment. Copyright © 2013 Wiley Periodicals, Inc.

  1. Recent developments in complex metal oxide photoelectrodes

    NASA Astrophysics Data System (ADS)

    Abdi, Fatwa F.; Berglund, Sean P.

    2017-05-01

    Photoelectrochemical (PEC) water splitting, a process that directly produces hydrogen from water and sunlight using semiconductor materials, is an attractive form of renewable energy production. The hydrogen that is produced can be easily transported, stored, and utilized as a fuel without the emission of greenhouse gasses. However, many scientific and engineering challenges need to be overcome before PEC water splitting can be implemented on a large scale. One of the biggest challenges is the identification of suitable semiconductor materials to use in the construction of photoelectrodes. This topical review highlights a promising class of materials, complex metal oxides, which can be used as photoelectrodes for PEC water splitting. The advantages and limitations of complex metal oxides are first discussed, and strategies to overcome the limitations are outlined using the model case of bismuth vanadate (BiVO4), one of the highest performing complex metal oxide photoanodes reported to date. Building on the success story of BiVO4, we discuss pathways towards achieving even higher water splitting performance, including bandgap engineering as well as the development of alternative complex metal oxides with more appropriate bandgaps for obtaining high solar-to-hydrogen efficiency. Several classes of complex metal oxides (e.g. delafossites, tungstates, vanadates, spinels) are presented as promising candidates for photoelectrode materials. Finally, we conclude by summarizing the key properties of these complex metal oxides and providing an outlook towards expedited discovery of new and novel complex metal oxides for use as photoelectrodes.

  2. Mesoporous magnesium oxide nanoparticles derived via complexation-combustion for enhanced performance in carbon dioxide capture.

    PubMed

    Hiremath, Vishwanath; Shavi, Raghavendra; Gil Seo, Jeong

    2017-03-10

    Magnesium oxide (MgO) is a promising candidate for carbon dioxide (CO2) capture at high temperature applicable to pre-combustion capture in an integrated gasification combined cycle (IGCC) scheme. In this work, mesoporous MgO nanoparticles were synthesized via simple complexation-combustion method by using glycine (G) and urea (U) as fuels (F). The obtained sorbents were thoroughly characterized in terms of the crystalline structure, morphology, nature of the fuel, F/O ratio, and their consequent effects on CO2 sorption. It was observed that due to the complexation followed by combustion in the presence of glycine, MgO with crystallite size as small as∼8nm could be derived. The synthesized MgO nanoparticles exhibited exceptionally high CO2 sorption at elevated temperatures. Furthermore, CO2 sorption isotherms in assistance with FT-IR and DSC experiments demonstrated that the low CO2 uptake at ambient temperature (25-100°C) may be due to the formation of monodentate carbonates, whereas predominant bicarbonates enhance the CO2 uptake at elevated temperatures (100-300°C). MgO-1.5(G) obtained the highest sorption corresponding to 1.34mmol/g at 200°C.

  3. Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal-Organic Frameworks.

    PubMed

    Gómez-Gualdrón, Diego A; Moghadam, Peyman Z; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

    2016-01-13

    Metal-organic frameworks (MOFs) can exhibit exceptionally high surface areas, which are experimentally estimated by applying the BET theory to measured nitrogen isotherms. The Brunauer, Emmett, and Teller (BET)-estimated nitrogen monolayer loading is thus converted to a "BET area," but the meaning of MOF BET areas remains under debate. Recent emphasis has been placed on the usage of four so-called "BET consistency criteria." Using these criteria and simulated nitrogen isotherms for perfect crystals, we calculated BET areas for graphene and 25 MOFs having different pore-size distributions. BET areas were compared with their corresponding geometrically calculated, nitrogen-accessible surface areas (NASAs). Analysis of simulation snapshots elucidated the contributions of "pore-filling" and "monolayer-formation" to the nitrogen adsorption loadings in different MOF pores, revealing the origin of inaccuracies in BET-calculated monolayer loadings, which largely explain discrepancies between BET areas and NASAs. We also find that even if all consistency criteria are satisfied, the BET calculation can significantly overestimate the true monolayer loading, especially in MOFs combining mesopores (d ≥ 20 Å) and large micropores (d = 10-20 Å), due to the overlap of pore-filling and monolayer-formation regimes of these two kinds of pores. While it is not always possible to satisfy all consistency criteria, it is critical to minimize the deviation from these criteria during BET range selection to consistently compare BET areas of different MOFs and for comparing simulated and experimental BET areas of a given MOF. To accurately assess the quality of a MOF sample, it is best to compare experimental BET areas with simulated BET areas rather than with calculated NASAs.

  4. PdCl2-loading mesoporous copper oxide as a novel and environmentally friendly catalyst for diethyl carbonate synthesis

    NASA Astrophysics Data System (ADS)

    Zhang, Pingbo; Zhou, Yan; Fan, Mingming; Jiang, Pingping

    2015-03-01

    PdCl2-loading mesoporous copper oxide (PdCl2/mCuO) catalysts were successfully synthesized via a hard template with copper carbonate basic (Cu2(OH)2CO3), cupric nitrate (Cu(NO3)2·3H2O) and copper citrate (Cu2C6H4O7·2.5H2O) as the copper(II) precursors, respectively. Their catalytic performances were investigated in the synthesis of diethyl carbonate (DEC) by oxidative carbonylation of ethanol with CO and O2. The catalysts were characterized by TGA, XRD, nitrogen adsorption-desorption analysis and SEM with the aim of establishing their composition, morphology and structure. It was observed that the catalysts all showed a good selectivity to diethyl carbonate. However, due to a better mesoporous structure such as a bigger surface area, more uniform particle size and less agglomeration, the PdCl2/mCuO-1 catalyst prepared with Cu2(OH)2CO3 precursor showed a better catalytic activity that the conversion of EtOH was about 4.8% and the STY of DEC was 97.1 mg g-1 h-1. This was because the highly developed mesoporous structure could generate a bigger surface area, which benefited the contact between reactants and active sites, improved the conversion of ethanol, and thus enhanced the catalytic performance. Furthermore, a synthetic procedure diagram about "wet impregnation" method of mesoporous CuO prepared with Cu2(OH)2CO3 precursor was given to illustrate these results intuitively.

  5. Oxidation of a mustard gas analogue using an aldehyde/O2 system catalyzed by V-doped mesoporous silica.

    PubMed

    Livingston, Stephanie R; Landry, Christopher C

    2008-10-08

    Vanadium-doped mesoporous silica was shown to be an effective heterogeneous catalyst for the oxidation of a mustard gas analogue, 2-chloroethyl ethyl sulfide (CEES), in the presence of an aldehyde and molecular oxygen. The oxidation was shown to involve a radical mechanism, which was indicated by the appearance of an induction period when the reaction occurred in the presence of a free radical scavenger. The reaction was initially selective for the oxidation of CEES to the sulfoxide, CEESO, although oxidation of the sulfoxide to the sulfone occurred once all the CEES had been oxidized. Chemical analysis indicated that V species did not leach from the silica support when the reaction was performed in the fluorinated solvent HFE-7100.

  6. Au/metal oxides for low temperature CO oxidation

    SciTech Connect

    Srinivas, G.; Wright, J.; Bai, C.S.; Cook, R.

    1996-12-31

    Oxidation of carbon monoxide is important for several operations including fuel cells and carbon dioxide lasers. Room temperature CO oxidation has been investigated on a series of Au/metal oxide catalysts at conditions typical of spacecraft atmospheres; CO = 50 ppm, CO{sub 2} = 7,000 ppm, H{sub 2}O = 40% (RH) at 25{degrees}C, balance = air, and gas hourly space velocities of 7,000-60,000 hr{sup -1}. The addition of Au increases the room temperature CO oxidation activity of the metal oxides dramatically. All the Au/metal oxides deactivate during the CO oxidation reaction, especially in the presence of CO{sub 2} in the feed. The stability of the Au/metal oxide catalysts decreases in the following order: TiO{sub 2} > Fe{sub 2}O{sub 3} > NiO > Co{sub 3}O{sub 4}. The stability appears to decrease with an increase in the basicity of the metal oxides. In situ FTIR of CO adsorption on Au/TiO{sub 2} at 25{degrees}C indicates the formation of adsorbed CO, carboxylate, and carbonate species on the catalyst surface.

  7. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

    1984-01-06

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

  8. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  9. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang

    2016-11-04

    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the 'nanocasting' technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  10. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang

    2016-11-01

    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the ‘nanocasting’ technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  11. Mesoporous VN prepared by solid-solid phase separation

    SciTech Connect

    Yang Minghui; Ralston, Walter T.; Tessier, Franck; Allen, Amy J.; DiSalvo, Francis J.

    2013-01-15

    We recently reported a simple route to prepare mesoporous, conducting nitrides from Zn containing ternary transition metal oxides. Those materials result from the condensation of atomic scale voids created by the loss of Zn by evaporation, the replacement of 3 oxygen anions by 2 nitrogen anions, and in most cases the loss of oxygen to form water on the reduction of the transition metal. In this report, we present a different route to prepare mesoporous VN from K containing vanadium oxides. In this case, ammonolysis results in a multiphase solid product that contains VN, and other water soluble compounds such as KOH or KNH{sub 2}. On removing the K containing products by washing with degassed water, only mesoporous VN remains. VN materials with different pore sizes (10 nm-20 nm) were synthesized at 600 Degree-Sign C by varying the reaction time, while larger pores are obtained at higher temperatures (50 nm at 800 Degree-Sign C). - Graphical Abstract: The synthesis process of mesoporous VN from solid-solid separation. Highlights: Black-Right-Pointing-Pointer Mesoporous VN has been prepared by solid-solid phase separation. Black-Right-Pointing-Pointer Mesoporous VN was characterized by Rietveld refinement of PXRD, SEM and nitrogen physisorption. Black-Right-Pointing-Pointer VN materials with different pore sizes (10 nm-50 nm) were synthesized.

  12. Metal Alkoxides - Models for Metal Oxides.

    DTIC Science & Technology

    1982-07-29

    metal bonded adaptations of the well known hollandite structure and closely -elated to the cluster found for CsNbCi1 1 . Triangulo Mo3 and W3 units are... triangulo complex- es as is shown in Figure 2. In both cases, the molybdenum atoms are surrounded by six oxygen ligands in a distorted octahedral manner

  13. [Metal-Organic Frameworks: A New Class of Mesoporous Materials and Potential Possibilities of Their Use in Pharmaceutical Technology].

    PubMed

    Wyszogrodzka, Gabriela; Dorożyński, Przemysław

    2015-01-01

    Metal-organic frameworks (MOFs) belong to the new class of mesoporous, hybrid materials composed of metal ions and organic binding ligands. Their unique features: wide range of chemical building components, which enables obtaining biocompatible materials, and high surface area and loading capacity, make them promising drug delivery vehicles for therapeutic agents. The ability to tune their structures and porosities provides better adjustment for adsorbed drug molecule. Moreover, MOFs functionalized with ligands or antibodies can be used in cancer targeted therapy. Through the incorporation of paramagnetic metal ions into the structure, MOFs are suited to serve as magnetic resonance imaging (MRI) contrast agents. Combining drug delivery ability with imaging properties of MOFs indicates their potential use as theranostic agents and makes possible monitoring drug delivery within the body after administration in the real time. The aim of the present study is to characterize a new class of compounds and to present potential possibilities of their use as excipients in pharmaceutical technology .

  14. Immobilization of Thiadiazole Derivatives on Magnetite Mesoporous Silica Shell Nanoparticles in Application to Heavy Metal Removal from Biological Samples

    SciTech Connect

    Emadi, Masoomeh; Shams, Esmaeil

    2010-12-02

    In this report magnetite was synthesized by a coprecipitation method, then coated with a layer of silica. Another layer of mesoporous silica was added by a sol-gel method, then 5-amino-1,3,4-thiadiazole-thiol (ATT) was immobilized onto the synthesized nanoparticles with a simple procedure. This was followed by a series of characterizations, including transmission electron microscopy (TEM), FT-IR spectrum, elemental analysis and XRD. Heavy metal uptake of the modified nanoparticles was examined by atomic absorption spectroscopy. For further investigation we chose Cu{sup 2+} as the preferred heavy metal to evaluate the amount of adsorption, as well as the kinetics and mechanism of adsorption. Finally, the capacity of our nanoparticles for the heavy metal removal from blood was shown. We found that the kinetic rate of Cu{sup 2+} adsorption was 0.05 g/mg/min, and the best binding model was the Freundlich isotherm.

  15. Trace metal concentrations in oxidation ponds

    SciTech Connect

    Suffern, J.S.; Fitzgerald, C.M.; Szluha, A.T.

    1981-11-01

    Heavy metal concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the wastewater, sludge, and biotic components of the Oak Ridge National Laboratory oxidation ponds were examined to determine whether metals accumulated in tilapia. Results indicated that metal levels in the wastewater and biotic components are generally low and that the major metal reservoir is the sludge. Metals did not accumulate beyond established standards in the muscle or liver of tilapia grown in the oxidation ponds. This result may be partially due to the rapid growth rates of these fish (1-2 g fish/sup -1//day/sup -1/), with new tissue developing more rapidly than metals can accumulate. Another factor may be that the high concentrations of organic complexes in the ponds lower the availability of metals to the biota.

  16. [Fe(CN)6]4- decorated mesoporous gelatin thin films for colorimetric detection and as sorbents of heavy metal ions.

    PubMed

    Shi, Li; Huang, Hubiao; Sun, Luwei; Lu, Yanping; Du, Binyang; Mao, Yiyin; Li, Junwei; Ye, Zhizhen; Peng, Xinsheng

    2013-09-28

    [Fe(CN)6](4-) decorated mesoporous gelatin films, acting as colorimetric sensors and sorbents for heavy metal ions, were prepared by incorporating [Fe(CN)6](4-) ions into the mesoporous gelatin films through electrostatic interaction. Gelatin-Prussian blue (PB) and gelatin-PB analogue composite films were successfully synthesized by immersing the [Fe(CN)6](4-) decorated gelatin films into aqueous solutions of metal ions, such as Fe(3+), Cu(2+), Co(2+), Pb(2+) and Cd(2+) (all as nitrates). The in situ formation process of PB or its analogues in the films was investigated using quartz crystal microbalance (QCM) measurements. According to the different colors of the PB nanoparticles and its analogues, the [Fe(CN)6](4-) decorated mesoporous gelatin films demonstrated colorimetric sensor abilities for detecting the corresponding metal ions by the naked eye with sufficient sensitivity at 1 ppm level and a quite short response time of 5 minutes. Moreover, due to the [Fe(CN)6](4-) functionality and other functional groups of gelatin itself, this [Fe(CN)6](4-) decorated mesoporous gelatin film shows a tens times higher adsorption ability for heavy metal ions in water than that of activated carbon. Due to both the efficient detection and high adsorption ability for heavy metal ions, this film has wide potential applications for the detection and purification of heavy metal ions from polluted water.

  17. Design and functionalization of photocatalytic systems within mesoporous silica.

    PubMed

    Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

    2014-06-01

    In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described.

  18. Facile synthesis and unique physicochemical properties of three-dimensionally ordered macroporous magnesium oxide, gamma-alumina, and ceria-zirconia solid solutions with crystalline mesoporous walls.

    PubMed

    Li, Huining; Zhang, Lei; Dai, Hongxing; He, Hong

    2009-05-18

    Three-dimensionally (3D) ordered macroporous (3DOM) MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) with polycrystalline mesoporous walls have been successfully fabricated with the triblock copolymer EO(106)PO(70)EO(106) (Pluronic F127) and regularly packed monodispersive polymethyl methacrylate (PMMA) microspheres as the template and magnesium, aluminum, cerium and zirconium nitrate(s), or aluminum isopropoxide as the metal source. The as-synthesized metal oxides were characterized by means of techniques such as X-ray diffraction (XRD), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), Fourier transform infrared (FT-IR), high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy/selected area electron diffraction (HRTEM/SAED), BET, carbon dioxide temperature-programmed desorption (CO(2)-TPD), and hydrogen temperature-programmed reduction (H(2)-TPR). It is shown that the as-fabricated MgO, gamma-Al(2)O(3), Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples possessed single-phase polycrystalline structures and displayed a 3DOM architecture; the MgO, Ce(0.6)Zr(0.4)O(2), and Ce(0.7)Zr(0.3)O(2) samples exhibited worm-hole-like mesoporous walls, whereas the gamma-Al(2)O(3) samples exhibited 3D ordered mesoporous walls. The solvent (ethanol or water) nature and concentration, metal precursor, surfactant, and drying condition have an important impact on the pore structure and surface area of the final product. The introduction of surfactant F127 to the synthesis system could significantly enhance the surface areas of the 3DOM metal oxides. With PMMA and F127 in a 40% ethanol solution, one can generate well-arrayed 3DOM MgO with a surface area of 243 m(2)/g and 3DOM Ce(0.6)Zr(0.4)O(2) with a surface area of 100 m(2)/g; with PMMA and F127 in an ethanol-HNO(3) solution, one can obtain 3DOM gamma-Al(2)O(3)with a surface area of 145 m(2)/g. The 3DOM MgO and 3DOM gamma-Al(2)O(3) samples showed

  19. Multilevel metallization method for fabricating a metal oxide semiconductor device

    NASA Technical Reports Server (NTRS)

    Hollis, B. R., Jr.; Feltner, W. R.; Bouldin, D. L.; Routh, D. E. (Inventor)

    1978-01-01

    An improved method is described of constructing a metal oxide semiconductor device having multiple layers of metal deposited by dc magnetron sputtering at low dc voltages and low substrate temperatures. The method provides multilevel interconnections and cross over between individual circuit elements in integrated circuits without significantly reducing the reliability or seriously affecting the yield.

  20. Development of techniques for processing metal-metal oxide systems

    NASA Technical Reports Server (NTRS)

    Johnson, P. C.

    1976-01-01

    Techniques for producing model metal-metal oxide systems for the purpose of evaluating the results of processing such systems in the low-gravity environment afforded by a drop tower facility are described. Because of the lack of success in producing suitable materials samples and techniques for processing in the 3.5 seconds available, the program was discontinued.

  1. Antimicrobial activity of the metals and metal oxide nanoparticles.

    PubMed

    Dizaj, Solmaz Maleki; Lotfipour, Farzaneh; Barzegar-Jalali, Mohammad; Zarrintan, Mohammad Hossein; Adibkia, Khosro

    2014-11-01

    The ever increasing resistance of pathogens towards antibiotics has caused serious health problems in the recent years. It has been shown that by combining modern technologies such as nanotechnology and material science with intrinsic antimicrobial activity of the metals, novel applications for these substances could be identified. According to the reports, metal and metal oxide nanoparticles represent a group of materials which were investigated in respect to their antimicrobial effects. In the present review, we focused on the recent research works concerning antimicrobial activity of metal and metal oxide nanoparticles together with their mechanism of action. Reviewed literature indicated that the particle size was the essential parameter which determined the antimicrobial effectiveness of the metal nanoparticles. Combination therapy with the metal nanoparticles might be one of the possible strategies to overcome the current bacterial resistance to the antibacterial agents. However, further studies should be performed to minimize the toxicity of metal and metal oxide nanoparticles to apply as proper alternatives for antibiotics and disinfectants especially in biomedical applications.

  2. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

    SciTech Connect

    Qiu, Yang; Huo, Jiajie; Jia, Fan; Shanks, Brent. H.; Li, Wenzhen

    2015-11-06

    Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 M KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential to use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.

  3. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

    DOE PAGES

    Qiu, Yang; Huo, Jiajie; Jia, Fan; ...

    2015-11-06

    Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 Mmore » KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential to use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.« less

  4. High surface area, electrically conductive nanocarbon-supported metal oxide

    DOEpatents

    Worsley, Marcus A.; Han, Thomas Yong-Jin; Kuntz, Joshua D.; Cervantes, Octavio; Gash, Alexander E.; Baumann, Theodore F.; Satcher, Jr., Joe H.

    2015-07-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  5. High surface area, electrically conductive nanocarbon-supported metal oxide

    SciTech Connect

    Worsley, Marcus A; Han, Thomas Yong-Jin; Kuntz, Joshua D; Cervanted, Octavio; Gash, Alexander E; Baumann, Theodore F; Satcher, Jr., Joe H

    2014-03-04

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  6. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Kim, Jeom-Soo; Johnson, Christopher S.

    2008-01-01

    An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li.sub.(2+2x)/(2+x)M'.sub.2x/(2+x)M.sub.(2-2x)/(2+x)O.sub.2-.delta., in which 0.ltoreq.x<1 and .delta. is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

  7. Gold stabilized aqueous sols immobilized on mesoporous CeO2-Al2O3 as catalysts for the preferential oxidation of carbon monoxide.

    PubMed

    Storaro, Loretta; Lenarda, Maurizio; Moretti, Elisa; Talon, Aldo; Porta, Francesca; Moltrasio, Bernardo; Canton, Patrizia

    2010-10-15

    Nanostructured Au/Al(2)O(3)-CeO(2) catalysts with a low content of precious metal (0.9% wt.) were prepared immobilizing two different stabilized Au sols on a high surface area Al(2)O(3)-CeO(2) mixed oxide with a uniform pore size distribution, synthesized by a one-pot methodology. The samples were characterized by elemental analysis, N(2) physisorption, XRPD, TEM and (27)Al-MAS NMR techniques. The catalytic activity of the two samples in the preferential oxidation of CO in excess of H(2) (CO-PROX) was comparatively evaluated in the 35-110 degrees C temperature range. The Au-THPS/AlCe20 sample, prepared immobilizing a sol obtained reducing an aqueous solution of gold tetrachloroaurate salt with bis[tetrakis(hydroxymethyl)phosphonium sulfate], resulted very active and selective at low temperatures and its catalytic activity was correlated with the structural characteristics of the metal particles and of the ordered mesoporous support. Copyright 2010 Elsevier Inc. All rights reserved.

  8. Effects of pore topology and iron oxide core on doxorubicin loading and release from mesoporous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Ronhovde, Cicily J.; Baer, John; Larsen, Sarah C.

    2017-06-01

    Mesoporous silica nanoparticles (MSNs) have a network of pores that give rise to extremely high specific surface areas, making them attractive materials for applications such as adsorption and drug delivery. The pore topology can be readily tuned to achieve a variety of structures such as the hexagonally ordered Mobil Crystalline Material 41 (MCM-41) and the disordered "wormhole" (WO) mesoporous silica (MS) structure. In this work, the effects of pore topology and iron oxide core on doxorubicin loading and release were investigated using MSNs with pore diameters of approximately 3 nm and sub-100 nm particle diameters. The nanoparticles were loaded with doxorubicin, and the drug release into phosphate-buffered saline (PBS, 10 mM, pH 7.4) at 37 °C was monitored by fluorescence spectroscopy. The release profiles were fit using the Peppas model. The results indicated diffusion-controlled release for all samples. Statistically significant differences were observed in the kinetic host-guest parameters for each sample due to the different pore topologies and the inclusion of an iron oxide core. Applying a static magnetic field to the iron oxide core WO-MS shell materials did not have a significant impact on the doxorubicin release. This is the first time that the effects of pore topology and iron oxide core have been isolated from pore diameter and particle size for these materials.

  9. Promotion effect of palladium on Co3O4 incorporated within mesoporous MCM-41 silica for CO Oxidation

    NASA Astrophysics Data System (ADS)

    Hassan, Hassan M. A.; Betiha, Mohamed A.; Elshaarawy, Reda F. M.; Samy El-Shall, M.

    2017-04-01

    Co3O4 incorporated within mesoporous MCM-41 silica have been successfully synthesized and promoted with Pd nanoparticles through a microwave irradiation (MWI) approach. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N2-physisorped, X-ray photoelectron spectroscopy (XPS), temperature program reduction of hydrogen (H2-TPR), temperature program desorption of oxygen (O2-TPD) and high resolution transmission electron microscopy (HRTEM) were adapted to characterize these prepared catalysts. Carbon monoxide oxidation as a model reaction was then used to assess the catalytic performance of these materials. In the light of H2-TPR and XPS results, revealed that the coexisting of Co3+ and Co2+ species as well as surface Co3+/Co2+ ratio within the hexagonal mesoporous of MCM-41, could create an ideal environment to accomplish most extreme catalytic activity. On the other hand, the enhanced CO oxidation by Pd nanoparticles deposition has been explained in the light of the enhancement of the redox ability and tuning the electronic structure of Co3O4, which improved the O2 activation and reduced the adsorption ability of CO simultaneously, which significantly boosted the catalytic performance of CO oxidation. This work provides insights into factors that could lead to improved low temperature CO oxidation performance in Pd-based catalysts.

  10. Process for etching mixed metal oxides

    DOEpatents

    Ashby, C.I.H.; Ginley, D.S.

    1994-10-18

    An etching process is described using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstrom range may be achieved by this method. 1 fig.

  11. Process for etching mixed metal oxides

    DOEpatents

    Ashby, Carol I. H.; Ginley, David S.

    1994-01-01

    An etching process using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstom range may be achieved by this method.

  12. Study on Metal/Metal oxide/Graphene Tunnel Junctions

    NASA Astrophysics Data System (ADS)

    Chen, Ke; Feng, Ying; Khalid Zahir, Raja

    2013-03-01

    Metal/metal-oxide/graphene (Metal = Al, Ti, Hf, Zr) tunnel junctions were fabricated by transferring single-layer graphene grown by chemical vapor deposition on Cu onto metal strips by either a wet or dry approach. The metal strips were prepared by dc magnetron sputtering through a shadow mask and were exposed to air for about 10 minutes for native oxides to grow prior to the transfer. Good tunneling properties were observed for all the junctions fabricated by either means of graphene transfer. The zero-bias resistance of these junctions all increases with time to a final value, indicating continuing oxidation of the metals with a self-limited oxidation rate. Some junctions show the final area-normalized zero-bias resistances and self-limited oxidation time scales for Al, Ti, Hf, Zr are about 0.15, 0.2, 6000, 1000 k Ωcm2 and 25, 90, 6, 9 hour, respectively. The tunneling spectra were studied at various temperature down to 4.2 K and analyzed by the Brinkman-Dynes-Rowell model to get the height and width of the tunnel barriers, taking into account the electron structure of graphene. The junctions are good candidates for chemical sensing applications.

  13. Confinement of a bioinspired nonheme Fe(II) complex in 2D hexagonal mesoporous silica with metal site isolation.

    PubMed

    Jollet, Véronique; Albela, Belén; Sénéchal-David, Katell; Jégou, Pascale; Kolodziej, Emilie; Sainton, Joëlle; Bonneviot, Laurent; Banse, Frédéric

    2013-08-28

    A mixed amine pyridine polydentate Fe(II) complex was covalently tethered in hexagonal mesoporous silica of the MCM-41 type. Metal site isolation was generated using adsorbed tetramethylammonium cations acting as a patterned silanol protecting mask and trimethylsilylazane as a capping agent. Then, the amine/pyridine ligand bearing a tethering triethoxysilane group was either grafted to such a pretreated silica surface prior to or after complexation to Fe(II). These two synthetic routes, denoted as two-step and one-step, respectively, were also applied to fumed silica for comparison, except that the silanol groups were capped after tethering the metal unit. The coordination of the targeted complex was monitored using UV-visible spectrophotometry and, according to XPS, the best control was achieved inside the channels of the mesoporous silica for the two-step route. For the solid prepared according to the one-step route, tethering of the complex occurred mainly at the entrance of the channel.

  14. Ammonium Fluoride Mediated Synthesis of Anhydrous Metal Fluoride-Mesoporous Carbon Nanocomposites for High-Performance Lithium Ion Battery Cathodes.

    PubMed

    Chun, Jinyoung; Jo, Changshin; Sahgong, Sunhye; Kim, Min Gyu; Lim, Eunho; Kim, Dong Hyeon; Hwang, Jongkook; Kang, Eunae; Ryu, Keun Ah; Jung, Yoon Seok; Kim, Youngsik; Lee, Jinwoo

    2016-12-28

    Metal fluorides (MFx) are one of the most attractive cathode candidates for Li ion batteries (LIBs) due to their high conversion potentials with large capacities. However, only a limited number of synthetic methods, generally involving highly toxic or inaccessible reagents, currently exist, which has made it difficult to produce well-designed nanostructures suitable for cathodes; consequently, harnessing their potential cathodic properties has been a challenge. Herein, we report a new bottom-up synthetic method utilizing ammonium fluoride (NH4F) for the preparation of anhydrous MFx (CuF2, FeF3, and CoF2)/mesoporous carbon (MSU-F-C) nanocomposites, whereby a series of metal precursor nanoparticles preconfined in mesoporous carbon were readily converted to anhydrous MFx through simple heat treatment with NH4F under solventless conditions. We demonstrate the versatility, lower toxicity, and efficiency of this synthetic method and, using XRD analysis, propose a mechanism for the reaction. All MFx/MSU-F-C prepared in this study exhibited superior electrochemical performances, through conversion reactions, as the cathode for LIBs. In particular, FeF3/MSU-F-C maintained a capacity of 650 mAh g(-1)FeF3 across 50 cycles, which is ∼90% of its initial capacity. We expect that this facile synthesis method will trigger further research into the development of various nanostructured MFx for use in energy storage and other applications.

  15. Monolithic Gyroidal Mesoporous Mixed Titanium–Niobium Nitrides

    PubMed Central

    2015-01-01

    Mesoporous transition metal nitrides are interesting materials for energy conversion and storage applications due to their conductivity and durability. We present ordered mixed titanium–niobium (8:2, 1:1) nitrides with gyroidal network structures synthesized from triblock terpolymer structure-directed mixed oxides. The materials retain both macroscopic integrity and mesoscale ordering despite heat treatment up to 600 °C, without a rigid carbon framework as a support. Furthermore, the gyroidal lattice parameters were varied by changing polymer molar mass. This synthesis strategy may prove useful in generating a variety of monolithic ordered mesoporous mixed oxides and nitrides for electrode and catalyst materials. PMID:25122534

  16. Monolithic gyroidal mesoporous mixed titanium-niobium nitrides.

    PubMed

    Robbins, Spencer W; Sai, Hiroaki; DiSalvo, Francis J; Gruner, Sol M; Wiesner, Ulrich

    2014-08-26

    Mesoporous transition metal nitrides are interesting materials for energy conversion and storage applications due to their conductivity and durability. We present ordered mixed titanium-niobium (8:2, 1:1) nitrides with gyroidal network structures synthesized from triblock terpolymer structure-directed mixed oxides. The materials retain both macroscopic integrity and mesoscale ordering despite heat treatment up to 600 °C, without a rigid carbon framework as a support. Furthermore, the gyroidal lattice parameters were varied by changing polymer molar mass. This synthesis strategy may prove useful in generating a variety of monolithic ordered mesoporous mixed oxides and nitrides for electrode and catalyst materials.

  17. Method for making monolithic metal oxide aerogels

    DOEpatents

    Coronado, Paul R.

    1999-01-01

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The containment vessel is enclosed within an aqueous atmosphere that is above the supercritical temperature and pressure of the solvent of the metal alkoxide solution.

  18. Mesoporous zirconium titanium oxides. Part 1: Porosity modulation and adsorption properties of xerogels.

    PubMed

    Griffith, Christopher S; Sizgek, G Devlet; Sizgek, Erden; Scales, Nicholas; Yee, Patrick J; Luca, Vittorio

    2008-11-04

    A series of zirconium titanium oxide mesophases containing 33 atom % Zr have been prepared using carboxylic acids of different alkyl chain lengths (Cy ) from y=4-18 through organic-inorganic polymer phase segregation as the gel transition is approached. Thermal treatment of these transparent gels up to 450 degrees C eliminated the organic template, and domain coarsening occurred affording stable worm-hole mesoporous materials of homogeneous composition and pore diameters varying from about 3 to 4 nm in fine increments. With such materials, it was subsequently possible to precisely study the adsorption of vanadium oxo-anions and cations from aqueous solutions and, more particularly, probe the kinetics of intraparticle mass transport as a function of the associated pore dimension. The kinetics of mass transport through the pore systems was investigated using aqueous vanadyl (VO2+) and orthovanadate (VO3(OH)2-) probe species at concentrations ranging from 10 to 200 ppm (0.2 to 4 mmol/L) and pH values of 0 and 10.5, respectively. In the case of both of these vanadium species, the zirconium titanate mesophases displayed relatively slow kinetics, taking in excess of about 500 min to achieve maximum uptake. By using a pseudo-second-order rate law, it was possible to extract the instantaneous and overall rate of the adsorption processes and then relate these to the pore diameters. Both the instantaneous and overall rates of adsorption increased with increasing surface area and pore diameter over the studied pore size range. However, the equilibrium adsorption capacity increased linearly with pore diameter only for the higher concentrations and was independent of pore diameter for the lower concentration. These results have been interpreted using a model in which discrete adsorption occurs at low concentrations and is then followed by multilayer adsorption at higher concentration.

  19. Batch fabrication of mesoporous boron-doped nickel oxide nanoflowers for electrochemical capacitors

    SciTech Connect

    Yang, Jing-He; Yu, Qingtao; Li, Yamin; Mao, Liqun; Ma, Ding

    2014-11-15

    Highlights: • A new facile liquid-phase method has been employed for synthesis boron-doped NiO nanoflowers. • The specific surface area of NiO is as high as 200 m{sup 2} g{sup −1}. • NiO nanoflowers exhibit a high specific capacitance of ∼1309 F g{sup −1} at a charge and discharge current density of 3 A g{sup −1}. • NiO nanoflowers have excellent cycling ability and even after 2500 cycles there is no significant reduction in specific capacitance. - Abstract: Boron-doped nickel oxide (B-NiO) nanoflowers are prepared by simple thermal decomposition of nickel hydroxide. B-NiO is porous sphere with a diameter of about 400 nm. B-NiO nanoflowers are composed of approximately 30 nm nanoplates and the thickness of the nanosheets is approximately 3 nm. The specific surface area of the material is as high as 200 m{sup 2} g{sup −1} and the pore size distribution curves of B-NiO has three typical peaks in the range of mesoporous (5 nm, 13 nm and 18 nm). As an electrode for supercapacitors, the crystalline B-NiO nanoflowers have favorable characteristics, for instance, a specific capacitance of 1309 F g{sup −1} at a current density of 3 A g{sup −1} and no significant reduction in Coulombic efficiency after 2500 cycles at 37.5 A g{sup −1}. This remarkable electrochemical performance will make B-NiO nanoflowers a promising electrode material for high performance supercapacitors.

  20. Antitumor Activities of Metal Oxide Nanoparticles

    PubMed Central

    Vinardell, Maria Pilar; Mitjans, Montserrat

    2015-01-01

    Nanoparticles have received much attention recently due to their use in cancer therapy. Studies have shown that different metal oxide nanoparticles induce cytotoxicity in cancer cells, but not in normal cells. In some cases, such anticancer activity has been demonstrated to hold for the nanoparticle alone or in combination with different therapies, such as photocatalytic therapy or some anticancer drugs. Zinc oxide nanoparticles have been shown to have this activity alone or when loaded with an anticancer drug, such as doxorubicin. Other nanoparticles that show cytotoxic effects on cancer cells include cobalt oxide, iron oxide and copper oxide. The antitumor mechanism could work through the generation of reactive oxygen species or apoptosis and necrosis, among other possibilities. Here, we review the most significant antitumor results obtained with different metal oxide nanoparticles.

  1. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Liu, Xiaobo; Amiinu, Ibrahim Saana; Liu, Shaojun; Cheng, Kun; Mu, Shichun

    2016-07-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures.The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures. Electronic supplementary information (ESI) available: The XPS fitted results, SEM and TEM images, the K-L equation, and some of the electrochemical

  2. The protective effect of the mesoporous host on the photo oxidation of fluorescent guests: a UV-Vis spectroscopy study.

    PubMed

    Miletto, Ivana; Massa, Annalisa; Ugazio, Elena; Musso, Giorgia; Caputo, Giuseppe; Berlier, Gloria

    2014-06-28

    The inclusion of fluorescent molecules within the pores of an inorganic host system is one of the most common ways used for the preparation of highly fluorescent nanosystems. The confinement of labile molecules usually leads to better performances mainly due to their protection against environmental parameters which can concur with the deactivation of the fluorescent ones. In this work the protective effect of the siliceous mesoporous host on photo oxidation of fluorescent guest molecules has been investigated under different experimental conditions, highlighting an outstanding photostability if compared to the performances exerted by the fluorescent dye in solution.

  3. Increased photocatalytic activity of TiO2 mesoporous microspheres from codoping with transition metals and nitrogen

    DOE PAGES

    Mathis, John E.; Lieffers, Justin J.; Mitra, Chandrima; ...

    2015-11-06

    The composition of anatase TiO2 was modified by codoping using combinations of a transition metal and nitrogen in order to increase its photocatalytic activity and extend it performance in the visible region of the electromagnetic spectrum. The transition metals (Mn, Co, Ni, Cu) were added during the hydrothermal preparation of mesoporous TiO2 particles, and the nitrogen was introduced by post-annealing in flowing ammonia gas at high temperature. The samples were analyzed by SEM, XRD, BET, inductively-coupled plasma spectroscopy, and diffuse reflectance UV-vis spectroscopy. The photocatalytic activity was assessed by observing the change in methylene blue concentrations under both UV-vis andmore » visible-only light irradiation. As a result, the photocatalytic activity of the (Mn,N), (Co,N), (Cu,N), and Ni,N) codoped TiO2 was significantly enhanced relative to (N) TiO2.« less

  4. Increased photocatalytic activity of TiO2 mesoporous microspheres from codoping with transition metals and nitrogen

    SciTech Connect

    Mathis, John E.; Lieffers, Justin J.; Mitra, Chandrima; Reboredo, Fernando A.; Bi, Z.; Bridges, Craig A.; Kidder, Michelle K.; Paranthaman, Mariappan Parans

    2015-11-06

    The composition of anatase TiO2 was modified by codoping using combinations of a transition metal and nitrogen in order to increase its photocatalytic activity and extend it performance in the visible region of the electromagnetic spectrum. The transition metals (Mn, Co, Ni, Cu) were added during the hydrothermal preparation of mesoporous TiO2 particles, and the nitrogen was introduced by post-annealing in flowing ammonia gas at high temperature. The samples were analyzed by SEM, XRD, BET, inductively-coupled plasma spectroscopy, and diffuse reflectance UV-vis spectroscopy. The photocatalytic activity was assessed by observing the change in methylene blue concentrations under both UV-vis and visible-only light irradiation. As a result, the photocatalytic activity of the (Mn,N), (Co,N), (Cu,N), and Ni,N) codoped TiO2 was significantly enhanced relative to (N) TiO2.

  5. Three-dimensionally ordered and wormhole-like mesoporous iron oxide catalysts highly active for the oxidation of acetone and methanol.

    PubMed

    Xia, Yunsheng; Dai, Hongxing; Jiang, Haiyan; Zhang, Lei; Deng, Jiguang; Liu, Yuxi

    2011-02-15

    Three-dimensionally (3D) ordered and wormhole-like mesoporous iron oxides (denoted as Fe-KIT6 and Fe-CA) were respectively prepared by adopting the 3D ordered mesoporous silica KIT-6-templating and modified citric acid-complexing strategies, and characterized by a number of analytical techniques. It is shown that the Fe-KIT6-400 and Fe-CA-400 catalysts derived after 400°C-calcination possessed high surface areas (113-165 m(2)/g), high surface adsorbed oxygen concentrations, and good low-temperature reducibility, giving 90% conversion below 189 and 208°C for acetone and methanol oxidation at 20,000 mL/(g h), respectively. It is believed that the good catalytic performance of Fe-CA-400 and Fe-KIT6-400 was related to factors such as higher surface area and oxygen adspecies concentration, better low-temperature reducibility, and 3D mesoporous architecture. Copyright © 2010 Elsevier B.V. All rights reserved.

  6. Effect of mesoporous g-C3N4 substrate on catalytic oxidation of CO over Co3O4

    NASA Astrophysics Data System (ADS)

    Yang, Heng; Lv, Kangle; Zhu, Junjiang; Li, Qin; Tang, Dingguo; Ho, Wingkei; Li, Mei; Carabineiro, Sónia A. C.

    2017-04-01

    Mesoporous graphitic carbon nitride (mpg-CN) was synthesized using Triton X-100, a surfactant containing a hydrophilic polyethylene oxide group and a tert-octyl-phenyl hydrophobic moiety, as a soft template. The obtained mpg-CN was used as a support for Co3O4, and this supported catalyst was used for CO oxidation. The effects of the amount of Triton X-100, weight ratio of Co3O4 to mpg-CN and calcination temperature on the catalytic performances for CO oxidation of Co3O4/mpg-CN composites were systematically studied. It was found that the presence of Triton X-100 not only retarded the polymerization of dicyandiamide, but also affected the microstructure of Co3O4. Bubbles formed because of the hydrophobic group of the surfactant Triton X-100 can be act as a soft template for the synthesis of mesoporous g-C3N4. The enhanced catalytic activity of Co3O4/mpg-CN was attributed to a synergistic effect, enlarged BET surface areas, increased Co3+ and lattice oxygen contents, and the porous structure of mpg-CN support. The high stability of 12.5% Co3O4/mpg-CN(1.0) makes it a promising catalyst for practical applications.

  7. Synthesis and characterization of different metal oxide nanostructures by simple electrolysis based oxidation of metals.

    PubMed

    Singh, Dinesh Pratap; Srivastava, Onkar Nath

    2009-09-01

    We report the Synthesis of different metal oxide (Cu2O, SnO2, Fe3O4 and PbO2) nanostructures by simple electrolysis based oxidation of metals (Cu, Sn, Fe and Pb). We have utilized the two electrode set up for the electrolysis and used different metal electrodes as anode and platinum as cathode. The synthesized nanomaterials were delaminated in the electrolyte. The microstructural characterization of synthesized materials in electrolytes after electrolysis at different electrode potentials revealed that the nanostructures strongly depend on the applied voltage between the electrodes. Various nanostructures (nanothreads, nanowires, nanocubes, nanotetrapods and hexagons-like) of metal oxides have been synthesized by this method. In case of copper electrode we have found nanothreads and nanowires of cuprous oxide. Tin electrode resulted nanothreads, nanotetrapod and nanocube like structures of tin oxide. Iron electrode resulted, nanowire like structures of iron oxide and lead sheet transformed into hexagon like and six petals like structures of lead oxide.

  8. PLUTONIUM METAL: OXIDATION CONSIDERATIONS AND APPROACH

    SciTech Connect

    Estochen, E.

    2013-03-20

    Plutonium is arguably the most unique of all metals when considered in the combined context of metallurgical, chemical, and nuclear behavior. Much of the research in understanding behavior and characteristics of plutonium materials has its genesis in work associated with nuclear weapons systems. However, with the advent of applications in fuel materials, the focus in plutonium science has been more towards nuclear fuel applications, as well as long term storage and disposition. The focus of discussion included herein is related to preparing plutonium materials to meet goals consistent with non-proliferation. More specifically, the emphasis is on the treatment of legacy plutonium, in primarily metallic form, and safe handling, packaging, and transport to meet non-proliferation goals of safe/secure storage. Elevated temperature oxidation of plutonium metal is the treatment of choice, due to extensive experiential data related to the method, as the oxide form of plutonium is one of only a few compounds that is relatively simple to produce, and stable over a large temperature range. Despite the simplicity of the steps required to oxidize plutonium metal, it is important to understand the behavior of plutonium to ensure that oxidation is conducted in a safe and effective manner. It is important to understand the effect of changes in environmental variables on the oxidation characteristics of plutonium. The primary purpose of this report is to present a brief summary of information related to plutonium metal attributes, behavior, methods for conversion to oxide, and the ancillary considerations related to processing and facility safety. The information provided is based on data available in the public domain and from experience in oxidation of such materials at various facilities in the United States. The report is provided as a general reference for implementation of a simple and safe plutonium metal oxidation technique.

  9. Synthesis, characterization, and electrochemical properties of ordered mesoporous carbons containing nickel oxide nanoparticles using sucrose and nickel acetate in a silica template

    SciTech Connect

    Cao Yulin; Cao Jieming Zheng Mingbo; Liu Jinsong; Ji Guangbin

    2007-02-15

    New ordered mesoporous carbons containing nickel oxide nanoparticles have been successfully synthesized by carbonization of sucrose in the presence of nickel acetate inside SBA-15 mesoporous silica template. The obtained samples were characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, and transmission electron microscopy (TEM). The NiO nanoparticles were embedded inside the mesoporous carbon framework due to the simultaneous pyrolysis of nickel acetate during carbonization. The electrochemical testing of the as-made nanocomposites showed a large specific capacitance of 230 F g{sup -1} using 2 M KOH as the electrolyte at room temperature. This is attributed to the nanometer-sized NiO formed inside mesoporous carbons and the high surface area of the mesopores in which the NiO nanoparticles are formed. Furthermore, the synthetic process is proposed as a simple and general method for the preparation of new functionalized mesoporous carbon materials, for various applications in catalysis, sensor or advanced electrode material. - Graphical abstract: Schematic drawings of synthesis routes for the NiOCMK materials.

  10. Understanding the synthesis, performance, and passivation of metal oxide photocathodes

    NASA Astrophysics Data System (ADS)

    Flynn, Cory James

    Metal oxides are ubiquitous in semiconductor technologies for their ease of synthesis, chemical stability, and tunable optical/electronic properties. These properties are especially important to fabricating efficient photoelectrodes for solar-energy applications. To counter inherent problems in these materials, new strategies were developed and successfully implemented on the widely-utilized p-type semiconductor, NiO. As the size of semiconductor materials shrink, the surface-to-volume ratio increases and surface defects dominate the performance of the materials. Surface defects can alter the optical and electronic characteristics of materials by changing the Fermi level, charge-carrier mobility, and surface reactivity. We first present a strategy to increase the electrical mobility of mesoporous metal oxide electrode materials by optimizing shape morphology. Transitioning from nanospheres to hexagonal nanoplatelets increased the charge-carrier mobility by one order of magnitude. We then employed this improved material with a new vapor-phase deposition method termed targeted atomic deposition (TAD) to selectively passivate defect sites in semiconductor nanomaterials. We demonstrated the capabilities of this passivation method by applying a TAD of aluminum onto NiO. By exploiting a temperature-dependent deposition process, we selectively passivated the highly reactive sites in NiO: oxygen dangling bonds associated with Ni vacancies. The TAD treatment completely passivated all measurable surface defects, optically bleached the material, and significantly improved all photovoltaic performance metrics in dye-sensitized solar cells. The technique was proven to be generic to numerous forms of NiO. While the implementation of TAD of Al was successful, the process involved pulsing two precursors to passivate the material. Ideally, the TAD process should require only a single precursor and continuous exposure. We utilized a continuous flow of diborane to perform a TAD of B

  11. All-metal mesoporous nanocolloids: solution-phase synthesis of core-shell Pd@Pt nanoparticles with a designed concave surface.

    PubMed

    Ataee-Esfahani, Hamed; Imura, Masataka; Yamauchi, Yusuke

    2013-12-16

    Colloidal Pd@Pt nanoparticles with uniform mesopores can be synthesized in one step by a facile solution-phase method involving slow reduction of metal species in strong acidic media. In this system, F127 micelles can directly act as a template to form the mesopores in the product, and the greater reducibility of the Pd species leads to the desired core-shell Pd@Pt nanocolloids. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kang, Sun-Ho

    2010-06-08

    An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which 0metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. The xLi.sub.2-yH.sub.y.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 material is prepared by preconditioning a precursor lithium metal oxide (i.e., xLi.sub.2M'O.sub.3.(1-x)LiMO.sub.2) with a proton-containing medium with a pH<7.0 containing an inorganic acid. Methods of preparing the electrodes are disclosed, as are electrochemical cells and batteries containing the electrodes.

  13. Dendrimers, mesoporous silicas and chitosan-based nanosorbents for the removal of heavy-metal ions: A review.

    PubMed

    Vunain, E; Mishra, A K; Mamba, B B

    2016-05-01

    The application of nanomaterials as nanosorbents in solving environmental problems such as the removal of heavy metals from wastewater has received a lot of attention due to their unique physical and chemical properties. These properties make them more superior and useful in various fields than traditional adsorbents. The present mini-review focuses on the use of nanomaterials such as dendrimers, mesoporous silicas and chitosan nanosorbents in the treatment of wastewater contaminated with toxic heavy-metal ions. Recent advances in the fabrication of these nanoscale materials and processes for the removal of heavy-metal ions from drinking water and wastewater are highlighted, and in some cases their advantages and limitations are given. These next-generation adsorbents have been found to perform very well in environmental remediation and control of heavy-metal ions in wastewater. The main objective of this review is to provide up-to-date information on the research and development in this particular field and to give an account of the applications, advantages and limitations of these particular nanosorbents in the treatment of aqueous solutions contaminated with heavy-metal ions.

  14. Efficient removal of heavy metal ions with biopolymer template synthesized mesoporous titania beads of hundreds of micrometers size.

    PubMed

    Wu, Na; Wei, Huanhuan; Zhang, Lizhi

    2012-01-03

    We demonstrated that mesoporous titania beads of uniform size (about 450 μm) and high surface area could be synthesized via an alginate biopolymer template method. These mesoporous titania beads could efficiently remove Cr(VI), Cd(II), Cr(III), Cu(II), and Co(II) ions from simulated wastewater with a facile subsequent solid-liquid separation because of their large sizes. We chose Cr(VI) removal as the case study and found that each gram of these titania beads could remove 6.7 mg of Cr(VI) from simulated wastewater containing 8.0 mg·L(-1) of Cr(VI) at pH = 2.0. The Cr(VI) removal process was found to obey the Langmuir adsorption model and its kinetics followed pseudo-second-order rate equation. The Cr(VI) removal mechanism of titania beads might be attributed to the electrostatic adsorption of Cr(VI) ions in the form of negatively charged HCrO(4)(-) by positively charged TiO(2) beads, accompanying partial reduction of Cr(VI) to Cr(III) by the reductive surface hydroxyl groups on the titania beads. The used titania beads could be recovered with 0.1 mol·L(-1) of NaOH solution. This study provides a promising micro/nanostructured adsorbent with easy solid-liquid separation property for heavy metal ions removal.

  15. Site-selective functionalization of periodic mesoporous organosilica (PMO) with macrocyclic host for specific and reversible recognition of heavy metal.

    PubMed

    Ye, Gang; Leng, Yuxiao; Bai, Feifei; Wei, Jichao; Wang, Jianchen; Chen, Jing

    2013-07-01

    A novel kind of macrocyclic-host-functionalized periodic mesoporous organosilica (PMO) with excellent and reversible recognition of Pb(II) was developed. The macrocyclic host molecule cis-dicyclohexano[18]crown-6, with strong affinity to Pb(II), was carefully modified as a bridged precursor to build the PMO material. To break down the limit of the functionalization degree for PMOs incorporated with large-sized moieties, a site-selective post-functionalization method was proposed to further decorate the external surface of the PMO material. The selective recognition ability of the upgraded PMO material towards Pb(II) was remarkably enhanced without destroying the mesoporous ordering. Solid-state (13)C and (29)Si NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), XRD, TEM, and nitrogen adsorption-desorption isotherm measurements were utilized for a full characterization of the structure, micromorphology, and surface properties. Reversible binding of Pb(II) was realized in the binding-elution cycle experiments. The mechanism of the supramolecular interaction between the macrocyclic host and metal ion was discussed. The synthetic strategy can be considered a general way to optimize the properties of PMOs as binding materials for practical use while preserving the mesostructure. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Removal of As(III) and As(V) from water by copper oxide incorporated mesoporous alumina.

    PubMed

    Pillewan, Pradnya; Mukherjee, Shrabanti; Roychowdhury, Tarit; Das, Sera; Bansiwal, Amit; Rayalu, Sadhana

    2011-02-15

    In the present manuscript a new adsorbent namely copper oxide incorporated mesoporous alumina (COIMA) for removal of arsenic from water is reported. The COIMA was prepared by treating mesoporous alumina with copper sulphate solution followed by calcination at 450°C in the presence of air. Various adsorption isotherm and kinetic parameters were computed using batch adsorption studies to determine the adsorption capacity for As(III) and As(V) and to understand the mechanism of adsorption. It was observed that incorporation of copper oxide improves the adsorption capacity of unmodified alumina from 0.92 to 2.16 mg g(-1) for As(III) and from 0.84 to 2.02 mg g(-1) for As(V). The results revealed that the adsorption follows Langmuir isotherm and pseudo-second-order kinetic models for both As(III) and As(V). The material is capable of simultaneously removing As(III) and As(V) with removal efficiencies of more than 95% for both As(III) and As(V). Assessment of the water quality before and after treatment with COIMA also confirmed that the there is no leaching of copper and other parameters were also within permissible limits of Indian drinking water standard indicating that the COIMA can be used for treatment of arsenic contaminated drinking water.

  17. Anti-epidermal growth factor receptor conjugated mesoporous zinc oxide nanofibers for breast cancer diagnostics

    NASA Astrophysics Data System (ADS)

    Ali, Md. Azahar; Mondal, Kunal; Singh, Chandan; Dhar Malhotra, Bansi; Sharma, Ashutosh

    2015-04-01

    We report the fabrication of an efficient, label-free, selective and highly reproducible immunosensor with unprecedented sensitivity (femto-molar) to detect a breast cancer biomarker for early diagnostics. Mesoporous zinc oxide nanofibers (ZnOnFs) are synthesized by electrospinning technique with a fiber diameter in the range of 50-150 nm. Fragments of ZnOnFs are electrophoretically deposited on an indium tin oxide glass substrate and conjugated via covalent or electrostatic interactions with a biomarker (anti-ErbB2; epidermal growth factor receptor 2). Oxygen plasma treatment of the carbon doped ZnOnFs generates functional groups (-COOH, -OH, etc.) that are effective for the conjugation of anti-ErbB2. ZnOnFs without plasma treatment that conjugate via electrostatic interactions were also tested for comparison. Label-free detection of the breast cancer biomarker by this point-of-care device is achieved by an electrochemical impedance technique that has high sensitivity (7.76 kΩ μM-1) and can detect 1 fM (4.34 × 10-5 ng mL-1) concentration. The excellent impedimetric response of this immunosensor provides a fast detection (128 s) in a wide detection test range (1.0 fM-0.5 μM). The oxy-plasma treated ZnOnF immunoelectrode shows a higher association constant (404.8 kM-1 s-1) indicating a higher affinity towards the ErbB2 antigen compared to the untreated ZnOnF immunoelectrode (165.6 kM-1 s-1). This sensor is about an order of magnitude more sensitive than the best demonstrated in the literature based on different nanomaterials and about three orders of magnitude better than the ELISA standard for breast cancer biomarker detection. This proposed point-of-care cancer diagnostic offers several advantages, such as higher stability, rapid monitoring, simplicity, cost-effectiveness, etc., and should prove to be useful for the detection of other bio- and cancer markers.We report the fabrication of an efficient, label-free, selective and highly reproducible immunosensor

  18. One-Pot Fabrication of Mesoporous Core-Shell Au@PtNi Ternary Metallic Nanoparticles and Their Enhanced Efficiency for Oxygen Reduction Reaction.

    PubMed

    Shi, Qiurong; Zhu, Chengzhou; Fu, Shaofang; Du, Dan; Lin, Yuehe

    2016-02-01

    Currently, Pt-based nanomaterials with tailorable shapes, structures, and morphologies are the most popular electrocatalysts for oxygen reduction reaction, which is a significant cathode reaction in fuel cells for renewable energy applications. We have successfully synthesized mesoporous core-shell Au@PtNi ternary metallic nanoparticles through a one-pot reduction method for cathodic materials used as oxygen reduction reaction catalysts. The as-synthesized nanoparticles exhibited superior catalytic activities and long-term stabilities compared with mesoporous core-shell Au@Pt nanoparticles and commercial Pt/C. The unique mesoporous core-shell structures as well as the alloy shells enable the enhanced electrochemical oxygen reduction reaction performances of the Pt-based materials via the electronic effect and geometric effect, holding great promise in fuel cell application.

  19. Enhancing stability and oxidation activity of cytochrome C by immobilization in the nanochannels of mesoporous aluminosilicates.

    PubMed

    Lee, Chia-Hung; Lang, Jun; Yen, Chun-Wan; Shih, Pei-Chun; Lin, Tien-Sung; Mou, Chung-Yuan

    2005-06-30

    Hydrothermally stable and structrurally ordered mesoporous and microporous aluminosilicates with different pore sizes have been synthesized to immobilize cytochrome c (cyt c): MAS-9 (pore size 90 A), MCM-48-S (27 A), MCM-41-S (25 A), and Y zeolites (7.4 A). The amount of cyt c adsorption could be increased by the introduction of aluminum into the framework of pure silica materials. Among these mesoprous silicas (MPS), MAS-9 showed the highest loading capacity due to its large pore size. However, cyt c immobilized in MAS-9 could undergo facile unfolding during hydrothermal treatments. MCM-41-S and MCM-48-S have the pore sizes that match well the size of cyt c (25 x 25 x 37 A). Hence the adsorbed cyt c in these two medium pore size MPS have the highest hydrothermal stability and overall catalytic activity. On the other hand, the pore size of NaY zeolite is so small that cyt c is mostly adsorbed only on the outer surface and loses its enzymatic activity rapidly. The improved stability and high catalytic activity of cyt c immobilized in MPS are attributed to the electrostatic attraction between the pore surface and cyt c and the confinement provided by nanochannels. We further observed that cyt c immobilized in MPS exists in both high and low spin states, as inferred from the ESR and UV-vis studies. This is different from the native cyt c, which shows primarily the low spin state. The high spin state arises from the replacement of Met-80 ligands of heme Fe (III) by water or silanol group on silica surface, which could open up the heme groove for easy access of oxidants and substrates to iron center and facilitate the catalytic activity. In the catalytic study, MAS-9-cyt c showed the highest specific activity toward the oxidation of polycyclic aromatic hydrocarbons (PAHs), which arises from the fast mass transfer rate of reaction substrate due to its large pore size. For pinacyanol (a hydrophilic substrate), MCM-41-S-cyt c and MCM-48-S-cyt c showed higher specific

  20. Chitosan-coated mesoporous microspheres of calcium silicate hydrate: environmentally friendly synthesis and application as a highly efficient adsorbent for heavy metal ions.

    PubMed

    Zhao, Jing; Zhu, Ying-Jie; Wu, Jin; Zheng, Jian-Qiang; Zhao, Xin-Yu; Lu, Bing-Qiang; Chen, Feng

    2014-03-15

    Chitosan-coated calcium silicate hydrate (CSH/chitosan) mesoporous microspheres formed by self-assembly of nanosheets have been synthesized in aqueous solution under ambient conditions without using any toxic surfactant or organic solvent. The method reported herein has advantages of simplicity, low cost and being environmentally friendly. The BET specific surface area of CSH/chitosan mesoporous microspheres is measured to be as high as ~356 m(2) g(-1), which is considerably high among calcium silicate materials. The as-prepared CSH/chitosan mesoporous microspheres are promising adsorbent and exhibit a quick and highly efficient adsorption behavior toward heavy metal ions of Ni(2+), Zn(2+), Cr(3+), Pb(2+) Cu(2+) and Cd(2+) in aqueous solution. The adsorption kinetics can be well fitted by the pseudo second-order model. The maximum adsorption amounts of Ni(2+), Zn(2+), Pb(2+), Cu(2+) and Cd(2+) on CSH/chitosan mesoporous microspheres are extremely high, which are 406.6, 400, 796, 425 and 578 mg/g, respectively. The CSH/chitosan adsorbent exhibits the highest affinity for Pb(2+) ions among five heavy metal ions. The adsorption capacities of the CSH/chitosan adsorbent toward heavy metal ions are relatively high compared with those reported in the literature.

  1. Enhanced H2 uptake in solvents confined in mesoporous metal-organic framework.

    PubMed

    Clauzier, Stephanie; Ho, Linh Ngoc; Pera-Titus, Marc; Coasne, Benoit; Farrusseng, David

    2012-10-24

    Hydrogen uptake at 298 K and 30 bar in hybrid sorbents consisting of n-hexane confined in MIL-101 is found to be 22 times larger than in sole n-hexane. The enhanced solubility in MIL-101, found to be 3 times larger than in mesoporous silica of similar pore size, highlights the key roles played by surface chemistry and accessible surface area.

  2. Nanopowder Metal Oxide for Photoluminescent Gas Sensing

    NASA Astrophysics Data System (ADS)

    Zhyrovetsky, V. M.; Popovych, D. I.; Savka, S. S.; Serednytski, A. S.

    2017-02-01

    Gas sensing properties of metal oxide nanopowders (ZnO, TiO2, WO3, SnO2) with average diameters of 40-60 nm were analyzed by room-temperature photoluminescence spectroscopy. The influence of gas environment (O2, N2, H2, CO, CO2) on the emission intensity was investigated for metal oxide nanopowders with surface doped by impurities (Pt, Ag, Au, Sn, Ni or Cu). Established physicochemical regularities of modification of surface electronic states of initial and doped nanopowders during gas adsorption. The nature of metal oxide nanopowder gas-sensing properties (adsorption capacity, sensitivity, selectivity) has been established and the design and optimal materials for the construction of the multi-component sensing matrix have been selected.

  3. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    2001-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  4. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    1999-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  5. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, B.S.; Gupta, R.P.

    1999-06-22

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

  6. Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods.

    PubMed

    Heo, Sungyeon; Kim, Jongwook; Ong, Gary K; Milliron, Delia J

    2017-09-13

    Low-temperature processed mesoporous nanocrystal thin films are platforms for fabricating functional composite thin films on flexible substrates. Using a random arrangement of anisotropic nanocrystals can be a facile solution to generate pores without templates. However, the tendency for anisotropic particles to spontaneously assemble into a compact structure must be overcome. Here, we present a method to achieve random networking of nanorods during solution phase deposition by switching their ligand-stabilized colloidal nature into a charge-stabilized nature by a ligand-stripping chemistry. Ligand-stripped tungsten suboxide (WO2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventing nanorods from densely packing. Porosity and pore size distribution of thin films are controlled by changing the aspect ratio of the nanorods. This template-free mesoporous structure, achieved without annealing, provides a framework for introducing guest components, therefore enabling our fabrication of inorganic nanocomposite electrochromic films on flexible substrates. Following infilling of niobium polyoxometalate clusters into pores and successive chemical condensation, a WOx-NbOx composite film is produced that selectively controls visible and near-infrared light transmittance without any annealing required. The composite shows rapid switching kinetics and can be stably cycled between optical states over 2000 times. This simple strategy of using anisotropic nanocrystals gives insight into mesoporous thin film fabrication with broader applications for flexible devices.

  7. Mesoporous carbonates and method of making

    DOEpatents

    Fryxell, Glen; Liu, Jun; Zemanian, Thomas S.

    2004-06-15

    Mesoporous metal carbonate structures are formed by providing a solution containing a non-ionic surfactant and a calcium acetate salt, adding sufficient base to react with the acidic byproducts to be formed by the addition of carbon dioxide, and adding carbon dioxide, thereby forming a mesoporous metal carbonate structure containing the metal from said metal salt.

  8. Effect of competitive ions on the arsenic removal by mesoporous hydrous zirconium oxide from drinking water

    SciTech Connect

    Bortun, Anatoly; Bortun, Mila; Pardini, James; Khainakov, Sergei A.

    2010-11-15

    Adsorption properties of 302-type commercially available hydrous zirconium oxide (302-HZO) towards arsenic and some competitive anions and cations have been studied under batch and column conditions. Due to amphoteric properties, anion exchange performance of hydrous zirconium oxide is pH dependent. Media exhibits high affinity towards arsenic in a broad pH range, with high adsorption capacity at pH < 8. It was shown that silicate and phosphate ions are arsenic's main competitors affecting media adsorption capacity. Presence of transition metal cations in <1 ppm does not affect 302-HZO capacity on arsenic, whereas alkaline-earth cations improve arsenic removal. The possibility for significant increase of 302-HZO adsorption capacity on arsenic at pH > 8 by using 'solid acidifier' technique is discussed. Results of 302-HZO field trials are presented.

  9. Metal Oxide Materials and Decontamination Methodology

    DTIC Science & Technology

    1991-01-15

    polyoxometalates as photocatalysts for oxidative degradation. The abstract for this paper, reference 15, is as follows. This paper is undergoing revision and...substrates catalyzed by representative semiconductor metal oxides (anatase TiO2 , SnO2, cubic W03, and CdS) and photoredox active early transition metal...326"] = k4,I[THT]/k[TNT] + kic) is consistent with this data and the observation of saturation kinetics in TNT. Upon addition of 02, TiO2 (with or

  10. Regeneration of sulfated metal oxides and carbonates

    DOEpatents

    Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

    1978-03-28

    Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

  11. Mesoporous CuO-TiO2 microspheres for efficient catalytic oxidation of CO and photodegradation of methylene blue

    NASA Astrophysics Data System (ADS)

    Chowdhury, Ipsita Hazra; Ghosh, Sourav; Basak, Somjyoti; Naskar, Milan Kanti

    2017-05-01

    Mesoporous CuO-TiO2 microspheres were synthesized by a simple solution based process. The synthesized products were characterized by XRD, FTIR, Raman spectroscopy, N2 adsorption-desorption study, FESEM, TEM, XPS and UV-vis spectroscopy. The catalytic performances for oxidation of CO and photocatalytic degradation of methylene blue (MB) were studied with the synthesized microspheres. For higher concentration of CuO in the microspheres, the T50 (50% conversion) and T100 (100% conversion) of CO oxidations were found to be 139 °C and 168 °C, respectively. For lower concentration of CuO in the microspheres having BET surface area of 67.7 m2 g-1 showed the maximum (about 93%) photodegradation of MB.

  12. Role of metal oxides in chemical evolution

    NASA Astrophysics Data System (ADS)

    Kamaluddin

    2013-06-01

    Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

  13. Reduction of metal oxides through mechanochemical processing

    DOEpatents

    Froes, Francis H.; Eranezhuth, Baburaj G.; Senkov, Oleg N.

    2000-01-01

    The low temperature reduction of a metal oxide using mechanochemical processing techniques. The reduction reactions are induced mechanically by milling the reactants. In one embodiment of the invention, titanium oxide TiO.sub.2 is milled with CaH.sub.2 to produce TiH.sub.2. Low temperature heat treating, in the range of 400.degree. C. to 700.degree. C., can be used to remove the hydrogen in the titanium hydride.

  14. Metal ion binding to iron oxides

    NASA Astrophysics Data System (ADS)

    Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

    2006-06-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

  15. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

    SciTech Connect

    Dong, Xinbo; Wang, Danjun; Li, Kebin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

    2014-09-15

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

  16. Micro–mesoporous iron oxides with record efficiency for the decomposition of hydrogen peroxide: morphology driven catalysis for the degradation of organic contaminants

    EPA Science Inventory

    A template-free solid-state synthesis of a morphologically controlled and highly organized iron(III)oxide micro–mesoporous Fenton catalyst has been engineered through a simple two-step synthetic procedure. The 3D nanoassembly of hematite nanoparticles (5–7 nm) organized into a ro...

  17. Micro–mesoporous iron oxides with record efficiency for the decomposition of hydrogen peroxide: morphology driven catalysis for the degradation of organic contaminants

    EPA Science Inventory

    A template-free solid-state synthesis of a morphologically controlled and highly organized iron(III)oxide micro–mesoporous Fenton catalyst has been engineered through a simple two-step synthetic procedure. The 3D nanoassembly of hematite nanoparticles (5–7 nm) organized into a ro...

  18. Nanostructured metal-oxides for use as high power and energy density storage electrodes

    NASA Astrophysics Data System (ADS)

    Mondragón-Rodríguez, G. C.; Saruhan, Bilge

    2014-06-01

    The most significant advantage of double layer supercapacitors over batteries is their ability of being almost continuously charged and discharged without degradation. This is why batteries and supercapacitors are complementary to each other. The supercapacitors can supply power to the system when there are surges or energy bursts relying on their fast charge/discharge ability while the batteries can supply the bulk energy since they can store and deliver larger amount of energy over a longer period of time resulting in a higher discharge capacitance. With the introduction of new electrodes, super-capacitors will provide higher energy densities and charge rapidly with longer lifetimes, relying on the addition of pseudo-capacitance as well as higher surface areas. Pseudo-capacitance is achieved by the use of metal-oxides yielding faradaic reactions over redox couples. Capacitive charge-storage properties of mesoporous films made of complex metal-oxides preferably in core + shell architecture are superior to those of nonporous crystalline metal-oxides. RuO2 yields the highest energy densities however is not attractive for commercial use due to high cost. Other promising candidates are MnO2, Co2O3, NiO, etc. which need to be improved for achievement of long-term stability. Additionally, the type of electrolyte is important in terms of supercapacitor's performance and thus, needs to be optimized considering the characteristics of the employed electrode material. This work describes the fabrication and performance of mesoporous double oxides (MnCu, MnNi, MnCo) in aqueous electrolytes. Thin films are deposited by sputtering technique on graphite foils. Specific capacitance, energy and power densities are calculated and the role of electrolyte on electrode performance is discussed.

  19. Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents, whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. Details addressing the design, synthesis and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental clean-up necessary after 40 years of weapons grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  20. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  1. Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design

    PubMed Central

    Dumée, Ludovic F.; Lemoine, Jean-Baptiste; Ancel, Alice; Hameed, Nishar; He, Li; Kong, Lingxue

    2015-01-01

    The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation. PMID:28347094

  2. Advanced metal oxide varistor concepts

    NASA Astrophysics Data System (ADS)

    Philipp, H. R.; Mahan, G. D.; Levinson, L. M.

    1984-07-01

    Zinc oxide varistors are ZnO-based ceramic semiconductor devices with highly nonlinear current-voltage characteristics similar to back-to-back Zener diodes but with much greater current, voltage, and energy-handling capabilities. Zinc oxide varistors have proven useful in a variety of applications, particularly as high-quality voltage suppression devices for the protection of ac and dc electric power transmission systems against the effects of transient overvoltages due to switching surges and lightning strikes. Simple varistor systems that use Bi or Pr as the varistor-forming additive and Co or Mn as the varistor-performance ingredient were studied. Commercial varistor materials generally use Bi as the varistor-forming ingredient, and the sintering process in such material probably proceeds in the liquid phase. Varistor materials that use Pr as the varistor-forming ingredient are also produced commercially.

  3. Mechanical Instability of Oxidized Metal Clusters

    NASA Astrophysics Data System (ADS)

    Celino, Massimo; Cleri, Fabrizio; D'Agostino, Gregorio; Rosato, Vittorio

    1996-09-01

    A mechanism to explain the complete oxidation of small metal clusters is proposed, based on the occurrence of a mechanical instability driven by the expansion of the progressively oxidized cluster surface and the subsequent stress relaxation. Molecular dynamics simulations of spherical Pd clusters show that an expanded surface layer is capable of straining the inner core of the cluster up to the point of inducing cavitation. These findings allow the interpretation of recent experimental results in which oxidized Pd clusters exhibit a hollow spherical shape.

  4. Metal oxide electrocatalysts for alternative energy technologies

    NASA Astrophysics Data System (ADS)

    Pacquette, Adele Lawren

    This dissertation focuses on the development of metal oxide electrocatalysts with varying applications for alternative energy technologies. Interest in utilizing clean, renewable and sustainable sources of energy for powering the planet in the future has received much attention. This will address the growing concern of the need to reduce our dependence on fossil fuels. The facile synthesis of metal oxides from earth abundant metals was explored in this work. The electrocatalysts can be incorporated into photoelectrochemical devices, fuel cells, and other energy storage devices. The first section addresses the utilization of semiconductors that can harness solar energy for water splitting to generate hydrogen. An oxysulfide was studied in order to combine the advantageous properties of the stability of metal oxides and the visible light absorbance of metal chalcogenides. Bi 2O2S was synthesized under facile hydrothermal conditions. The band gap of Bi2O2S was smaller than that of its oxide counterpart, Bi2O3. Light absorption by Bi 2O2S was extended to the visible region (>600 nm) in comparison to Bi2O3. The formation of a composite with In 2O3 was formed in order to create a UV irradiation protective coating of the Bi2O2S. The Bi2O2S/In 2O3 composite coupled with a dye CrTPP(Cl) and cocatalysts Pt and Co3O4 was utilized for water splitting under light irradiation to generate hydrogen and oxygen. The second section focuses on improving the stability and light absorption of semiconductors by changing the shapes and morphologies. One of the limitations of semiconductor materials is that recombination of electron-hole pairs occur within the bulk of the materials instead of migration to the surface. Three-dimensional shapes, such as nanorods, can prevent this recombination in comparison to spherical particles. Hierarchical structures, such as dendrites, cubes, and multipods, were synthesized under hydrothermal conditions, in order to reduce recombination and improve

  5. Microbial-mediated method for metal oxide nanoparticle formation

    DOEpatents

    Rondinone, Adam J.; Moon, Ji Won; Love, Lonnie J.; Yeary, Lucas W.; Phelps, Tommy J.

    2015-09-08

    The invention is directed to a method for producing metal oxide nanoparticles, the method comprising: (i) subjecting a combination of reaction components to conditions conducive to microbial-mediated formation of metal oxide nanoparticles, wherein said combination of reaction components comprise: metal-reducing microbes, a culture medium suitable for sustaining said metal-reducing microbes, an effective concentration of one or more surfactants, a reducible metal oxide component containing one or more reducible metal species, and one or more electron donors that provide donatable electrons to said metal-reducing microbes during consumption of the electron donor by said metal-reducing microbes; and (ii) isolating said metal oxide nanoparticles, which contain a reduced form of said reducible metal oxide component. The invention is also directed to metal oxide nanoparticle compositions produced by the inventive method.

  6. Metal oxide chemistry in solution: the early transition metal polyoxoanions.

    PubMed

    Day, V W; Klemperer, W G

    1985-05-03

    Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces.

  7. Synthesis of nanostructured hybrid sorbent materials using organosilane self-assembly on mesoporous ceramic oxides

    SciTech Connect

    Fryxell, Glen E.

    2007-01-30

    The single most important factor in determining quality of life in human society is the availability of pure, clean drinking water. Wars have been fought, and will continue to be fought, over access and control of clean water. Drinking water has two major classes of contamination, biological contamination and chemical contamination. Bacterial contamination can be dealt with by a number of well-established technologies (e.g. chlorination, ozone, UV, etc.), but chemical contamination is a somewhat more challenging target. Common organic contaminants, such as pesticides, agricultural chemicals, industrial solvents, and fuels can be removed by treatment with UV/ozone, activated carbon or plasma technologies. Toxic heavy metals like mercury, lead and cadmium can be partially addressed by using traditional sorbent materials like alumina, but these materials bind metal ions non-specifically and can easily be saturated with harmless, ubiquitous species like calcium, magnesium and zinc (which are actually nutrients, and don’t need to be removed). Another weakness of these traditional sorbent materials is that metal ion sorption to a ceramic oxide surface is a reversible process, meaning they can easily desorb back into the drinking water supply.

  8. Multi-metal oxide ceramic nanomaterial

    SciTech Connect

    O'Brien, Stephen; Liu, Shuangyi; Huang, Limin

    2016-06-07

    A convenient and versatile method for preparing complex metal oxides is disclosed. The method uses a low temperature, environmentally friendly gel-collection method to form a single phase nanomaterial. In one embodiment, the nanomaterial consists of Ba.sub.AMn.sub.BTi.sub.CO.sub.D in a controlled stoichiometry.

  9. Oxidative decomposition of formaldehyde by metal oxides at room temperature

    NASA Astrophysics Data System (ADS)

    Sekine, Yoshika

    Formaldehyde (HCHO) is still a major indoor air pollutant in Japanese air-tight houses and is the subject of numerous complaints regarding health disorders. Authors have developed a passive-type air-cleaning material and an air cleaner using manganese oxide (77% MnO 2) as an active component and successfully reduced indoor HCHO concentrations in newly built multi-family houses. In this study, the reactivity between manganese oxide and HCHO was discussed. We tested the removal efficiencies of several metal oxides for HCHO in a static reaction vessel and found manganese oxide could react with HCHO and release carbon dioxide even at room temperature. The reactivity and mechanisms were discussed for the proposed chemical reactions. A mass balance study proved that a major product through the heterogeneous reaction between manganese oxide and HCHO was carbon dioxide. Harmful by-products (HCOOH and CO) were not found.

  10. Mesoporous Fluorinated Metal-Organic Frameworks with Exceptional Adsorption of Fluorocarbons and CFCs

    SciTech Connect

    Chen, Teng-Hao; Popov, Ilya; Kaveevivitchai, Watchareeya; Chuang, Yu-Chun; Chen, Yu-Sheng; Jacobson, Allan J.; Miljani,; #263; Ognjen, Š.

    2016-02-08

    Two mesoporous fluorinated metal–organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate- and tetrazolate-based ligands. The tetrazolate-based framework MOFF-5 has an accessible surface area of 2445 m2g-1, the highest among fluorinated MOFs. Crystals of MOFF-5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)—the latter two being ozone-depleting substances and potent greenhouse species—with weight capacities of up to 225%. The material exhibits an apparent preference for the adsorption of non-spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride.

  11. Reactor process using metal oxide ceramic membranes

    DOEpatents

    Anderson, Marc A.

    1994-01-01

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane. Also disclosed is a method regenerating a porous metal oxide ceramic membrane used in a photoelectrochemical catalytic process by periodically removing the reactants and regenerating the membrane using a variety of chemical, thermal, and electrical techniques.

  12. Reactor process using metal oxide ceramic membranes

    DOEpatents

    Anderson, M.A.

    1994-05-03

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane. Also disclosed is a method regenerating a porous metal oxide ceramic membrane used in a photoelectrochemical catalytic process by periodically removing the reactants and regenerating the membrane using a variety of chemical, thermal, and electrical techniques. 2 figures.

  13. Mesoporous silicates prepared using preorganized templates in supercritical fluids.

    PubMed

    Pai, Rajaram A; Humayun, Raashina; Schulberg, Michelle T; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J

    2004-01-23

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

  14. Mesoporous Silicates Prepared Using Preorganized Templates in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Pai, Rajaram A.; Humayun, Raashina; Schulberg, Michelle T.; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J.

    2004-01-01

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

  15. A Mesoporous Indium Metal-Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones.

    PubMed

    Reinares-Fisac, Daniel; Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles; Gándara, Felipe

    2016-07-27

    With the aim of developing new highly porous, heterogeneous Lewis acid catalysts for multicomponent reactions, a new mesoporous metal-organic framework, InPF-110 ([In3O(btb)2(HCOO)(L)], (H3btb = 1,3,5-tris(4-carboxyphenyl)benzene acid, L = methanol, water, or ethanol), has been prepared with indium as the metal center. It exhibits a Langmuir surface area of 1470 m(2) g(-1), and its structure consists of hexagonal pores with a 2.8 nm aperture, which allows the diffusion of multiple substrates. This material presents a large density of active metal sites resulting in outstanding catalytic activity in the formation of substituted α-aminonitriles through the one-pot Strecker reaction of ketones. In this respect, InPF-110 stands out compared to other catalysts for this reaction due to the small catalyst loadings required, and without the need for heat or solvents. Furthermore, X-ray single crystal diffraction studies clearly show the framework-substrate interaction through coordination to the accessible indium sites.

  16. Ultrahigh–current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF3 framework

    PubMed Central

    Wang, Hansen; Lin, Dingchang; Liu, Yayuan; Li, Yuzhang; Cui, Yi

    2017-01-01

    Lithium (Li) metal is the ultimate solution for next-generation high–energy density batteries but is plagued from commercialization by infinite relative volume change, low Coulombic efficiency due to side reactions, and safety issues caused by dendrite growth. These hazardous issues are further aggravated under high current densities needed by the increasing demand for fast charging/discharging. We report a one-step fabricated Li/Al4Li9-LiF nanocomposite (LAFN) through an “overlithiation” process of a mesoporous AlF3 framework, which can simultaneously mitigate the abovementioned problems. Reaction-produced Al4Li9-LiF nanoparticles serve as the ideal skeleton for Li metal infusion, helping to achieve a near-zero volume change during stripping/plating and suppressed dendrite growth. As a result, the LAFN electrode is capable of working properly under an ultrahigh current density of 20 mA cm−2 in symmetric cells and manifests highly improved rate capability with increased Coulombic efficiency in full cells. The simple fabrication process and its remarkable electrochemical performances enable LAFN to be a promising anode candidate for next-generation lithium metal batteries. PMID:28913431

  17. Ultrahigh–current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF3 framework

    DOE PAGES

    Wang, Hansen; Lin, Dingchang; Liu, Yayuan; ...

    2017-09-08

    Lithium (Li) metal is the ultimate solution for next-generation high–energy density batteries but is plagued from commercialization by infinite relative volume change, low Coulombic efficiency due to side reactions, and safety issues caused by dendrite growth. These hazardous issues are further aggravated under high current densities needed by the increasing demand for fast charging/discharging. We report a one-step fabricated Li/Al4Li9-LiF nanocomposite (LAFN) through an “overlithiation” process of a mesoporous AlF3 framework, which can simultaneously mitigate the abovementioned problems. Reaction-produced Al4Li9-LiF nanoparticles serve as the ideal skeleton for Li metal infusion, helping to achieve a near-zero volume change during stripping/plating andmore » suppressed dendrite growth. As a result, the LAFN electrode is capable of working properly under an ultrahigh current density of 20 mA cm–2 in symmetric cells and manifests highly improved rate capability with increased Coulombic efficiency in full cells. Here, the simple fabrication process and its remarkable electrochemical performances enable LAFN to be a promising anode candidate for next-generation lithium metal batteries.« less

  18. Hydrophobic modification of Pd/SiO2 @single-site mesoporous silicas by triethoxyfluorosilane: enhanced catalytic activity and selectivity for one-pot oxidation.

    PubMed

    Nakatsuka, Kazuki; Mori, Kohsuke; Okada, Shusuke; Ikurumi, Shohei; Kamegawa, Takashi; Yamashita, Hiromi

    2014-07-01

    To enhance the catalytic activity in a selective one-pot oxidation using in-situ generated H(2)O(2), a hydrophobically modified core-shell catalyst was synthesized by means of a simple silylation reaction using the fluorine-containing silylation agent triethoxyfluorosilane (TEFS, SiF(OEt)(3)). The catalyst consisted of a Pd-supported silica nanosphere and a mesoporous silica shell containing isolated Ti(IV) and F ions bonded with silicon (SiF bond). Structural analyses using XRD and N(2) adsorption-desorption suggested that the mesoporous structure and large surface area of the mesoporous shells were retained even after the modification. During the one-pot oxidation of sulfide, catalytic activity was enhanced significantly by increasing the amount of fluorine in the shell. A hydrophobic surface enhanced adsorption of the hydrophobic reactant into the mesopore, while the less hydrophobic oxygenated products efficiently diffused into the outside of the shell, which improved the catalytic activity and selectivity. In addition, the present methodology can be used to enhance the catalytic activity and selectivity in the one-pot oxidation of cyclohexane by using an Fe-based core-shell catalytic system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preparation with a facile template-free method of uniform-sized mesoporous microspheres of rare earth (La, Ce, Pr, Nd) oxides

    SciTech Connect

    Ji, Pengfei; Xing, Mingyang; Bagwasi, Segomotso; Tian, Baozhu; Chen, Feng; Zhang, Jinlong

    2011-11-15

    Highlights: {yields} Mesoporous microspheres of light rare earth hydroxycarbonates and oxides were fabricated. {yields} The supersaturated urea has important effect on formation of mesoporous microspheres. {yields} The influences of [cation]/[urea] ratio and amount of water on the formation of spherical crystallites were discussed. -- Abstract: Mesoporous microspheres of light rare earth (La, Ce, Pr, Nd) hydroxycarbonates and oxides were successfully fabricated by a facile surfactant free hydrothermal method in supersaturated aqueous urea solution. The techniques of XRD, TEM, SEM, TG/DTA and N{sub 2} adsorption-desorption were employed to investigate the structure and formation process of mesoporous microspheres. It was revealed that supersaturated urea not only serve as a reactant and pH modifier in the reaction system but also guide the oriented assembly of hydroxycarbonate crystallites into microspheres by acting as a structure-directing agent. The microspheres of rare earth oxides could easily be obtained by simple calcination of corresponding hydroxycarbonates precursors without undergoing morphology changes. In addition, the influences of rare earth precursor and urea concentrations on the formation of microspheres were also investigated.

  20. Wet oxidation of ordered mesoporous carbon FDU-15 by using (NH4)2S2O8 for fast adsorption of Sr(II): An investigation on surface chemistry and adsorption mechanism

    NASA Astrophysics Data System (ADS)

    Song, Yang; Ye, Gang; Chen, Jing; Lv, Dachao; Wang, Jianchen

    2015-12-01

    Surface modification of ordered mesoporous carbon (OMC) by wet oxidation provides an oxygen-enriched platform for complexation of metal ions. Here, we present a comprehensive study on the surface chemistry and textual property of OMC FDU-15 modified by wet oxidation using (NH4)2S2O8 as a benign oxidant. And, for the first time, the adsorption behavior and mechanism of wet-oxidized OMC FDU-15 toward Sr(II) in aqueous solutions were investigated. The mesostructural regularity of the OMC FDU-15 was well-reserved under wet oxidation. Compared to OMC CMK-type counterparts prepared via nanocasting, the OMC FDU-15 by soft template method showed much-enhanced structural stability. Due to the introduction of abundant oxygen-containing species, the oxidized OMC FDU-15 exhibited excellent hydrophilicity and dispersibility in aqueous solutions. The adsorption behavior toward Sr(II) was fully investigated, showing a super-fast adsorption kinetics (< 5 min to reach equilibrium) and a Langmuir adsorption isotherm. Moreover, an in-depth X-ray photoelectron spectroscopy analysis through deconvolution of high resolution C1s and O1s spectra was implemented to identify the chemical species of the surface functional groups, while probing the adsorption mechanism. The results suggested that oxygen donor atoms in Csbnd O single bonds mainly contribute to the adsorption of Sr(II) via formation of metal-ligand complexation.

  1. A general approach to crystalline and monomodal pore size mesoporous materials.

    PubMed

    Poyraz, Altug S; Kuo, Chung-Hao; Biswas, Sourav; King'ondu, Cecil K; Suib, Steven L

    2013-01-01

    Mesoporous oxides attract a great deal of interest in many fields, including energy, catalysis and separation, because of their tunable structural properties such as surface area, pore volume and size, and nanocrystalline walls. Here we report thermally stable, crystalline, thermally controlled monomodal pore size mesoporous materials. Generation of such materials involves the use of inverse micelles, elimination of solvent effects, minimizing the effect of water content and controlling the condensation of inorganic frameworks by NO(x) decomposition. Nanosize particles are formed in inverse micelles and are randomly packed to a mesoporous structure. The mesopores are created by interconnected intraparticle voids and can be tuned from 1.2 to 25 nm by controlling the nanoparticle size. Such phenomena allow the preparation of multiple phases of the same metal oxide and syntheses of materials having compositions throughout much of the periodic table, with different structures and thermal stabilities as high as 800 °C.

  2. Method for producing nanostructured metal-oxides

    DOEpatents

    Tillotson, Thomas M.; Simpson, Randall L.; Hrubesh, Lawrence W.; Gash, Alexander

    2006-01-17

    A synthetic route for producing nanostructure metal-oxide-based materials using sol-gel processing. This procedure employs the use of stable and inexpensive hydrated-metal inorganic salts and environmentally friendly solvents such as water and ethanol. The synthesis involves the dissolution of the metal salt in a solvent followed by the addition of a proton scavenger, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively. Using this method synthesis of metal-oxide nanostructured materials have been carried out using inorganic salts, such as of Fe.sup.3+, Cr.sup.3+, Al.sup.3+, Ga.sup.3+, In.sup.3+, Hf.sup.4+, Sn.sup.4+, Zr.sup.4+, Nb.sup.5+, W.sup.6+, Pr.sup.3+, Er.sup.3+, Nd.sup.3+, Ce.sup.3+, U.sup.3+ and Y.sup.3+. The process is general and nanostructured metal-oxides from the following elements of the periodic table can be made: Groups 2 through 13, part of Group 14 (germanium, tin, lead), part of Group 15 (antimony, bismuth), part of Group 16 (polonium), and the lanthanides and actinides. The sol-gel processing allows for the addition of insoluble materials (e.g., metals or polymers) to the viscous sol, just before gelation, to produce a uniformly distributed nanocomposites upon gelation. As an example, energetic nanocomposites of Fe.sub.xO.sub.y gel with distributed Al metal are readily made. The compositions are stable, safe, and can be readily ignited to thermitic reaction.

  3. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  4. Ring Opening of Naphthenic Molecules Over Metal Containing Mesoporous Y Zeolite Catalyst.

    PubMed

    Lee, You-Jin; Kim, Eun Sang; Kim, Tae-Wan; Kim, Chul-Ung; Jeong, Kwang-Eun; Lee, Chang-Ha; Jeong, Soon-Yong

    2015-07-01

    Mesoporous Y zeolite (Meso-Y) with a uniform mesopore was synthesized via pseudomorphic syn- thesis. The Meso-Y supported Ni-W catalyst (NiW/Meso-Y) was introduced as a catalyst for the selective ring opening of naphthenic rings. The catalytic test for the ring opening of naphthalene as a model compound of multi-ring aromatics was performed using a batch-type reaction system with both sulfided 20 wt% NiW/Meso-Y and NiW/Y catalysts under different reaction conditions. The catalytic results reveal that the Meso-Y supported NiW catalyst experiences a naphthalene conversion similar to the NiW/Y catalyst, but the NiW/Meso-Y catalyst has higher product yields for BTEX (benzene, toluene, ethyl benzene, and xylene) and the middle distillate than those of the NiW/Y catalyst at a low reaction temperature. These results suggest that the mesoporosity of the NiW/Meso-Y catalyst is more advantageous for the ring opening reaction of multi-ring aromatics due to the easier access for the bulky molecules compared to the NiW/Y catalyst.

  5. Transition metal oxide nanowires synthesized by heating metal substrates

    SciTech Connect

    Yan, Hui; Sun, Yi; He, Lin; Nie, Jia-Cai

    2011-11-15

    Highlights: {center_dot} This paper describes a simple and general method to synthesize 3d metal oxide nanowires. {center_dot} Self-catalysis growth mechanism was proposed to explain the growth of the nanowires. {center_dot} The temperature range for the growth of nanowires was estimated by taking into account the Gibbs free energy of reaction. {center_dot} This synthesis approach could be applied to synthesize other one-dimensional structures, such as FeSe and Bi{sub 2}Te{sub 3} nanowires. -- Abstract: Here we reported a simple method to synthesize transition metal oxide nanowires. Copper oxide (CuO), zinc oxide (ZnO), and cobalt oxide (Co{sub 3}O{sub 4}) nanowires were synthesized by heating the copper, zinc, and cobalt substrates under atmosphere condition. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to analyze the morphology and microstructure of the nanowires. According to our experimental results, self-catalysis growth mechanism was proposed to explain the growth of the nanowires. The temperature window for the growth of nanowires was estimated by taking into account the Gibbs free energy of reaction. The synthesis approach observed in our experiment could be applied to synthesize other one-dimensional structures, such as FeSe and Bi{sub 2}Te{sub 3} nanowires.

  6. Nickel(II) oxide nanostructure derived from metal-organic frameworks and its adsorption capability

    NASA Astrophysics Data System (ADS)

    Ru, Shuai; Xu, Lina; Xiao, Hongping; Li, Xinhua

    2016-11-01

    Nanosized nickel(II) oxide (NiO) was obtained by oxidation of ([(Ni2(nic)4(H2O)] n , nic = nicotinic acid), a metal-organic framework (MOF), at 350 °C. Nanosized NiO assembled to form block NiO having a mesoporous structure similar to the porous structure of activated carbon block. This bulk NiO exhibits excellent adsorbing capability, with 100% higher adsorption capacities than the [(Ni2(nic)4(H2O)] n MOF towards toluene and water steam; therefore, it can find potential application in gas adsorption. Moreover, this bulk NiO can be synthesized using a facile, environment-friendly, and cost-effective method, and exhibits excellent hydrothermal stability, which is not commonly observed for MOFs.

  7. Electroplating lithium transition metal oxides

    PubMed Central

    Zhang, Huigang; Ning, Hailong; Busbee, John; Shen, Zihan; Kiggins, Chadd; Hua, Yuyan; Eaves, Janna; Davis, Jerome; Shi, Tan; Shao, Yu-Tsun; Zuo, Jian-Min; Hong, Xuhao; Chan, Yanbin; Wang, Shuangbao; Wang, Peng; Sun, Pengcheng; Xu, Sheng; Liu, Jinyun; Braun, Paul V.

    2017-01-01

    Materials synthesis often provides opportunities for innovation. We demonstrate a general low-temperature (260°C) molten salt electrodeposition approach to directly electroplate the important lithium-ion (Li-ion) battery cathode materials LiCoO2, LiMn2O4, and Al-doped LiCoO2. The crystallinities and electrochemical capacities of the electroplated oxides are comparable to those of the powders synthesized at much higher temperatures (700° to 1000°C). This new growth method significantly broadens the scope of battery form factors and functionalities, enabling a variety of highly desirable battery properties, including high energy, high power, and unprecedented electrode flexibility. PMID:28508061

  8. Mesoporous Silicon Hollow Nanocubes Derived from Metal-Organic Framework Template for Advanced Lithium-Ion Battery Anode.

    PubMed

    Yoon, Taeseung; Bok, Taesoo; Kim, Chulhyun; Na, Younghoon; Park, Soojin; Kim, Kwang S

    2017-05-23

    Controlling the morphology of nanostructured silicon is critical to improving the structural stability and electrochemical performance in lithium-ion batteries. The use of removable or sacrificial templates is an effective and easy route to synthesize hollow materials. Herein, we demonstrate the synthesis of mesoporous silicon hollow nanocubes (m-Si HCs) derived from a metal-organic framework (MOF) as an anode material with outstanding electrochemical properties. The m-Si HC architecture with the mesoporous external shell (∼15 nm) and internal void (∼60 nm) can effectively accommodate volume variations and relieve diffusion-induced stress/strain during repeated cycling. In addition, this cube architecture provides a high electrolyte contact area because of the exposed active site, which can promote the transportation of Li ions. The well-designed m-Si HC with carbon coating delivers a high reversible capacity of 1728 mAhg(-1) with an initial Coulombic efficiency of 80.1% after the first cycle and an excellent rate capability of >1050 mAhg(-1) even at a 15 C-rate. In particular, the m-Si HC anode effectively suppresses electrode swelling to ∼47% after 100 cycles and exhibits outstanding cycle stability of 850 mAhg(-1) after 800 cycles at a 1 C-rate. Moreover, a full cell (2.9 mAhcm(-2)) comprising a m-Si HC-graphite anode and LiCoO2 cathode exhibits remarkable cycle retention of 72% after 100 cycles at a 0.2 C-rate.

  9. Mesoporous NiCo2O4-decorated reduced graphene oxide as a novel platform for electrochemical determination of rutin.

    PubMed

    Cui, Shiqiang; Li, Li; Ding, Yaping; Zhang, Jiangjiang; Yang, Hua; Wang, Yingzi

    2017-03-01

    The glassy carbon electrode (GCE) modified with mesoporous NiCo2O4-decorated reduced graphene oxide (NiCo2O4/rGO) was first applied for the electrochemical determination of rutin. The synthesized NiCo2O4 and NiCo2O4/rGO were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) method. The sensor not only showed a satisfactory linear range (0.1-150μM) and detection limit (0.01μM) but also exhibited the good anti-interference abilities, low price, high stability, as well as favorable precision and accuracy. The present work is meaningful to expand functionalized graphene composites to sensor fields and promote the development of rutin sensors.

  10. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  11. 40 CFR 721.10500 - Acrylated mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acrylated mixed metal oxides (generic... Specific Chemical Substances § 721.10500 Acrylated mixed metal oxides (generic). (a) Chemical substance and... mixed metal oxides (PMN P-06-341) is subject to reporting under this section for the significant...

  12. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  13. 40 CFR 721.5549 - Lithiated metal oxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Lithiated metal oxide. 721.5549... Substances § 721.5549 Lithiated metal oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as lithiated metal oxide (LiNiO2) (PMN...

  14. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  15. 40 CFR 721.5549 - Lithiated metal oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lithiated metal oxide. 721.5549... Substances § 721.5549 Lithiated metal oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as lithiated metal oxide (LiNiO2) (PMN...

  16. 40 CFR 721.5549 - Lithiated metal oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Lithiated metal oxide. 721.5549... Substances § 721.5549 Lithiated metal oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as lithiated metal oxide (LiNiO2) (PMN...

  17. 40 CFR 721.5549 - Lithiated metal oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lithiated metal oxide. 721.5549... Substances § 721.5549 Lithiated metal oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as lithiated metal oxide (LiNiO2) (PMN...

  18. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  19. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  20. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  1. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  2. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  3. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  4. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  5. 40 CFR 721.5549 - Lithiated metal oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Lithiated metal oxide. 721.5549... Substances § 721.5549 Lithiated metal oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as lithiated metal oxide (LiNiO2) (PMN...

  6. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  7. 40 CFR 721.10500 - Acrylated mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acrylated mixed metal oxides (generic... Specific Chemical Substances § 721.10500 Acrylated mixed metal oxides (generic). (a) Chemical substance and... mixed metal oxides (PMN P-06-341) is subject to reporting under this section for the significant...

  8. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  9. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  10. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  11. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  12. Polymorphism Control in Nanostructured Metal Oxides

    NASA Astrophysics Data System (ADS)

    Sood, Shantanu

    Polymorphic phase transformations are common to all nanocrystalline binary metal oxides. The polymorphic nature of such metal oxides makes available a large number of phases with differing crystal structures, each stable under certain conditions of temperature, pressure, and/or particle size. These different crystal structures translate to unique physical and chemical properties for each structural class of polymorphs. Thus predicting when polymorphic phase transitions are likely to occur becomes important to the synthesis of stable functional materials with desired properties. Theoretical calculations using a heuristic approach have resulted in an accurate estimation of the critical particle size predicting metastable to stable phase transitions. This formula is applied to different case studies: for anatase to rutile titania; gamma-Alumina to alpha-Alumina; and tetragonal to monoclinic zirconia. The theoretical values calculated have been seen to be very close to the experimental results from the literature. Manifestation of the effect of phase transitions in nanostructured metal oxides was provided in the study of metastable to stable phase transitions in WO3. Nanowires of tungsten trioxide have been synthesized in-situ inside an electron microscope. Such structure of tungsten trioxide result due to a metastable to stable phase transformation, from the cubic to the monoclinic phase. The transformation is massive and complete. The structures formed are unique one-dimensional nanowires. Such a method can be scaled inside any equipment equipped with an electron gun, for example lithography systems either using STEM or E-beam lithography. Another study on nanowire formation in binary metal oxides involved the synthesis of stable orthorhombic MoO3 by means of blend electrospinning. Both a traditional single jet electrospinning set up and a novel high-throughput process to get high aspect ratio nanowires. The latter is a jet-controlled and flow controlled

  13. Design of a Metal Oxide-Organic Framework (MoOF) Foam Microreactor: Solar-Induced Direct Pollutant Degradation and Hydrogen Generation.

    PubMed

    Zhu, Liangliang; Fu Tan, Chuan; Gao, Minmin; Ho, Ghim Wei

    2015-12-16

    A macroporous carbon network combined with mesoporous catalyst immobilization by a template method gives a metal-oxide-organic framework (MoOF) foam microreactor that readily soaks up pollutants and localizes solar energy in itself, leading to effective degradation of water pollutants (e.g., methyl orange (MO) and also hydrogen generation. The cleaned-up water can be removed from the microreactor simply by compression, and the microreactor used repeatedly.

  14. Bimetallic oxamato complexes synthesized into mesoporous matrix as precursor to tunable nanosized oxide

    SciTech Connect

    Kalinke, Lucas H.G.; Stumpf, Humberto O.; Mazali, Italo O.; Cangussu, Danielle

    2015-10-15

    Highlights: • The bimetallic oxamato complexes as single-source precursor. • We prepared into a porous silica glass tunable nanosized oxide powders. • X-ray diffraction shows the formation of CeO{sub 2}/CuO and spinel cobaltite. • The different number of IDC allows control of the nanoparticle size. - Abstract: The bimetallic complexes were employed to prepare into a porous silica glass tunable nanosized oxide powders through the single source precursor (SSP) method. These materials were prepared by first anchoring of [Cu(opba)]{sup 2−} [opba = ortho-phenylenebis(oxamato)], second by reaction in situ with second metal [Co(II) or Ce(III)] and followed by a thermal treatment. The different number of impregnation–decomposition cycles (IDC) allows control of the nanoparticle size. X-ray diffraction shows the formation of mixture CeO{sub 2}–CuO and spinel copper cobaltite. Raman spectroscopy confirmed the formation of such phases. Transmission electron microscopy images revealed that spinel cobaltite particles (8 IDC) present a mean size of about 9 nm, whereas for the CeO{sub 2}–CuO phase the particle diameters are 4 nm (2 IDC) and 8 nm (6 IDC). For CeO{sub 2}–CuO the diffuse reflectance spectroscopy indicates a consistent red shift in band gap from 3.41 to 2.87 eV with increasing of particle size due to quantum confinement effect.

  15. Design of an ultrasmall Au nanocluster-CeO2 mesoporous nanocomposite catalyst for nitrobenzene reduction.

    PubMed

    Chong, Hanbao; Li, Peng; Xiang, Ji; Fu, Fangyu; Zhang, Dandan; Ran, Xiaorong; Zhu, Manzhou

    2013-08-21

    In this work we are inspired to explore gold nanoclusters supported on mesoporous CeO2 nanospheres as nanocatalysts for the reduction of nitrobenzene. Ultrasmall Au nanoclusters (NCs) and mesoporous CeO2 nanospheres were readily synthesized and well characterized. Due to their ultrasmall size, the as-prepared Au clusters can be easily absorbed into the mesopores of the mesoporous CeO2 nanospheres. Owing to the unique mesoporous structure of the CeO2 support, Au nanoclusters in the Au@CeO2 may effectively prevent the aggregation which usually results in a rapid decay of the catalytic activity. It is notable that the ultrasmall gold nanoclusters possess uniform size distribution and good dispersibility on the mesoporous CeO2 supports. Compared to other catalyst systems with different oxide supports, the as-prepared Au nanocluster-CeO2 nanocomposite nanocatalysts showed efficient catalytic performance in transforming nitrobenzene into azoxybenzene. In addition, a plausible mechanism was deeply investigated to explain the transforming process. Au@CeO2 exhibited efficient catalytic activity for reduction of nitrobenzene. This strategy may be easily extended to fabricate many other heterogeneous catalysts including ultrasmall metal nanoclusters and mesoporous oxides.

  16. Reactor vessel using metal oxide ceramic membranes

    DOEpatents

    Anderson, Marc A.; Zeltner, Walter A.

    1992-08-11

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane.

  17. A New Class of Highly Dispersed VOx Catalysts on Mesoporous Silica: Synthesis, Characterization, and Catalytic Activity in the Partial Oxidation of Ethanol

    SciTech Connect

    Kwak, Ja Hun; Herrera, Jose E.; Hu, Jian Zhi; Wang, Yong; Peden, Charles HF

    2006-01-26

    The morphology of vanadium oxide supported on a titania-modified mesoporous silica (MCM-41), obtained by means of a careful grafting process through atomic layer deposition, was studied using a variety of characterization techniques. The XRD together with TEM, 51V-NMR, Raman, FTIR and DRS-UV-Vis results showed that the vanadia species are extremely well dispersed onto the surface of the mesoporous support; the dispersion being stable upon thermal treatments up to 400 °C. Studies of the catalytic activity of these materials were performed using the partial oxidation of ethanol as a probe reaction. The results indicate an intrinsic relationship between dispersion, the presence of a TiO2-VOx phase, and catalytic activity for oxidation and dehydration.

  18. Facile and Mild Strategy to Construct Mesoporous CeO2-CuO Nanorods with Enhanced Catalytic Activity toward CO Oxidation.

    PubMed

    Chen, Guozhu; Xu, Qihui; Yang, Ying; Li, Cuncheng; Huang, Taizhong; Sun, Guoxin; Zhang, Shuxiang; Ma, Dongling; Li, Xu

    2015-10-28

    CeO2-CuO nanorods with mesoporous structure were synthesized by a facile and mild strategy, which involves an interfacial reaction between Ce2(SO4)3 precursor and NaOH ethanol solution at room temperature to obtain mesoporous CeO2 nanorods, followed by a solvothermal treatment of as-prepared CeO2 and Cu(CH3COO)2. Upon solvothermal treatment, CuO species is highly dispersed onto the CeO2 nanorod surface to form CeO2-CuO composites, which still maintain the mesoporous feature. A preliminary CO catalytic oxidation study demonstrated that the CeO2-CuO samples exhibited strikingly high catalytic activity, and a high CO conversion rate was observed without obvious loss in activity even after thermal treatment at a high temperature of 500 °C. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H2-TPR) analysis revealed that there is a strong interaction between CeO2 and CuO. Moreover, it was found that the introduction of CuO species into CeO2 generates oxygen vacancies, which is highly likely to be responsible for high catalytic activity toward CO oxidation of the mesoporous CeO2-CuO nanorods.

  19. A Review of Recent Developments of Mesoporous Materials.

    PubMed

    Suib, Steven L

    2017-06-29

    This personal account concerns novel recent discoveries in the area of mesoporous materials. Most of the papers discussed have been published within the last two to three years. A major emphasis of most of these papers is the synthesis of unique mesoporous materials by a variety of synthetic methods. Many of these articles focus on the control of the pore sizes and shapes of mesoporous materials. Synthetic methods of various types have been used for such control of porosity including soft templating, hard templating, nano-casting, electrochemical methods, surface functionalization, and trapping of species in pores. The types of mesoporous materials range from carbon materials, metal oxides, metal sulfides, metal nitrides, carbonitriles, metal organic frameworks (MOFs), and composite materials. The vast majority of recent publications have centered around biological applications with a majority dealing with drug delivery systems. Several other bio-based articles on mesoporous systems concern biomass conversion and biofuels, magnetic resonance imaging (MRI) studies, ultrasound therapy, enzyme immobilization, antigen targeting, biodegradation of inorganic materials, applications for improved digestion, and antitumor activity. Numerous nonbiological applications of mesoporous materials have been pursued recently. Some specific examples are photocatalysis, photo-electrocatalysis, lithium ion batteries, heterogeneous catalysis, extraction of metals, extraction of lanthanide and actinide species, chiral separations and catalysis, capturing and the mode of binding of carbon dioxide (CO2 ), optical devices, and magneto-optical devices. Of this latter class of applications, heterogeneous catalysis is predominant. Some of the types of catalytic reactions being pursued include hydrogen generation, selective oxidations, aminolysis, Suzuki coupling and other coupling reactions, oxygen reduction reactions (ORR), oxygen evolution reactions (OER), and bifunctional catalysis. For

  20. Topological crystalline insulators in transition metal oxides.

    PubMed

    Kargarian, Mehdi; Fiete, Gregory A

    2013-04-12

    Topological crystalline insulators possess electronic states protected by crystal symmetries, rather than time-reversal symmetry. We show that the transition metal oxides with heavy transition metals are able to support nontrivial band topology resulting from mirror symmetry of the lattice. As an example, we consider pyrochlore oxides of the form A2M2O7. As a function of spin-orbit coupling strength, we find two Z2 topological insulator phases can be distinguished from each other by their mirror Chern numbers, indicating a different topological crystalline insulators. We also derive an effective k·p Hamiltonian, similar to the model introduced for Pb(1-x)Sn(x)Te, and discuss the effect of an on-site Hubbard interaction on the topological crystalline insulator phase using slave-rotor mean-field theory, which predicts new classes of topological quantum spin liquids.

  1. NMR in Copper-Oxide Metals

    SciTech Connect

    Varma, C.M.

    1996-10-01

    The anomalous part of the NMR relaxation rate of copper nuclei in the normal state of copper-oxide metals is calculated using the orbital magnetic parts of the fluctuations derived in a recent theory to explain the long wavelength transport anomalies. Oxygen and yttrium reside on lattice sites at which the anomalous contribution is absent at all hole densities. The frequency, momentum dependence, and the form factor of the fluctuations is predicted. {copyright} {ital 1996 The American Physical Society.}

  2. Catalytic evaluation on liquid phase oxidation of vanillyl alcohol using air and H2O2 over mesoporous Cu-Ti composite oxide

    NASA Astrophysics Data System (ADS)

    Saha, Subrata; Hamid, Sharifah Bee Abd; Ali, Tammar Hussein

    2017-02-01

    A mesoporous, highly crystalline Cu-Ti composite oxide catalyst was prepared via facile, simple and modified solution method varying Cu and Ti ratio for selective liquid phase oxidation of vanillyl alcohol. Various spectroscopic procedures were employed to systematically characterize the catalyst structural and physicochemical properties. The defect chemistry of the catalyst was confirmed from the presence of surface defects revealed through HRTEM imagery between the TiO2 (101) and Cu3TiO4 (012) planes, complemented by the XRD profiling. Further, presence of oxygen vacancy evidenced by O 1s XPS spectra were observed on the catalyst surface. Moreover, the stoichiometry of Cu and Ti in the catalyst synthesis protocol was notably found to be the vital determinant to alter the redox properties of Cu-Ti composite oxide catalyst supported by H2-TPR. O2-TPD analysis. Moreover, a rational investigation was done using different oxidants such as air and H2O2 with variables reaction conditions. The catalyst was active for liquid phase oxidation of vanillyl alcohol to vanillin with performance of 66% conversion and 71% selectivity using H2O2 in base free condition. And also, catalytic activity was significantly improved by 94% conversion with 86% selectivity to vanillin in liquid phase aerobic oxidation at the optimum reaction conditions. To expand the superiority of the catalyst, three times reusability study was also examined with appreciable catalytic activity.

  3. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

    PubMed

    Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

    2015-04-28

    Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption.

  4. Metal oxide nanoparticles with low toxicity.

    PubMed

    Ng, Alan Man Ching; Guo, Mu Yao; Leung, Yu Hang; Chan, Charis M N; Wong, Stella W Y; Yung, Mana M N; Ma, Angel P Y; Djurišić, Aleksandra B; Leung, Frederick C C; Leung, Kenneth M Y; Chan, Wai Kin; Lee, Hung Kay

    2015-10-01

    A number of different nanomaterials produced and incorporated into various products are rising. However, their environmental hazards are frequently unknown. Here we consider three different metal oxide compounds (SnO2, In2O3, and Al2O3), which have not been extensively studied and are expected to have low toxicity. This study aimed to comprehensively characterize the physicochemical properties of these nanomaterials and investigate their toxicity on bacteria (Escherichia coli) under UV illumination and in the dark, as well as on a marine diatom (Skeletonema costatum) under ambient illumination/dark (16-8h) cycles. The material properties responsible for their low toxicity have been identified based on comprehensive experimental characterizations and comparison to a metal oxide exhibiting significant toxicity under illumination (anatase TiO2). The metal oxide materials investigated exhibited significant difference in surface properties and interaction with the living organisms. In order for a material to exhibit significant toxicity, it needs to be able to both form a stable suspension in the culture medium and to interact with the cell walls of the test organism. Our results indicated that the observed low toxicities of the three nanomaterials could be attributed to the limited interaction between the nanoparticles and cell walls of the test organisms. This could occur either due to the lack of significant attachment between nanoparticles and cell walls, or due to their tendency to aggregate in solution. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Method for producing metal oxide aerogels

    DOEpatents

    Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

    1995-01-01

    A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

  6. Method for producing metal oxide aerogels

    DOEpatents

    Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

    1995-04-25

    A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

  7. Adsorptive interaction of bisphenol A with mesoporous titanosilicate/reduced graphene oxide nanocomposite materials: FT-IR and Raman analyses

    NASA Astrophysics Data System (ADS)

    Nguyen-Huy, Chinh; Kim, Nayoung; Nguyen-Phan, Thuy-Duong; Yoo, Ik-Keun; Woo Shin, Eun

    2014-09-01

    Nanocomposite materials containing graphene oxide have attracted tremendous interest as catalysts and adsorbents for water purification. In this study, mesoporous titanosilicate/reduced graphene oxide composite materials with different Ti contents were employed as adsorbents for removing bisphenol A (BPA) from water systems. The adsorptive interaction between BPA and adsorption sites on the composite materials was investigated by Fourier transform infrared (FT-IR) and Raman spectroscopy. Adsorption capacities of BPA at equilibrium, q e (mg/g), decreased with increasing Ti contents, proportional to the surface area of the composite materials. FT-IR observations for fresh and spent adsorbents indicated that BPA adsorbed onto the composite materials by the electrostatic interaction between OH functional groups contained in BPA and on the adsorbents. The electrostatic adsorption sites on the adsorbents were categorized into three hydroxyl groups: Si-OH, Ti-OH, and graphene-OH. In Raman spectra, the intensity ratios of D to G band were decreased after the adsorption of BPA, implying adsorptive interaction of benzene rings of BPA with the sp2 hybrid structure of the reduced graphene oxide.

  8. Adsorptive interaction of bisphenol A with mesoporous titanosilicate/reduced graphene oxide nanocomposite materials: FT-IR and Raman analyses

    PubMed Central

    2014-01-01

    Nanocomposite materials containing graphene oxide have attracted tremendous interest as catalysts and adsorbents for water purification. In this study, mesoporous titanosilicate/reduced graphene oxide composite materials with different Ti contents were employed as adsorbents for removing bisphenol A (BPA) from water systems. The adsorptive interaction between BPA and adsorption sites on the composite materials was investigated by Fourier transform infrared (FT-IR) and Raman spectroscopy. Adsorption capacities of BPA at equilibrium, q e (mg/g), decreased with increasing Ti contents, proportional to the surface area of the composite materials. FT-IR observations for fresh and spent adsorbents indicated that BPA adsorbed onto the composite materials by the electrostatic interaction between OH functional groups contained in BPA and on the adsorbents. The electrostatic adsorption sites on the adsorbents were categorized into three hydroxyl groups: Si-OH, Ti-OH, and graphene-OH. In Raman spectra, the intensity ratios of D to G band were decreased after the adsorption of BPA, implying adsorptive interaction of benzene rings of BPA with the sp2 hybrid structure of the reduced graphene oxide. PMID:25258598

  9. Hydrous metal oxide catalysts for oxidation of hydrocarbons

    SciTech Connect

    Miller, J.E.; Dosch, R.G.; McLaughlin, L.I.

    1993-07-01

    This report describes work performed at Sandia under a CRADA with Shell Development of Houston, Texas aimed at developing hydrous metal oxide (HMO) catalysts for oxidation of hydrocarbons. Autoxidation as well as selective oxidation of 1-octene was studied in the presence of HMO catalysts based on known oxidation catalysts. The desired reactions were the conversion of olefin to epoxides, alcohols, and ketones, HMOs seem to inhibit autoxidation reactions, perhaps by reacting with peroxides or radicals. Attempts to use HMOs and metal loaded HMOs as epoxidation catalysts were unsuccessful, although their utility for this reaction was not entirely ruled out. Likewise, alcohol formation from olefins in the presence of HMO catalysts was not achieved. However, this work led to the discovery that acidified HMOs can lead to carbocation reactions of hydrocarbons such as cracking. An HMO catalyst containing Rh and Cu that promotes the reaction of {alpha}-olefins with oxygen to form methyl ketones was identified. Although the activity of the catalyst is relatively low and isomerization reactions of the olefin simultaneously occur, results indicate that these problems may be addressed by eliminating mass transfer limitations. Other suggestions for improving the catalyst are also made. 57 refs.

  10. N/S-heterocyclic contaminant removal from fuels by the mesoporous metal-organic framework MIL-100: the role of the metal ion.

    PubMed

    Van de Voorde, Ben; Boulhout, Mohammed; Vermoortele, Frederik; Horcajada, Patricia; Cunha, Denise; Lee, Ji Sun; Chang, Jong-San; Gibson, Emma; Daturi, Marco; Lavalley, Jean-Claude; Vimont, Alexandre; Beurroies, Isabelle; De Vos, Dirk E

    2013-07-03

    The influence of the metal ion in the mesoporous metal trimesate MIL-100(Al(3+), Cr(3+), Fe(3+), V(3+)) on the adsorptive removal of N/S-heterocyclic molecules from fuels has been investigated by combining isotherms for adsorption from a model fuel solution with microcalorimetric and IR spectroscopic characterizations. The results show a clear influence of the different metals (Al, Fe, Cr, V) on the affinity for the heterocyclic compounds, on the integral adsorption enthalpies, and on the uptake capacities. Among several factors, the availability of coordinatively unsaturated sites and the presence of basic sites next to the coordinative vacancies are important factors contributing to the observed affinity differences for N-heterocyclic compounds. These trends were deduced from IR spectroscopic observation of adsorbed indole molecules, which can be chemisorbed coordinatively or by formation of hydrogen bonded species. On the basis of our results we are able to propose an optimized adsorbent for the deep and selective removal of nitrogen contaminants out of fuel feeds, namely MIL-100(V).

  11. Impact dynamics of oxidized liquid metal drops

    NASA Astrophysics Data System (ADS)

    Xu, Qin; Brown, Eric; Jaeger, Heinrich M.

    2013-04-01

    With exposure to air, many liquid metals spontaneously generate an oxide layer on their surface. In oscillatory rheological tests, this skin is found to introduce a yield stress that typically dominates the elastic response but can be tuned by exposing the metal to hydrochloric acid solutions of different concentration. We systematically studied the normal impact of eutectic gallium-indium (eGaIn) drops under different oxidation conditions and show how this leads to two different dynamical regimes. At low impact velocity (or low Weber number), eGaIn droplets display strong recoil and rebound from the impacted surface when the oxide layer is removed. In addition, the degree of drop deformation or spreading during impact is controlled by the oxide skin. We show that the scaling law known from ordinary liquids for the maximum spreading radius as a function of impact velocity can still be applied to the case of oxidized eGaIn if an effective Weber number We is employed that uses an effective surface tension factoring in the yield stress. In contrast, no influence on spreading from different oxidations conditions is observed for high impact velocity. This suggests that the initial kinetic energy is mostly damped by bulk viscous dissipation. Results from both regimes can be collapsed in an impact phase diagram controlled by two variables, the maximum spreading factor Pm=R0/Rm, given by the ratio of initial to maximum drop radius, and the impact number K=We/Re4/5, which scales with the effective Weber number We as well as the Reynolds number Re. The data exhibit a transition from capillary to viscous behavior at a critical impact number Kc≈0.1.

  12. Method for inhibiting oxidation of metal sulfide-containing material

    DOEpatents

    Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

    2006-12-26

    The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

  13. Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation

    PubMed Central

    2014-01-01

    Mesoporous tungsten trioxide (WO3) was prepared from tungstic acid (H2WO4) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO3 sample (denoted as WO3-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO3-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores. N2 physisorption studies show a Brunauer-Emmett-Teller (BET) surface area up to 57 m2 g-1 together with type IV isotherms and uniform distribution of a nanoscale pore size in the mesopore region. Scanning electron microscopy (SEM) images exhibit well-connected tiny spherical WO3 particles with a diameter of ca. 5 to 20 nm composing the mesoporous network. The WO3-DDA electrode generated photoanodic current density of 1.1 mA cm-2 at 1.0 V versus Ag/AgCl under visible light irradiation, which is about three times higher than that of the untemplated WO3. O2 (1.49 μmol; Faraday efficiency, 65.2%) was evolved during the 1-h photoelectrolysis for the WO3-DDA electrode under the conditions employed. The mesoporous electrode turned out to work more efficiently for visible-light-driven water oxidation relative to the untemplated WO3 electrode. PMID:25313301

  14. Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation.

    PubMed

    Li, Dong; Chandra, Debraj; Saito, Kenji; Yui, Tatsuto; Yagi, Masayuki

    2014-01-01

    Mesoporous tungsten trioxide (WO3) was prepared from tungstic acid (H2WO4) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO3 sample (denoted as WO3-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO3-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores. N2 physisorption studies show a Brunauer-Emmett-Teller (BET) surface area up to 57 m(2) g(-1) together with type IV isotherms and uniform distribution of a nanoscale pore size in the mesopore region. Scanning electron microscopy (SEM) images exhibit well-connected tiny spherical WO3 particles with a diameter of ca. 5 to 20 nm composing the mesoporous network. The WO3-DDA electrode generated photoanodic current density of 1.1 mA cm(-2) at 1.0 V versus Ag/AgCl under visible light irradiation, which is about three times higher than that of the untemplated WO3. O2 (1.49 μmol; Faraday efficiency, 65.2%) was evolved during the 1-h photoelectrolysis for the WO3-DDA electrode under the conditions employed. The mesoporous electrode turned out to work more efficiently for visible-light-driven water oxidation relative to the untemplated WO3 electrode.

  15. The synthesis of clusters of iron oxides in mesopores of monodisperse spherical silica particles

    NASA Astrophysics Data System (ADS)

    Stovpiaga, E. Yu.; Eurov, D. A.; Kurdyukov, D. A.; Smirnov, A. N.; Yagovkina, M. A.; Grigorev, V. Yu.; Romanov, V. V.; Yakovlev, D. R.; Golubev, V. G.

    2017-08-01

    The method of obtaining nanoclusters α-Fe2O3 in the pores of monodisperse spherical particles of mesoporous silica ( mSiO2) by a single impregnation of the pores with a melt of crystalline hydrate of ferric nitrate and its subsequent thermal destruction has been proposed. Fe3O4 nanoclusters are synthesized from α-Fe2O3 in the pores by reducing in thermodynamically equilibrium conditions. Then particles containing Fe3O4 were annealed in oxygen for the conversion of Fe3O4 back to α-Fe2O3. In the result, the particles with the structure of the core-shell mSiO2/Fe3O4@ mSiO2/α-Fe2O3 are obtained. The composition and structure of synthesized materials as well as the field dependence of the magnetic moment on the magnetic field strength have been investigated.

  16. Biomarker sensing using nanostructured metal oxide sensors

    NASA Astrophysics Data System (ADS)

    Kalyanasundaram, Krithika

    Resistive Chemical sensors are those gas sensitive materials, typically semiconducting metal oxides, that change their electrical properties in response to a change in the ambient. The key features of a chemosensor are sensitivity, selectivity, response time and sensor stability. The hypothesis of this work is that, since metal oxides are polymorphic compounds, the crystal structure of the specific polymorph determines the relative gas selectivity of the material; also that the morphology of the sensing element determines the gas sensitivity limit. This work focuses on the synthesis of nanostructured metal oxides for chemosensors used in selective 'biomarker' detection. Biomarkers are chemical compounds, products of human metabolism which act as specific disease markers. The biomarkers studied in this work include NO, isoprene, NH3, ethanol and acetone which can all be found in exhaled human breath and which allow the non-invasive detection of a range of diseases. Sensors based on three different metal oxides-MoO3, WO 3, and TiO2 were fabricated using sol-gel, electrospinning and spray pyrolysis techniques and tested both as single elements and in an array configuration (electronic nose). The effects of the processing method used, grain size and shape and crystal phase of the material produced, and temperature effects of postsynthesis processing and sensing have been evaluated. Structural characterization has been carried out using X-Ray Diffraction, Scanning and High Resolution Transmission Electron Microscopy, while spectroscopic measurements using XPS, Raman and In-situ FTIR provide valuable information about the surface-analyte interactions. This work has shown that the use of monoclinic polymorph of WO3 yields a selective response to NO, while the other phase of the same oxide give a non-selective chemical response. The orthorhombic phase of MoO 3 exhibits specificity to NH3. An explanation for the variable sensing properties is given based on the gas

  17. Positioning metal-organic framework nanoparticles within the context of drug delivery - A comparison with mesoporous silica nanoparticles and dendrimers.

    PubMed

    Wuttke, Stefan; Lismont, Marjorie; Escudero, Alberto; Rungtaweevoranit, Bunyarat; Parak, Wolfgang J

    2017-04-01

    Nanotechnology enables the creation of delivery vehicles able to overcome physiologically imposed barriers, allowing new approaches for reducing the unwanted side effects of systemic delivery of drug, increasing targeting efficiency and so improving therapy efficacy. Owing to the considerable advances in material sciences and pharmaceutics, a broad range of different inorganic or organic drug nanocarriers have been developed. Furthermore, researchers have shown that the combination of inorganic and organic chemistries in one single material, named metal-organic framework (MOF), offers structural designability at the molecular level together with tunable porosity and chemical functionalisability. While the MOF size can be controlled at the nanometer scale, these features are of paramount interest in the development of the next generation of drug delivery systems. After a short state-of-the-art about MOF technology and within the drug delivery context, this paper discusses the benefits of using MOF nanoparticles compared to dendrimers and mesoporous silica nanoparticles in order to understand the challenges that must still be overcome.

  18. Mesoporous zeolite-supported noble metal catalysts for low-temperature hydrogenation of aromatics in distillate fuels

    SciTech Connect

    Reddy, K.M.; Song, C.

    1996-12-31

    The present work is concerned with deep hydrogenation of aromatics in distillate fuels at low temperatures using mesoporous zeolite-supported noble metal catalysts. This work is a part of our on-going effort to develop advanced thermally stable jet fuels from coal-derived liquids and petroleum. Saturation of naphthalene and its derivatives from only reduces aromatics contents of jet fuels, but also generates decalins which show much higher thermal stability than long-chain alkanes in jet fuels at high temperature. This work also has a bearing on developing new catalytic processes for low-temperature hydrogenation of distillate fuels. The Clean Air Act Amendments of 1990 and new regulations call for the production and use of more environmentally friendly transportation fuels with lower contents of sulfur and aromatics. High aromatic content in distillate fuels lowers the fuel quality and contributes significantly to the formation of environmentally harmful emissions. California Air Resources Board (CARB) has passed legislative measures to limit the sulfur and aromatic contents of diesel fuel to 0.05 wt% and 10 vol%, respectively, effective October 1993. Currently, conventional hydrotreating technology is adapted for aromatics saturation. Some studies have shown that complete hydrogenation of aromatics is not possible owing to equilibrium limitations under typical hydrotreating conditions, and existing middle distillate hydrotreaters designed to reduce sulfur and nitrogen levels would lower the diesel aromatics only marginally.

  19. Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

    PubMed

    Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

    2012-01-21

    Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

  20. Sorption mechanisms of metals to graphene oxide

    SciTech Connect

    Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.; Na, Chongzheng; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is an electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.

  1. Soft-Templating Synthesis and Properties of Mesoporous Alumina-Titania

    SciTech Connect

    Morris, Stacy M; Horton, Jr, Joe A; Jaroniec, Mietek

    2010-01-01

    Mesoporous alumina-titania materials, having various molar compositions of aluminum and titanium, were synthesized via cooperative self-assembly of the corresponding metal alkoxides and Pluronic P123 triblock copolymer (soft template) in ethanolic solution under acidic conditions. The resulting mixed metal oxides possess ordered mesopores at low to equal molar compositions of titanium in relation to aluminum (up to 50%) and worm-like mesostructures at higher molar compositions of titanium (50-75%). In addition, these mesoporous oxides exhibit high BET surface areas (up to 438 m2/g), large pore widths (from 7.37 to 18.55 nm) and pore volumes (from 0.16 to 0.64 cm3/g), narrow pore size distributions, crystalline pore walls and high thermal stability.

  2. Process for producing metal compounds from graphite oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  3. Process for Producing Metal Compounds from Graphite Oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  4. Reduced graphene oxide-metal/metal oxide composites: facile synthesis and application in water purification.

    PubMed

    Sreeprasad, T S; Maliyekkal, Shihabudheen M; Lisha, K P; Pradeep, T

    2011-02-15

    This paper describes a versatile, and simple synthetic route for the preparation of a range of reduced graphene oxide (RGO)-metal/metal oxide composites and their application in water purification. The inherent reduction ability of RGO has been utilized to produce the composite structure from the respective precursor ions. Various spectroscopic and microscopic techniques were employed to characterize the as-synthesized composites. The data reveal that the RGO-composites are formed through a redox-like reaction between RGO and the metal precursor. RGO is progressively oxidized primarily to graphene oxide (GO) and the formed metal nanoparticles are anchored onto the carbon sheets. Metal ion scavenging applications of RGO-MnO(2) and RGO-Ag were demonstrated by taking Hg(II) as the model pollutant. RGO and the composites give a high distribution coefficient (K(d)), greater than 10 L g(-1) for Hg(II) uptake. The K(d) values for the composites are found to be about an order of magnitude higher compared to parent RGO and GO for this application. A methodology was developed to immobilize RGO-composites on river sand (RS) using chitosan as the binder. The as-supported composites are found to be efficient adsorbent candidates for field application.

  5. Inhibiting Metal Oxide Atomic Layer Deposition: Beyond Zinc Oxide.

    PubMed

    Sampson, Matthew D; Emery, Jonathan D; Pellin, Michael J; Martinson, Alex B F

    2017-04-05

    Atomic layer deposition (ALD) of several metal oxides is selectivity inhibited on alkanethiol self-assembled monolayers (SAMs) on Au, and the eventual nucleation mechanism is investigated. The inhibition ability of the SAM is significantly improved by the in situ H2-plasma pretreatment of the Au substrate prior to the gas-phase deposition of a long-chain alkanethiol, 1-dodecanethiol (DDT). This more rigorous surface preparation inhibits even aggressive oxide ALD precursors, including trimethylaluminum and water, for at least 20 cycles. We study the effect that the ALD precursor purge times, growth temperature, alkanethiol chain length, alkanethiol deposition time, and plasma treatment time have on Al2O3 ALD inhibition. This is the first example of Al2O3 ALD inhibition from a vapor-deposited SAM. The inhibitions of Al2O3, ZnO, and MnO ALD processes are compared, revealing the versatility of this selective surface treatment. Atomic force microscopy and grazing-incidence X-ray fluorescence further reveal insight into the mechanism by which the well-defined surface chemistry of ALD may eventually be circumvented to allow metal oxide nucleation and growth on SAM-modified surfaces.

  6. Surface studies of gas sensing metal oxides.

    PubMed

    Batzill, Matthias; Diebold, Ulrike

    2007-05-21

    The relation of surface science studies of single crystal metal oxides to gas sensing applications is reviewed. Most metal oxide gas sensors are used to detect oxidizing or reducing gases and therefore this article focuses on surface reduction processes and the interaction of oxygen with these surfaces. The systems that are discussed are: (i) the oxygen vacancy formation on the surface of the ion conductor CeO(2)(111); (ii) interaction of oxygen with TiO(2) (both adsorption processes and the incorporation of oxygen into the TiO(2)(110) lattice are discussed); (iii) the varying surface composition of SnO(2)(101) and its consequence for the adsorption of water; and (iv) Cu modified ZnO(0001)-Zn surfaces and its interaction with oxygen. These examples are chosen to give a comprehensive overview of surface science studies of different kinds of gas sensing materials and to illustrate the potential that surface science studies have to give fundamental insight into gas sensing phenomena.

  7. Functionalized Mesoporous Silica via an Aminosilane Surfactant Ion Exchange Reaction: Controlled Scaffold Design and Nitric Oxide Release

    PubMed Central

    2015-01-01

    Nitric oxide-releasing mesoporous silica nanoparticles (MSNs) were prepared using an aminosilane-template surfactant ion exchange reaction. Initially, bare silica particles were synthesized under basic conditions in the presence of cetyltrimethylammonium bromide (CTAB). These particles were functionalized with nitric oxide (NO) donor precursors (i.e., secondary amines) via the addition of aminosilane directly to the particle sol and a commensurate ion exchange reaction between the cationic aminosilanes and CTAB. N-Diazeniumdiolate NO donors were formed at the secondary amines to yield NO-releasing MSNs. Tuning of the ion exchange-based MSN modification approach allowed for the preparation of monodisperse particles ranging from 30 to 1100 nm. Regardless of size, the MSNs stored appreciable levels of NO (0.4–1.5 μmol mg–1) with tunable NO release durations (1–33 h) dependent on the aminosilane modification. Independent control of NO release properties and particle size was achieved, demonstrating the flexibility of this novel MSN synthesis over conventional co-condensation and surface grafting strategies. PMID:26717238

  8. Characterizing Surface Acidic Sites in Mesoporous-Silica-Supported Tungsten Oxide Catalysts Using Solid State NMR and Quantum Chemistry Calculations

    SciTech Connect

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Hu, Mary Y.; Turcu, Romulus VF; Peden, Charles HF

    2011-10-18

    The acidic sites in dispersed tungsten oxide supported on SBA-15 mesoporous silica were investigated using a combination of pyridine titration, both fast-, and slow-MAS {sup 15}N NMR, static {sup 2}H NMR, and quantum chemistry calculations. It is found that the bridged acidic -OH groups in surface adsorbed tungsten dimers (i.e., W-OH-W) are the Broensted acid sites. The unusually strong acidity of these Broensted acid sites is confirmed by quantum chemistry calculations. In contrast, terminal W-OH sites are very stable and only weakly acidic as are terminal Si-OH sites. Furthermore, molecular interactions between pyridine molecules and the dimer Broensted and terminal W-OH sites for dispersed tungsten oxide species is strong. This results in restricted molecular motion for the interacting pyridine molecules even at room temperature, i.e., a reorientation mainly about the molecular 2-fold axis. This restricted reorientation makes it possible to estimate the relative ratio of the Broensted (tungsten dimer) to the weakly acidic terminal W-OH sites in the catalyst using the slow-MAS {sup 1}H-{sup 15}N CP PASS method.

  9. Functionalized Mesoporous Silica via an Aminosilane Surfactant Ion Exchange Reaction: Controlled Scaffold Design and Nitric Oxide Release.

    PubMed

    Soto, Robert J; Yang, Lei; Schoenfisch, Mark H

    2016-01-27

    Nitric oxide-releasing mesoporous silica nanoparticles (MSNs) were prepared using an aminosilane-template surfactant ion exchange reaction. Initially, bare silica particles were synthesized under basic conditions in the presence of cetyltrimethylammonium bromide (CTAB). These particles were functionalized with nitric oxide (NO) donor precursors (i.e., secondary amines) via the addition of aminosilane directly to the particle sol and a commensurate ion exchange reaction between the cationic aminosilanes and CTAB. N-Diazeniumdiolate NO donors were formed at the secondary amines to yield NO-releasing MSNs. Tuning of the ion exchange-based MSN modification approach allowed for the preparation of monodisperse particles ranging from 30 to 1100 nm. Regardless of size, the MSNs stored appreciable levels of NO (0.4-1.5 μmol mg(-1)) with tunable NO release durations (1-33 h) dependent on the aminosilane modification. Independent control of NO release properties and particle size was achieved, demonstrating the flexibility of this novel MSN synthesis over conventional co-condensation and surface grafting strategies.

  10. Heavy metal removal from water/wastewater by nanosized metal oxides: a review.

    PubMed

    Hua, Ming; Zhang, Shujuan; Pan, Bingcai; Zhang, Weiming; Lv, Lu; Zhang, Quanxing

    2012-04-15

    Nanosized metal oxides (NMOs), including nanosized ferric oxides, manganese oxides, aluminum oxides, titanium oxides, magnesium oxides and cerium oxides, provide high surface area and specific affinity for heavy metal adsorption from aqueous systems. To date, it has become a hot topic to develop new technologies to synthesize NMOs, to evaluate their removal of heavy metals under varying experimental conditions, to reveal the underlying mechanism responsible for metal removal based on modern analytical techniques (XAS, ATR-FT-IR, NMR, etc.) or mathematical models, and to develop metal oxide-based materials of better applicability for practical use (such as granular oxides or composite materials). The present review mainly focuses on NMOs' preparation, their physicochemical properties, adsorption characteristics and mechanism, as well as their application in heavy metal removal. In addition, porous host supported NMOs are particularly concerned because of their great advantages for practical application as compared to the original NMOs. Also, some magnetic NMOs were included due to their unique separation performance.

  11. The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

    SciTech Connect

    Vogt, Patrick; Bierwagen, Oliver

    2015-02-23

    The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga{sub 2}O{sub 3}, In{sub 2}O{sub 3}, and SnO{sub 2} on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga{sub 2}O, In{sub 2}O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO{sub 2}, somewhat lower for In{sub 2}O{sub 3}, and the lowest for Ga{sub 2}O{sub 3}. Our findings can be generalized to further oxides that possess related sub-oxides.

  12. Limits of ZnO Electrodeposition in Mesoporous Tin Doped Indium Oxide Films in View of Application in Dye-Sensitized Solar Cells.

    PubMed

    Dunkel, Christian; von Graberg, Till; Smarsly, Bernd M; Oekermann, Torsten; Wark, Michael

    2014-04-23

    Well-ordered 3D mesoporous indium tin oxide (ITO) films obtained by a templated sol-gel route are discussed as conductive porous current collectors. This paper explores the use of such films modified by electrochemical deposition of zinc oxide (ZnO) on the pore walls to improve the electron transport in dye-sensitized solar cells (DSSCs). Mesoporous ITO film were dip-coated with pore sizes of 20-25 nm and 40-45 nm employing novel poly(isobutylene)-b-poly(ethylene oxide) block copolymers as structure-directors. After electrochemical deposition of ZnO and sensitization with the indoline dye D149 the films were tested as photoanodes in DSSCs. Short ZnO deposition times led to strong back reaction of photogenerated electrons from non-covered ITO to the electrolyte. ITO films with larger pores enabled longer ZnO deposition times before pore blocking occurred, resulting in higher efficiencies, which could be further increased by using thicker ITO films consisting of five layers, but were still lower compared to nanoporous ZnO films electrodeposited on flat ITO. The major factors that currently limit the application are the still low thickness of the mesoporous ITO films, too small pore sizes and non-ideal geometries that do not allow obtaining full coverage of the ITO surface with ZnO before pore blocking occurs.

  13. Limits of ZnO Electrodeposition in Mesoporous Tin Doped Indium Oxide Films in View of Application in Dye-Sensitized Solar Cells

    PubMed Central

    Dunkel, Christian; von Graberg, Till; Smarsly, Bernd M.; Oekermann, Torsten; Wark, Michael

    2014-01-01

    Well-ordered 3D mesoporous indium tin oxide (ITO) films obtained by a templated sol-gel route are discussed as conductive porous current collectors. This paper explores the use of such films modified by electrochemical deposition of zinc oxide (ZnO) on the pore walls to improve the electron transport in dye-sensitized solar cells (DSSCs). Mesoporous ITO film were dip-coated with pore sizes of 20–25 nm and 40–45 nm employing novel poly(isobutylene)-b-poly(ethylene oxide) block copolymers as structure-directors. After electrochemical deposition of ZnO and sensitization with the indoline dye D149 the films were tested as photoanodes in DSSCs. Short ZnO deposition times led to strong back reaction of photogenerated electrons from non-covered ITO to the electrolyte. ITO films with larger pores enabled longer ZnO deposition times before pore blocking occurred, resulting in higher efficiencies, which could be further increased by using thicker ITO films consisting of five layers, but were still lower compared to nanoporous ZnO films electrodeposited on flat ITO. The major factors that currently limit the application are the still low thickness of the mesoporous ITO films, too small pore sizes and non-ideal geometries that do not allow obtaining full coverage of the ITO surface with ZnO before pore blocking occurs. PMID:28788618

  14. A General Silica-Templating Synthesis of Alkaline Mesoporous Carbon Catalysts for Highly Efficient H2S Oxidation at Room Temperature.

    PubMed

    Zhang, Zixiao; Jiang, Wuyou; Long, Donghui; Wang, Jitong; Qiao, Wenming; Ling, Licheng

    2017-01-25

    A general synthesis of alkaline mesoporous carbons (AMCs) is developed based on a simplified silica-templating method for room-temperature catalytic oxidation of H2S. The key to the success relies on dissolving the silica templates to create the interconnected mesoporous structure as well as leaving parts of the alkaline products in the pores; both of them are prerequisites for H2S oxidation. By adjusting the alkaline etching degree and organic/inorganic ratio, the porosity and basicity of the AMC could be simultaneously tuned, allowing the AMCs direct use for H2S catalytic oxidation with an unprecedented removal capacities of 4.49 ± 0.12 g/g. Such excellent catalytic performance should be attributed to the developed pore structure that stores the product sulfur and the strong basicity that promotes the dissociation of H2S into HS(-) ions. Moreover, this simplified silica-templating method could be easily extended to the preparation of various silica templated mesoporous carbon catalysts. All these AMCs demonstrate a successful combination of low cost with high performance, which may well be the answer for the technical development of industrial H2S removal.

  15. Polymer-assisted aqueous deposition of metal oxide films

    DOEpatents

    Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM

    2003-07-08

    An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

  16. The Effect of Metal Oxide on Nanoparticles from Thermite Reactions

    ERIC Educational Resources Information Center

    Moore, Lewis Ryan

    2006-01-01

    The purpose of this research was to determine how metal oxide used in a thermite reaction can impact the production of nanoparticles. The results showed the presence of nanoparticles (less than 1 micron in diameter) of at least one type produced by each metal oxide. The typical particles were metallic spheres, which ranged from 300 nanometers in…

  17. Synthesis and electronic applications of oxide-metal eutectic composites

    SciTech Connect

    Holder, J. D.; Cochran, J. K.; Hill, D. N.; Chapman, A. T.; Clark, G. W.

    1980-01-01

    A review is given of important developments in the synthesis of oxide-metal eutectic composites and the composite application in the continuing development of field emitters. Known metal oxide-metal binary and ternary eutectic systems are listed. The synthesis, electrical conductivity, thermodynamics, and applications are discussed. (FS)

  18. The Synthesis of Functional Mesoporous Materials

    SciTech Connect

    Fryxell, Glen E.

    2006-11-01

    The ability to decorate a silica surface with specific ligand fields and/or metal complexes creates powerful new capabilities for catalysis, chemical separations and sensor development. Integrating this with the ability to control the spacing of these complexes across the surface, as well as the symmetry and size of the pore structure, allows the synthetic chemist to hierarchically tailor these structured nanomaterials to specific needs. The next step up the “scale ladder” is provided by the ability to coat these mesoporous materials onto complex shapes, allowing for the intimate integration of these tailored materials into device interfaces. The ability to tailor the pore structure of these mesoporous supports is derived from the surfactant templated synthesis of mesoporous materials, an area which has seen an explosion of activity over the last decade.[1,2] The ability to decorate the surface with the desired functionality requires chemical modification of the oxide interface, most commonly achieved using organosilane self-assembly.[3-6] This manuscript describes recent results from the confluence of these two research areas, with a focus on synthetic manipulation of the morphology and chemistry of the interface, with the ultimate goal of binding metal centers in a chemically useful manner.

  19. Impacts of metal and metal oxide nanoparticles on marine organisms.

    PubMed

    Baker, Tony J; Tyler, Charles R; Galloway, Tamara S

    2014-03-01

    Increasing use of metal and metal oxide nanoparticles [Me(O)NPs] in products means many will inevitably find their way into marine systems. Their likely fate here is sedimentation following hetero-aggregation with natural organic matter and/or free anions, putting benthic, sediment-dwelling and filter feeding organisms most at risk. In marine systems, Me(O)NPs can absorb to micro-organisms with potential for trophic transfer following consumption. Filter feeders, especially bivalves, accumulate Me(O)NPs through trapping them in mucus prior to ingestion. Benthic in-fauna may directly ingest sedimented Me(O)NPs. In fish, uptake is principally via the gut following drinking, whilst Me(O)NPs caught in gill mucus may affect respiratory processes and ion transport. Currently, environmentally-realistic Me(O)NP concentrations are unlikely to cause significant adverse acute health problems, however sub-lethal effects e.g. oxidative stresses have been noted in many organisms, often deriving from dissolution of Ag, Cu or Zn ions, and this could result in chronic health impacts. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  20. Orbital physics in transition-metal oxides

    PubMed

    Tokura; Nagaosa

    2000-04-21

    An electron in a solid, that is, bound to or nearly localized on the specific atomic site, has three attributes: charge, spin, and orbital. The orbital represents the shape of the electron cloud in solid. In transition-metal oxides with anisotropic-shaped d-orbital electrons, the Coulomb interaction between the electrons (strong electron correlation effect) is of importance for understanding their metal-insulator transitions and properties such as high-temperature superconductivity and colossal magnetoresistance. The orbital degree of freedom occasionally plays an important role in these phenomena, and its correlation and/or order-disorder transition causes a variety of phenomena through strong coupling with charge, spin, and lattice dynamics. An overview is given here on this "orbital physics," which will be a key concept for the science and technology of correlated electrons.

  1. Mercerized mesoporous date pit activated carbon—A novel adsorbent to sequester potentially toxic divalent heavy metals from water

    PubMed Central

    Aldawsari, Abdullah; Hameed, B. H.; Alqadami, Ayoub Abdullah; Siddiqui, Masoom Raza; Alothman, Zeid Abdullah; Ahmed, A. Yacine Badjah Hadj

    2017-01-01

    A substantive approach converting waste date pits to mercerized mesoporous date pit activated carbon (DPAC) and utilizing it in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) was reported. In general, rapid heavy metals adsorption kinetics for Co range: 25–100 mg/L was observed, accomplishing 77–97% adsorption within 15 min, finally, attaining equilibrium in 360 min. Linear and non-linear isotherm studies revealed Langmuir model applicability for Cd(II) and Pb(II) adsorption, while Freundlich model was fitted to Zn(II) and Cu(II) adsorption. Maximum monolayer adsorption capacities (qm) for Cd(II), Pb(II), Cu(II), and Zn(II) obtained by non-linear isotherm model at 298 K were 212.1, 133.5, 194.4, and 111 mg/g, respectively. Kinetics modeling parameters showed the applicability of pseudo-second-order model. The activation energy (Ea) magnitude revealed physical nature of adsorption. Maximum elution of Cu(II) (81.6%), Zn(II) (70.1%), Pb(II) (96%), and Cd(II) (78.2%) were observed with 0.1 M HCl. Thermogravimetric analysis of DPAC showed a total weight loss (in two-stages) of 28.3%. Infra-red spectral analysis showed the presence of carboxyl and hydroxyl groups over DPAC surface. The peaks at 820, 825, 845 and 885 cm-1 attributed to Zn–O, Pb–O, Cd–O, and Cu–O appeared on heavy metals saturated DPAC, confirmed their binding on DPAC during the adsorption. PMID:28910368

  2. Mercerized mesoporous date pit activated carbon-A novel adsorbent to sequester potentially toxic divalent heavy metals from water.

    PubMed

    Aldawsari, Abdullah; Khan, Moonis Ali; Hameed, B H; Alqadami, Ayoub Abdullah; Siddiqui, Masoom Raza; Alothman, Zeid Abdullah; Ahmed, A Yacine Badjah Hadj

    2017-01-01

    A substantive approach converting waste date pits to mercerized mesoporous date pit activated carbon (DPAC) and utilizing it in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) was reported. In general, rapid heavy metals adsorption kinetics for Co range: 25-100 mg/L was observed, accomplishing 77-97% adsorption within 15 min, finally, attaining equilibrium in 360 min. Linear and non-linear isotherm studies revealed Langmuir model applicability for Cd(II) and Pb(II) adsorption, while Freundlich model was fitted to Zn(II) and Cu(II) adsorption. Maximum monolayer adsorption capacities (qm) for Cd(II), Pb(II), Cu(II), and Zn(II) obtained by non-linear isotherm model at 298 K were 212.1, 133.5, 194.4, and 111 mg/g, respectively. Kinetics modeling parameters showed the applicability of pseudo-second-order model. The activation energy (Ea) magnitude revealed physical nature of adsorption. Maximum elution of Cu(II) (81.6%), Zn(II) (70.1%), Pb(II) (96%), and Cd(II) (78.2%) were observed with 0.1 M HCl. Thermogravimetric analysis of DPAC showed a total weight loss (in two-stages) of 28.3%. Infra-red spectral analysis showed the presence of carboxyl and hydroxyl groups over DPAC surface. The peaks at 820, 825, 845 and 885 cm-1 attributed to Zn-O, Pb-O, Cd-O, and Cu-O appeared on heavy metals saturated DPAC, confirmed their binding on DPAC during the adsorption.

  3. Role of Metal Oxide Electron-Transport Layer Modification on the Stability of High Performing Perovskite Solar Cells.

    PubMed

    Singh, Trilok; Singh, Jai; Miyasaka, Tsutomu

    2016-09-22

    Organic-inorganic hybrid perovskite light absorbers have recently emerged as a "holy grail" for next generation thin-film photovoltaics with excellent optoelectronics properties and low fabrication cost. In a very short span of time, we have witnessed a pronounced and unexpected progress in organic- inorganic perovskite solar cells (PSCs) with a vertical rise in power conversion efficiency from 3.8 to 22.1 %. In this manuscript we focus specifically on the recent development of metal oxide-based electron-transporting layer (ETL) modification for high performing PSCs and their stability. This review highlights various methodologies to modify existing compact/scaffold layers for improving device performance and stability. Various aspects of the ETL are discussed with different metal oxide compact layers in their relation to modification in mesoporous layers towards the design of a cell structure with high performance and stability.

  4. Facile synthesis of mesoporous spinel NiCo2O4 nanostructures as highly efficient electrocatalysts for urea electro-oxidation

    NASA Astrophysics Data System (ADS)

    Ding, Rui; Qi, Li; Jia, Mingjun; Wang, Hongyu

    2014-01-01

    Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo2O4 materials exhibit typical agglomerate mesoporous nanostructures with a large surface area (190.1 m2 g-1) and high mesopore volume (0.943 cm3 g-1). Remarkably, the NiCo2O4 shows much higher catalytic activity, lower overpotential, better stability and greater tolerance towards urea electro-oxidation compared to those of cobalt oxide (Co3O4) synthesized by the same procedure. The NiCo2O4 electrode delivers a current density of 136 mA cm-2 mg-1 at 0.7 V (vs. Hg/HgO) in 1 M KOH and 0.33 M urea electrolytes accompanied with a desirable stability. The impressive electrocatalytic activity is largely ascribed to the high intrinsic electronic conductivity, superior mesoporous nanostructures and rich surface Ni active species of the NiCo2O4 materials, which can largely boost the interfacial electroactive sites and charge transfer rates for urea electro-oxidation, indicating promising applications in future wastewater remediation, hydrogen production and fuel cells.Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry

  5. Metal oxide membranes for gas separation

    DOEpatents

    Anderson, Marc A.; Webster, Elizabeth T.; Xu, Qunyin

    1994-01-01

    A method for permformation of a microporous ceramic membrane onto a porous support includes placing a colloidal suspension of metal oxide particles on one side of the porous support and exposing the other side of the porous support to a drying stream of gas or a reactive gas stream so that the particles are deposited on the drying side of the support as a gel. The gel so deposited can be sintered to form a supported ceramic membrane having mean pore sizes less than 30 Angstroms and useful for ultrafiltration, reverse osmosis, or gas separation.

  6. Metal oxide membranes for gas separation

    DOEpatents

    Anderson, M.A.; Webster, E.T.; Xu, Q.

    1994-08-30

    A method for formation of a microporous ceramic membrane onto a porous support includes placing a colloidal suspension of metal oxide particles on one side of the porous support and exposing the other side of the porous support to a drying stream of gas or a reactive gas stream so that the particles are deposited on the drying side of the support as a gel. The gel so deposited can be sintered to form a supported ceramic membrane having mean pore sizes less than 30 Angstroms and useful for ultrafiltration, reverse osmosis, or gas separation. 4 figs.

  7. Preferential orientation of metal oxide superconducting materials

    DOEpatents

    Capone, Donald W.; Poeppel, Roger B.

    1991-01-01

    A polycrystalline metal oxide such as YBa.sub.2 Cu.sub.3 O.sub.7-X (where 0

  8. Metallic oxide switches using thick film technology

    NASA Technical Reports Server (NTRS)

    Patel, D. N.; Williams, L., Jr.

    1974-01-01

    Metallic oxide thick film switches were processed on alumina substrates using thick film technology. Vanadium pentoxide in powder form was mixed with other oxides e.g., barium, strontium copper and glass frit, ground to a fine powder. Pastes and screen printable inks were made using commercial conductive vehicles and appropriate thinners. Some switching devices were processed by conventional screen printing and firing of the inks and commercial cermet conductor terminals on 96% alumina substrates while others were made by applying small beads or dots of the pastes between platinum wires. Static, and dynamic volt-ampere, and pulse tests indicate that the switching and self-oscillatory characteristics of these devices could make them useful in memory element, oscillator, and automatic control applications.

  9. Chemical Sensors Based on Metal Oxide Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  10. Covalent bonding in heavy metal oxides

    NASA Astrophysics Data System (ADS)

    Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.; Ilton, Eugene S.

    2017-04-01

    Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalencies are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n + 1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.

  11. Large-scale template-free synthesis of ordered mesoporous platinum nanocubes and their electrocatalytic properties

    NASA Astrophysics Data System (ADS)

    Cao, Yanqin; Yang, Yong; Shan, Yufeng; Fu, Chaoli; Viet Long, Nguyen; Huang, Zhengren; Guo, Xiangxin; Nogami, Masayuki

    2015-11-01

    Here we report a facile, one-pot and template-free approach to synthesize mesoporous monocrystalline Pt nanocubes with uniform shapes and sizes, in which small Pt particles with a size of ~5 nm are three-dimensionally and periodically built up into cubes with a size of ~50 nm. The forming process is illustrated through a novel meso-crystal self-assembly mechanism. Very interestingly, the mesoporous structures are ordered, which are thought to be beneficial to increase their catalytic activity. Compared with nonporous Pt nanoparticles and porous Pt nanoparticles without order, the ordered mesoporous Pt nanocubes exhibit a highly improved electrocatalytic ability for methanol and formic acid oxidation, and are potentially applicable as electrocatalysts for direct methanol and formic acid fuel cells. Furthermore, this approach can be used to synthesize other Pt-series metallic mesoporous nanoparticles, such as Pd.Here we report a facile, one-pot and template-free approach to synthesize mesoporous monocrystalline Pt nanocubes with uniform shapes and sizes, in which small Pt particles with a size of ~5 nm are three-dimensionally and periodically built up into cubes with a size of ~50 nm. The forming process is illustrated through a novel meso-crystal self-assembly mechanism. Very interestingly, the mesoporous structures are ordered, which are thought to be beneficial to increase their catalytic activity. Compared with nonporous Pt nanoparticles and porous Pt nanoparticles without order, the ordered mesoporous Pt nanocubes exhibit a highly improved electrocatalytic ability for methanol and formic acid oxidation, and are potentially applicable as electrocatalysts for direct methanol and formic acid fuel cells. Furthermore, this approach can be used to synthesize other Pt-series metallic mesoporous nanoparticles, such as Pd. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05772h

  12. An aptamer-targeting photoresponsive drug delivery system using ``off-on'' graphene oxide wrapped mesoporous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Tang, Yuxia; Hu, Hao; Zhang, Molly Gu; Song, Jibin; Nie, Liming; Wang, Shouju; Niu, Gang; Huang, Peng; Lu, Guangming; Chen, Xiaoyuan

    2015-03-01

    We have developed a novel aptamer-targeting photoresponsive drug delivery system by non-covalent assembly of a Cy5.5-AS1411 aptamer conjugate on the surface of graphene oxide wrapped doxorubicin (Dox)-loaded mesoporous silica nanoparticles (MSN-Dox@GO-Apt) for light-mediated drug release and aptamer-targeted cancer therapy. The two ``off-on'' switches of the MSN-Dox@GO-Apt were controlled by aptamer targeting and light triggering, respectively. The Cy5.5-AS1411 ligand provides MSN-Dox@GO-Apt with nucleolin specific targeting and real-time indicator abilities by ``off-on'' Cy5.5 fluorescence recovery. The GO acts as a gatekeeper to prevent the loaded Dox from leaking in the absence of laser irradiation, and to control the Dox release in response to laser irradiation. When the GO wrapping falls off upon laser irradiation, the ``off-on'' photoresponsive drug delivery system is activated, thus inducing chemotherapy. Interestingly, with an increase in laser power, the synergism of chemotherapy and photothermal therapy in a single MSN-Dox@GO-Apt platform led to much more effective cancer cell killing than monotherapies, providing a new approach for treatment against cancer.We have developed a novel aptamer-targeting photoresponsive drug delivery system by non-covalent assembly of a Cy5.5-AS1411 aptamer conjugate on the surface of graphene oxide wrapped doxorubicin (Dox)-loaded mesoporous silica nanoparticles (MSN-Dox@GO-Apt) for light-mediated drug release and aptamer-targeted cancer therapy. The two ``off-on'' switches of the MSN-Dox@GO-Apt were controlled by aptamer targeting and light triggering, respectively. The Cy5.5-AS1411 ligand provides MSN-Dox@GO-Apt with nucleolin specific targeting and real-time indicator abilities by ``off-on'' Cy5.5 fluorescence recovery. The GO acts as a gatekeeper to prevent the loaded Dox from leaking in the absence of laser irradiation, and to control the Dox release in response to laser irradiation. When the GO wrapping falls off upon

  13. Co(2+)@Mesoporous Silica Monoliths: Tailor-Made Nanoreactors for Confined Soft Chemistry.

    PubMed

    Delahaye, Emilie; Moulin, Robinson; Aouadi, Merwen; Trannoy, Virgile; Beaunier, Patricia; Fornasieri, Giulia; Bleuzen, Anne

    2015-11-16

    Mesoporous silica monoliths with various ordered nanostructures containing transition metal M(2+) cations in variable amounts were elaborated and studied. A phase diagram depicting the different phases as a function of the M(2+) salt/tetramethyl orthosilicate (TMOS) and surfactant P123/TMOS ratios was established. Thermal treatment resulted in mesoporous monoliths containing isolated, accessible M(2+) species or condensed metal oxides, hydroxides, and salts, depending on the strength of the interactions between the metal species and the ethylene oxide units of P123. The ordered mesoporosity of the monoliths containing accessible M(2+) ions was used as a nanoreactor for the elaboration of various transition metal compounds (Prussian blue analogues, Hofmann compounds, metal-organic frameworks), and this opens the way to the elaboration of a large range of nanoparticles of multifunctional materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Method of making controlled morphology metal-oxides

    DOEpatents

    Ozcan, Soydan; Lu, Yuan

    2016-05-17

    A method of making metal oxides having a preselected morphology includes preparing a suspension that includes a solvent, polymeric nanostructures having multiplicities of hydroxyl surface groups and/or carboxyl surface groups, and a metal oxide precursor. The suspension has a preselected ratio of the polymeric nanostructures to the metal oxide precursor of at least 1:3, the preselected ratio corresponding to a preselected morphology. Subsequent steps include depositing the suspension onto a substrate, removing the solvent to form a film, removing the film from the substrate, and annealing the film to volatilize the polymeric nanostructures and convert the metal oxide precursor to metal oxide nanoparticles having the preselected morphology or to a metal oxide nanosheet including conjoined nanoparticles having the preselected morphology.

  15. Electrostatic potentials for metal-oxide surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Streitz, F. H.; Mintmire, J. W.

    1994-10-01

    As most technologically important metals will form oxides readily, any complete study of adhesion at real metal surfaces must include the metal-oxide interface. The role of this ubiquitous oxide layer cannot be overlooked, as the adhesive properties of the oxide or oxide-metal system can be expected to differ profoundly from the adhesive properties of a bare metal surface. We report on the development of a computational method for molecular-dynamics simulations, which explicitly includes variable charge transfer between anions and cations. This method is found to be capable of describing the elastic properties, surface energies, and surface relaxation of crystalline metal oxides accurately. We discuss in detail results using this method for α-alumina and several of its low-index faces.

  16. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  17. Magnesium oxide for improved heavy metals removal

    SciTech Connect

    Schiller, J.E.; Khalafalla, S.E.

    1984-01-01

    To improve technology for treating process water, US Bureau of Mines research has shown that magnesium oxide (MgO) has many advantages over lime or caustic soda for precipitating heavy metals. Sludge produced by MgO occupies only 0.2-0.3 times as much volume as the precipitate made using a soluble base. While a settled, lime-formed precipitate is easily resuspended, the MgO-metal hydroxide sludge becomes cemented together on standing. Settling of the metal hydroxides from a dilute suspension is more complete than precipitates formed with other bases. Virtually any metal that can be precipitated by raising the pH can be treated using MgO. A three-fold to four-fold stoichiometric excess of solid reagent is added. The mixture is reacted for five to 10 minutes. Polymer is added, and settling or filtration completes the process. Because of the greater cost of MgO compared with lime, large-scale practice of this technology will probably be limited to water containing 50 mg/L (3 gr per gal) or less of dissolved metals. For such dilute solutions, chemicals are not a large fraction of total treatment costs, so more desirable sludge properties might justify higher chemical expenses. While the MgO process is technically suitable for widespread application, the extent to which it is adopted will probably be determined by a trade-off between the greater cost of MgO compared with lime and the superior properties of the precipitates and their corresponding ultimate disposal costs.

  18. Thin films of metal oxides on metal single crystals: Structure and growth by scanning tunneling microscopy

    SciTech Connect

    Galloway, Heather Claire

    1995-12-01

    Detailed studies of the growth and structure of thin films of metal oxides grown on metal single crystal surfaces using Scanning Tunneling Microscopy (STM) are presented. The oxide overlayer systems studied are iron oxide and titanium oxide on the Pt(III) surface. The complexity of the metal oxides and large lattice mismatches often lead to surface structures with large unit cells. These are particularly suited to a local real space technique such as scanning tunneling microscopy. In particular, the symmetry that is directly observed with the STM elucidates the relationship of the oxide overlayers to the substrate as well as distinguishing, the structures of different oxides.

  19. Simple transition metal oxides (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Schuller, Ivan K.; Basaran, Ali C.; de la Venta, Jose; Ramirez, Juan Gabriel; Saerbeck, Thomas; Valmianski, Ilya; Wang, Siming

    2016-10-01

    Hybrid materials allow the engineering of new material properties by creative uses of proximity effects. When two dissimilar materials are in close physical proximity the properties of each one may be radically modified or occasionally a completely new material emerges. In the area of magnetism, controlling the magnetic properties of ferromagnetic thin films without magnetic fields is an on- going challenge with multiple technological implications for low- energy consumption memory and logic devices. Interesting possibilities include ferromagnets in proximity to dissimilar materials such as antiferromagnets or oxides that undergo metal-insulator transitions. The proximity of ferromagnets to antiferromagnets has given rise to the extensively studied Exchange Bias[1]. Our recent investigations in this field have addressed crucial issues regarding the importance of the antiferromagnetic [2-3] and ferromagnetic [4] bulk for the Exchange Bias and the unusual short time dynamics [5]. In a series of recent studies, we have investigated the magnetic properties of different hybrids of ferromagnets (Ni, Co and Fe) and oxides, which undergo metal-insulator and structural phase transitions. Both the static as well as dynamical properties of the ferromagnets are drastically affected. Static properties such as the coercivity, anisotropy and magnetization [6-8] and dynamical properties such as the microwave response are clearly modified by the proximity effect and give raise to interesting perhaps useful properties. Work supported by US-AFOSR and US-DOE

  20. Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis

    NASA Astrophysics Data System (ADS)

    Li, Keyan; Zhao, Yongqin; Song, Chunshan; Guo, Xinwen

    2017-12-01

    Magnetic Fe3O4/CeO2 composites with highly ordered mesoporous structure and large surface area were synthesized by impregnation-calcination method, and the mesoporous CeO2 as support was synthesized via the hard template approach. The composition, morphology and physicochemical properties of the materials were characterized by XRD, SEM, TEM, XPS, Raman spectra and N2 adsorption/desorption analysis. The mesoporous Fe3O4/CeO2 composite played a dual-function role as both adsorbent and Fenton-like catalyst for removal of organic dye. The methylene blue (MB) removal efficiency of mesoporous Fe3O4/CeO2 was much higher than that of irregular porous Fe3O4/CeO2. The superior adsorption ability of mesoporous materials was attributed to the abundant oxygen vacancies on the surface of CeO2, high surface area and ordered mesoporous channels. The good oxidative degradation resulted from high Ce3+ content and the synergistic effect between Fe and Ce. The mesoporous Fe3O4/CeO2 composite presented low metal leaching (iron 0.22 mg L-1 and cerium 0.63 mg L-1), which could be ascribed to the strong metal-support interactions for dispersion and stabilization of Fe species. In addition, the composite can be easily separated from reaction solution with an external magnetic field due to its magnetic property, which is important to its practical applications.