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

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

PubMed

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

2014-11-06

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.

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.

A general soft-enveloping strategy in the templating synthesis of mesoporous metal nanostructures.

PubMed

Fang, Jixiang; Zhang, Lingling; Li, Jiang; Lu, Lu; Ma, Chuansheng; Cheng, Shaodong; Li, Zhiyuan; Xiong, Qihua; You, Hongjun

2018-02-06

Metal species have a relatively high mobility inside mesoporous silica; thus, it is difficult to introduce the metal precursors into silica mesopores and suppress the migration of metal species during a reduction process. Therefore, until now, the controlled growth of metal nanocrystals in a confined space, i.e., mesoporous channels, has been very challenging. Here, by using a soft-enveloping reaction at the interfaces of the solid, liquid, and solution phases, we successfully control the growth of metallic nanocrystals inside a mesoporous silica template. Diverse monodispersed nanostructures with well-defined sizes and shapes, including Ag nanowires, 3D mesoporous Au, AuAg alloys, Pt networks, and Au nanoparticle superlattices are successfully obtained. The 3D mesoporous AuAg networks exhibit enhanced catalytic activities in an electrochemical methanol oxidation reaction. The current soft-enveloping synthetic strategy offers a robust approach to synthesize diverse mesoporous metal nanostructures that can be utilized in catalysis, optics, and biomedicine applications.

Environmental and Biomedical Applications of Iron Oxide/Mesoporous Silica Core-Shell Nanocomposites

NASA Astrophysics Data System (ADS)

Egodawatte, Shani Nirasha

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Jun, E-mail: zhqw1888@sohu.co; College of Chemical Engineering, Harbin Institute of Technology, Harbin 150001; Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, 150001

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 havingmore » 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« less

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 poremore » 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.« less

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

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo

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 Ni xCo (3-x)(CO 3) y and Ni xCo (3-x)O 4 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 Ni xCo (3-x)O 4. The micelle templated mesopores are interconnected and providemore » 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, Ni 2CoO 4 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 Ni 2CoO 4 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.« less

Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications† †Electronic supplementary information (ESI) available: Experimental section, additional characterization and reaction results. See DOI: 10.1039/c7sc04724j

PubMed Central

Fang, Ruiqi; Tian, Panliang; Yang, Xianfeng

2018-01-01

The development of efficient encapsulation strategies has attracted intense interest for preparing highly active and stable heterogeneous metal catalysts. However, issues related to low loadings, costly precursors and complex synthesis processes restrict their potential applications. Herein, we report a novel and general strategy to encapsulate various ultrafine metal-oxides nanoparticles (NPs) into the mesoporous KIT-6. The synthesis is facile, which only involves self-assembly of a metal–organic framework (MOF) precursor in the silica mesopores and a subsequent calcination process to transform the MOF into metal-oxide NPs. After the controlled calcination, the metal-oxide NPs produced from MOF decomposition are exclusively confined and uniformly distributed in the mesopores of KIT-6 with high metal loadings. Benefitting from the encapsulation effects, as-synthesized Co@KIT-6 materials exhibit superior catalytic activity and recycling stability in biomass-derived HMF oxidation under mild reaction conditions. PMID:29675231

Polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons as efficient metal-free electrocatalyst for hydrazine oxidation.

PubMed

Meng, Yuying; Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup; Liu, Zhongwu; Asefa, Tewodros

2014-10-08

We demonstrate that polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons can serve as efficient, metal-free electrocatalysts for hydrazine oxidation reaction, with low overpotential and high current density. The materials' structures and the nature and type of their included dopants, which can be controlled by varying the synthetic conditions, can affect the electrocatalytic properties of the materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

Mesoporous transition metal oxides quasi-nanospheres with enhanced electrochemical properties for supercapacitor applications.

PubMed

Wang, Lu; Duan, Guorong; Zhu, Junwu; Chen, Shen-Ming; Liu, Xiao-Heng; Palanisamy, Selvakumar

2016-12-01

In this report, we obtain mesoporous transition metal oxides quasi-nanospheres (includes MnO2, NiO, and Co3O4) by utilizing mesoporous silica nanospheres as a template for high-performance supercapacitor electrodes. All samples have a large specific surface area of approximately 254-325m(2)g(-1) and a relatively narrow pore size distribution in the region of 7nm. Utilization of a nanosized template resulted in a product with a relative uniform morphology and a small particle diameter in the region of 50-100nm. As supercapacitor electrodes, MnO2, NiO, and Co3O4 exhibit an outstanding capacity as high as 838-1185Fg(-1) at 0.5Ag(-1) and a superior long-term stability with minimal loss of 3-7% after 6000 cycles at 1Ag(-1). Their excellent electrochemical performances are attributed to favorable morphologies with a large surface area and a uniform architecture with abundant pores. The associated enhancement of electrolyte ion circulation within the electrode facilitates a significant increase in availability of Faradic reaction electroactive sites. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Synthesis of fluidized CO2 sorbents based on diamine coordinated to Metal-Organic Frameworks via direct conversion of metal oxides supported on mesoporous silica.

PubMed

Luz, Ignacio; Soukri, Mustapha; Lail, Marty

2018-06-06

A general and efficient method for shaping MOFs into fluidized forms has been developed via direct conversion of metal oxides supported on fluidized mesoporous silica. The resulting fluidized MOF hybrid materials containing diamines coordinated at the open metal sites have been studied as CO2 solid sorbents from post-combustion flue gas showing similar performance than their bulk counterparts. These novel fluidized MOF hybrid materials can be used for other applications involving fluidized bed reactor configurations, in which MOFs have never been considered. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of mesoporous materials

NASA Astrophysics Data System (ADS)

Cheng, Wei

Mesoporous materials are highly porous solids with pore sizes in the range of 20 to 500 A and a narrow pore size distribution. Creating a mesoporous morphology in transition metal oxides is expected to increase the kinetics of electrochemical photoelectrochemical processes due to the improved accessibility of electrolyte to electrode. The objective of the dissertation research is to prepare functional mesoporous materials based on transition metal oxides and to determine the effects of the mesoporous structure on the resulting charge transfer, electrochromism, and optical properties. In this dissertation, mesoporous tungsten oxide and niobium oxide were synthesized by incorporating tri-block copolymer surfactant templates into the sol-gel synthesis procedure. Both mesoporous materials have surface areas in the range of 130 m2/g with a narrow pore size distribution centered at ˜45A. Their electrochromic properties were characterized and found to be strongly influenced by the mesoporous morphology. Both mesoporous systems exhibit better electrochemical and optical reversibilities than the analogous sol-gel materials (without using surfactant) and the kinetics of bleaching is substantially faster. Coloration efficiencies for the mesoporous tungsten oxide and niobium oxide films are in the range of 16--37 cm 2/C and 12--16 cm2/C, respectively. Dye sensitized solar cells (DSSC) were fabricated using mesoporous niobium oxide as electrodes. Due to the higher surface area, the mesoporous electrodes have greater dye adsorption and electrolyte penetration compared to sol-gel electrodes, which leads to better electron injection, faster dye regeneration and thus, better cell performance. The mesoporous DSSC exhibits photocurrents of 2.9 mA and fill factors of 0.61. Open circuit voltages of the mesoporous DSSC are in the range of 0.6--0.83V.

Catalytic oxidation of soot on mesoporous ceria-based mixed oxides with cetyltrimethyl ammonium bromide (CTAB)-assisted synthesis.

PubMed

Zhu, Hongjian; Xu, Jing; Yichuan, Yuge; Wang, Zhongpeng; Gao, Yibo; Liu, Wei; Yin, Henan

2017-12-15

Mesoporous ceria and transition metal-doped ceria (M 0.1 Ce 0.9 O 2 (M=Mn, Fe, Co, Cu)) catalysts were synthesized via CTAB-assisted method. The physicochemical properties of the prepared catalysts were characterized by XRD, DLS analysis, SEM, BET, Raman, H 2 -TPR and in situ DRIFT techniques. The catalytic activity tests for soot oxidation were performed under tight contact of soot/catalyst mixtures in the presence of O 2 and NO+O 2 , respectively. The obtained results show that mesoporous ceria-based solid solutions can be formed with large surface areas and small crystallite size. Transition metals doping enhances the oxygen vacancies and improves redox properties of the solids, resulting in the increased NO oxidation capacity and NO x adsorption capacity. The soot oxidation activity in the presence of O 2 is enhanced by doping transition metal, which may be related to their high surface area, increased oxygen vacancies and improved redox properties. The soot combustion is accelerated by the NO 2 -assisted mechanism under NO+O 2 atmosphere, facilitating an intimate contact between the soot and the catalyst. Copyright © 2017 Elsevier Inc. All rights reserved.

Layer-by-Layer Motif Architectures: Programmed Electrochemical Syntheses of Multilayer Mesoporous Metallic Films with Uniformly Sized Pores.

PubMed

Jiang, Bo; Li, Cuiling; Qian, Huayu; Hossain, Md Shahriar A; Malgras, Victor; Yamauchi, Yusuke

2017-06-26

Although multilayer films have been extensively reported, most compositions have been limited to non-catalytically active materials (e.g. polymers, proteins, lipids, or nucleic acids). Herein, we report the preparation of binder-free multilayer metallic mesoporous films with sufficient accessibility for high electrocatalytic activity by using a programmed electrochemical strategy. By precisely tuning the deposition potential and duration, multilayer mesoporous architectures consisting of alternating mesoporous Pd layers and mesoporous PdPt layers with controlled layer thicknesses can be synthesized within a single electrolyte, containing polymeric micelles as soft templates. This novel architecture, combining the advantages of bimetallic alloys, multilayer architectures, and mesoporous structures, exhibits high electrocatalytic activity for both the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols.

PubMed

Sharma, Mukesh; Das, Biraj; Sharma, Mitu; Deka, Biplab K; Park, Young-Bin; Bhargava, Suresh K; Bania, Kusum K

2017-10-11

Solid-state grinding of palladium and copper salts allowed the growth of palladium/copper oxide interface at the zeolite-Y surface. The hybrid nanostructured material was used as reusable heterogeneous catalyst for selective oxidation of various benzyl alcohols. The large surface area provided by the zeolite-Y matrix highly influenced the catalytic activity, as well as the recyclability of the synthesized catalyst. Impregnation of PdO-CuO nanoparticles on zeolite crystallite leads to the generation of mesoporous channel that probably prevented the leaching of the metal-oxide nanoparticles and endorsed high mass transfer. Formation of mesoporous channel at the external surface of zeolite-Y was evident from transmission electron microscopy and surface area analysis. PdO-CuO nanoparticles were found to be within the range of 2-5 nm. The surface area of PdO-CuO-Y catalyst was found to be much lower than parent zeolite-Y. The decrease in surface area as well as the presence of hysteresis loop in the N 2 -adsoprtion isotherm further suggested successful encapsulation of PdO-CuO nanoparticles via the mesoporous channel formation. The high positive shifting in binding energy in both Pd and Cu was attributed to the influence of zeolite-Y framework on lattice contraction of metal oxides via confinement effect. PdO-CuO-Y catalyst was found to oxidize benzyl alcohol with 99% selectivity. On subjecting to microwave irradiation the same oxidation reaction was found to occur at ambient condition giving same conversion and selectivity.

Rational design of mesoporous metals and related nanomaterials by a soft-template approach.

PubMed

Yamauchi, Yusuke; Kuroda, Kazuyuki

2008-04-07

We review recent developments in the preparation of mesoporous metals and related metal-based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore-size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct-template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct-template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal-based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia\\3d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

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 ofmore » 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.« less

Isomorphic introduction of d(0) transition metals to mesoporous silica

NASA Astrophysics Data System (ADS)

Morey, Mark Sanson

1998-12-01

Early transition metals (Ti, V, Zr, Mo, W) have been incorporated in the mesoporous silicate system by hydrothermal and post-synthesis treatments. The materials were studied by diffraction, adsorption and spectroscopic techniques and were found to have catalytic, halogenation activity toward organic substrates at neutral pH. Intense interest has been shown in the new class of silica-based, mesoporous materials due to their high potential for catalytic applications. Their synthesis occurs via a cooperative self-assembly of surfactant/silicate pairs to form numerous, extended network structures upon silicate condensation based on liquid crystal phases of surfactant/water systems. Surfactant micelle removal by calcination generates a well defined pore system with a narrow pore size distribution. Of these phases, the cubic MCM-48 form possesses a high surface area (1200-1500msp2/g), a 3-D array of pores, and a large pore diameter (20-100A) so that selectivity for large (>10A kinetic diameter) molecules is possible. For this work, the MCM-48 phase was chosen since its branched, bi-continuous pore array would be less likely to clog during use than a one dimensional array. Two techniques for transition metal incorporation are compared consisting of hydrothermal and post-synthesis treatment. A brief description of an attempt to synthesize mesoporous molybdena will be included. The first approach consists of combining various metal and Si precursors in the starting gel, while exploring a broad region of the multi-component phase diagram. The second pathway involves grafting metal species on a pure silica, MCM-48 support by anchoring them to surface silanols using reactive metal alkoxides. Bulk structural characterization by X-ray powder diffraction and nitrogen adsorption shows that the pore structure is maintained after incorporation of metal species by both methods. Spectroscopic methods (FTIR/RAMAN and UV/VIS) are used to gain insight into the local metal

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). PMID:28347106

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoa, Nguyen Duc, E-mail: ndhoa@itims.edu.vn; Duy, Nguyen Van; Hieu, Nguyen Van, E-mail: hieu@itims.edu.vn

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 dioxidemore » (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.« less

A rational repeating template method for synthesis of 2D hexagonally ordered mesoporous precious metals.

PubMed

Takai, Azusa; Doi, Yoji; Yamauchi, Yusuke; Kuroda, Kazuyuki

2011-03-01

A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor-infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen-adsorption-desorption isotherm, and small-angle X-ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft-templating methods, can be prepared. This study has overcome the composition variation limitations of the soft-templating method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition metal-chelating surfactant micelle templates for facile synthesis of mesoporous silica nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hye Sun; Department of Materials Science and Engineering, Yonsei University, Seoul 120-749; Kim, Won Hee

2012-01-15

Highly ordered mesoporous silica nanoparticles with tunable morphology and pore-size are prepared by the use of a transition metal-chelating surfactant micelle complex using Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, and Zn{sup 2+} ions. These metal ions formed a metal-P123 micelle complex in an aqueous solution, while the metal ions are chelated to the hydrophilic domain such as the poly(ethylene oxide) group of a P123 surfactant. The different complexation abilities of the utilized transition metal ions play an important role in determining the formation of nano-sized ordered MSNs due to the different stabilization constant of the metal-P123 complex. Consequently, from amore » particle length of 1700 nm in the original mesoporous silica materials, the particle length of ordered MSNs through the metal-chelating P123 micelle templates can be reduced to a range of 180-800 nm. Furthermore, the variation of pore size shows a slight change from 8.8 to 6.6 nm. In particular, the Cu{sup 2+}-chelated MSNs show only decreased particle size to 180 nm. The stability constants for the metal-P123 complex are calculated on the basis of molar conductance measurements in order to elucidate the formation mechanism of MSNs by the metal-chelating P123 complex templates. In addition, solid-state {sup 29}Si, {sup 13}C-NMR and ICP-OES measurements are used for quantitative characterization reveal that the utilized metal ions affect only the formation of a metal-P123 complex in a micelle as a template. - Graphical abstract: Metal-chelating surfactant micelle templates support a simple and facile preparations of size-tunable ordered MSNs. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Facile preparation of mesoporous silica nanoparticles (MSNs) was achieved by metal-chelating surfactant micelle complex using Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, and Zn{sup 2+} ions. Black-Right-Pointing-Pointer Different complexation of metal ions plays an important role in determining the

Structural and morphological properties of mesoporous carbon coated molybdenum oxide films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayal, Saurabh, E-mail: saurabhdayal153@gmail.com; Kumar, C. Sasi, E-mail: csasimv@gmail.com

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. Themore » meso-porous carbon were found growing over molybdenum oxide layer as a result of segregation phenomena.« less

Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

NASA Astrophysics Data System (ADS)

Pal, Nabanita; Bhaumik, Asim

2012-05-01

Designing a suitable mesoporous framework material for the selective adsorption or immobilization of biomolecules is a very challenging area of research. Mesoporous ternary Co-Si-Al oxide materials with large mesopore and their nanoscale ordering have been reported. The synthesis of these ternary oxides are accomplished through evaporation induced self-assembly (EISA) method using Pluronic non-ionic surfactant F127 under non-aqueous sol-gel route. N2 sorption study revealed high BET surface areas for these materials. These materials exhibited very efficient and selective adsorption for the essential biomolecules like vitamin C (ascorbic acid), vitamin B6 (pyridoxine) and vitamin B3 (nicotinic acid) from their respective aqueous solutions.

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.

A Review of Recent Developments of Mesoporous Materials.

PubMed

Suib, Steven L

2017-12-01

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 (CO 2 ), 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

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

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

Adsorption studies of heavy metal ions on mesoporous aluminosilicate, novel cation exchanger.

PubMed

Sepehrian, H; Ahmadi, S J; Waqif-Husain, S; Faghihian, H; Alighanbari, H

2010-04-15

Mesoporous aluminosilicates, have been prepared with various mole ratios of Si/Al and Cethyltrimethylammonium bromide (CTAB). They have been characterized by XRD, nitrogen adsorption/desorption measurements, FT-IR and thermogravimetry. Adsorption behavior of heavy metal ions on this adsorbent have been studied and discussed. The results show that incorporation of aluminum ions in the framework of the mesoporous MCM-41 has transformed it into an effective cation exchanger. The K(d) values of several metal ions have been increased. Separation of Sr(II)-Ce(III), Sr(II)-U(VI) and Cd(II)-Ce(III) has been developed on columns of this novel mesoporous cation exchanger. 2009 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling

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 asmore » 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.« less

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.

Functionalized mesoporous silica supported copper(II) and nickel(II) catalysts for liquid phase oxidation of olefins.

PubMed

Nandi, Mahasweta; Roy, Partha; Uyama, Hiroshi; Bhaumik, Asim

2011-12-14

Highly ordered 2D-hexagonal mesoporous silica has been functionalized with 3-aminopropyltriethoxysilane (3-APTES). This is followed by its condensation with a dialdehyde, 4-methyl-2,6-diformylphenol to produce an immobilized Schiff-base ligand (I). This material is separately treated with methanolic solution of copper(II) chloride and nickel(II) chloride to obtain copper and nickel anchored mesoporous materials, designated as Cu-AMM and Ni-AMM, respectively. The materials have been characterized by Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance (DRS) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption studies and (13)C CP MAS NMR spectroscopy. The metal-grafted mesoporous materials have been used as catalysts for the efficient and selective epoxidation of alkenes, viz. cyclohexene, trans-stilbene, styrene, α-methyl styrene, cyclooctene and norbornene to their corresponding epoxides in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under mild liquid phase conditions.

Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

PubMed

Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

2015-04-09

The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Kinetic and catalytic analysis of mesoporous Co3O4 on the oxidation of morin

NASA Astrophysics Data System (ADS)

Xaba, Morena. S.; Meijboom, Reinout

2017-11-01

Herein we report on the synthesis, characterization and catalytic evaluation of mesoporous cobalt oxides on the oxidation of morin. These mesoporous cobalt oxides were synthesized using an inverse surfactant micelle method, they are connected, well-defined with intra-particle voids. These materials were calcined to different final heating temperatures of 150, 250, 350, 450 and 550 °C, and each mesoporous cobalt oxide catalyst showed unique physical properties and catalytic behavior. Morin oxidation was used as a model reaction in the presence of hydrogen peroxide to evaluate the kinetic and catalytic activity of calcined mesoporous cobalt oxides. The adsorption-desorption equilibrium rate constants of morin and hydrogen peroxide were found to be inversely proportional to the crystallite size of the mesoporous cobalt oxide, and the characteristic path length in which the mass transfer takes place was found to be directly proportional to the crystallite size. The materials were characterized using powder X-Ray Diffraction (p-XRD), N2-sorption isotherms (BET), hydrogen temperature programmed reduction (H2-TPR) and High Resolution-Transmission Electron Microscopy (HR-TEM). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of morin at λmax = 410 nm. The surface reaction in this system is described in terms of the well-established Langmuir-Hinshelwood model. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability is demonstrated.

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.

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 BiFeO 3 (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 TiO 2 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

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

Template-free synthesis of mesoporous nanoring-like Zn-Co mixed oxides with high lithium storage performance

NASA Astrophysics Data System (ADS)

Lu, Lun; Gao, Yan-Li; Yang, Zhi-Zheng; Wang, Cheng; Wang, Jin-Guo; Wang, Hui-Yuan; Jiang, Qi-Chuan

2018-04-01

Mesoporous nanoring-like Zn-Co mixed oxides are synthesized via a simple template-free solvothermal method with a subsequent annealing process. The ring-like nanostructures with hollow interiors are formed under the complexing effects of potassium sodium tartrate. Numerous mesopores are generated after the precursor is annealed at 500 °C. When applied as anode materials, the mesoporous nanoring-like Zn-Co mixed oxides can deliver a high discharge capacity of 1102 mAh g-1 after 200 cycles at 500 mA g-1. Even when the current density is increased to 2 A g-1, the mixed oxides can still retain a reversible capacity of 761 mAh g-1. Such high cycling stability and rate capability are mainly derived from the unique mesoporous ring-like nanostructures and the synergistic effects between Zn and Co based oxides.

Ce, Ti modified MCM-48 mesoporous photocatalysts: Effect of the synthesis route on support and metal ion properties

NASA Astrophysics Data System (ADS)

Mureseanu, Mihaela; Filip, Mihaela; Somacescu, Simona; Baran, Adriana; Carja, Gabriela; Parvulescu, Viorica

2018-06-01

New Ti-MCM-48 and CeTi-MCM-48 photocatalysts were obtained by impregnation of the MCM-48 silica support synthesized by a hydrothermal process with aqueous solution of Ti and Ce precursors. The immobilization of metal cations presented a low effect on the porosity, morphology and structure of MCM-48 mesoporous silica support as was evidenced by N2 adsorption-desorption, X-ray diffraction, SEM and TEM electron microscopy. EDAX analysis and X-ray photoelectron microscopy (XPS) indicated that titanium cations were present on the mesoporous silica surface only as Ti4+ species and the effect of ceria on titanium speciation was different, compared to the CeTi-MCM-48 sample, previously obtained by direct synthesis. The photocatalytic properties of mono- and bimetallic catalysts were evaluated in degradation of phenol from water and correlated with the active metallic species concentration, distribution, speciation and their interaction with the support or each other. An advanced oxidation mechanism for phenol degradation by radical species was proposed.

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.

Facile Synthesis of Wormhole-Like Mesoporous Tin Oxide via Evaporation-Induced Self-Assembly and the Enhanced Gas-Sensing Properties

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Peng, Kang; Dou, Yewei; Chen, Jiasheng; Zhang, Yue; An, Gai

2018-01-01

Wormhole-like mesoporous tin oxide was synthesized via a facile evaporation-induced self-assembly (EISA) method, and the gas-sensing properties were evaluated for different target gases. The effect of calcination temperature on gas-sensing properties of mesoporous tin oxide was investigated. The results demonstrate that the mesoporous tin oxide sensor calcined at 400 °C exhibits remarkable selectivity to ethanol vapors comparison with other target gases and has a good performance in the operating temperature and response/recovery time. This might be attributed to their high specific surface area and porous structure, which can provide more active sites and generate more chemisorbed oxygen spices to promote the diffusion and adsorption of gas molecules on the surface of the gas-sensing material. A possible formation mechanism of the mesoporous tin oxide and the enhanced gas-sensing mechanism are proposed. The mesoporous tin oxide shows prospective detecting application in the gas sensor fields.

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%. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Molten Salt Assisted Self-Assembly: Synthesis of Mesoporous LiCoO2 and LiMn2 O4 Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate.

PubMed

Saat, Gülbahar; Balci, Fadime Mert; Alsaç, Elif Pınar; Karadas, Ferdi; Dag, Ömer

2018-01-01

Mesoporous thin films of transition metal lithiates (TML) belong to an important group of materials for the advancement of electrochemical systems. This study demonstrates a simple one pot method to synthesize the first examples of mesoporous LiCoO 2 and LiMn 2 O 4 thin films. Molten salt assisted self-assembly can be used to establish an easy route to produce mesoporous TML thin films. The salts (LiNO 3 and [Co(H 2 O) 6 ](NO 3 ) 2 or [Mn(H 2 O) 4 ](NO 3 ) 2 ) and two surfactants (10-lauryl ether and cethyltrimethylammonium bromide (CTAB) or cethyltrimethylammonium nitrate (CTAN)) form stable liquid crystalline mesophases. The charged surfactant is needed for the assembly of the necessary amount of salt in the hydrophilic domains of the mesophase, which produces stable metal lithiate pore-walls upon calcination. The films have a large pore size with a high surface area that can be increased up to 82 m 2 g -1 . The method described can be adopted to synthesize other metal oxides and metal lithiates. The mesoporous thin films of LiCoO 2 show promising performance as water oxidation catalysts under pH 7 and 14 conditions. The electrodes, prepared using CTAN as the cosurfactant, display the lowest overpotentials in the literature among other LiCoO 2 systems, as low as 376 mV at 10 mA cm -2 and 282 mV at 1 mA cm -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soft-Templating Synthesis of Mesoporous Silica-Based Materials for Environmental Applications

NASA Astrophysics Data System (ADS)

Gunathilake, Chamila Asanka

Dissertation research is mainly focus on: 1) the development of mesoporous silica materials with organic pendant and bridging groups (isocyanurate, amidoxime, benzene) and incorporated metal (aluminum, zirconium, calcium, and magnesium) species for high temperature carbon dioxide (CO2) sorption, 2) phosphorous-hydroxy functionalized mesoporous silica materials for water treatment, and 3) amidoxime-modified ordered mesoporous silica materials for uranium sorption under seawater conditions. The goal is to design composite materials for environmental applications with desired porosity, surface area, and functionality by selecting proper metal oxide precursors, organosilanes, tetraethylorthosilicate, (TEOS), and block copolymer templates and by adjusting synthesis conditions. The first part of dissertation presents experimental studies on the merge of aluminum, zirconium, calcium, and magnesium oxides with mesoporous silica materials containing organic pendant (amidoxime) and bridging groups (isocyanurate, benzene) to obtain composite sorbents for CO2 sorption at ambient (0-25 °C) and elevated (60-120 °C) temperatures. These studies indicate that the aforementioned composite sorbents are fairly good for CO2 capture at 25 °C via physisorption mechanism and show a remarkably high affinity toward CO2 chemisorption at 60-120 °C. The second part of dissertation is devoted to silica-based materials with organic functionalities for removal of heavy metal ions such as lead from contaminated water and for recovery of metal ions such as uranium from seawater. First, ordered mesoporous organosilica (OMO) materials with diethylphosphatoethyl and hydroxyphosphatoethyl surface groups were examined for Pb2+ adsorption and showed unprecedented adsorption capacities up to 272 mg/g and 202 mg/g, respectively However, the amidoxime-modified OMO materials were explored for uranium extraction under seawater conditions and showed remarkable capacities reaching 57 mg of uranium per gram

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; ...

2015-02-19

Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO 3) 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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO 3) 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.

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jing, E-mail: mlczjsls123@163.com; Mu, Wentao, E-mail: mwt15035687833@163.com; Su, Liqing, E-mail: suliqing0163@163.com

Pd catalysts supported on Al-doped TiO{sub 2} 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 TiO{sub 2} 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 andmore » increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.« less

Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

PubMed

Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

2011-02-01

We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors.

PubMed

Nam, Inho; Kim, Nam Dong; Kim, Gil-Pyo; Park, Junsu; Yi, Jongheop

2012-07-01

A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.

Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

PubMed

Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

2016-02-21

A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

Porous Aluminum Oxide and Magnesium Oxide Films Using Organic Hydrogels as Structure Matrices

PubMed Central

Chen, Zimei

2018-01-01

We describe the synthesis of mesoporous Al2O3 and MgO layers on silicon wafer substrates by using poly(dimethylacrylamide) hydrogels as porogenic matrices. Hydrogel films are prepared by spreading the polymer through spin-coating, followed by photo-cross-linking and anchoring to the substrate surface. The metal oxides are obtained by swelling the hydrogels in the respective metal nitrate solutions and subsequent thermal conversion. Combustion of the hydrogel results in mesoporous metal oxide layers with thicknesses in the μm range and high specific surface areas up to 558 m2∙g−1. Materials are characterized by SEM, FIB ablation, EDX, and Kr physisorption porosimetry. PMID:29565802

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.

N, P-codoped Mesoporous Carbon Supported PtCox Nanoparticles and Their Superior Electrochemical toward Methanol Oxidation

NASA Astrophysics Data System (ADS)

Cui, Hangjun; Li, Yueming; Liu, Shimin

2018-03-01

In this report, a novel strategy by using the N, P co-doped mesoporous carbon structure as catalyst support to enhance the electrochemical catalytic activity of Pt-based catalysts is proposed. The as-synthesized PtCox@N, P-doped mesoporous carbon nanocomposties have been studied as an anode catalyst toward methanol oxidation, exhibiting greatly improved electrochemical activity and stability compared with Pt@mesoporous carbon. The synergistic effects of N, P dual-doping and porous carbon structure help to achieve better electron transport at the electrode surface, which eventually leads to greatly enhanced catalytic activity compared to the pristine Pt/mesoporous carbon.…

Hollow PdCo alloy nanospheres with mesoporous shells as high-performance catalysts for methanol oxidation.

PubMed

Sheng, Guoqing; Chen, Jiahui; Ye, Huangqing; Hu, Zhixiong; Fu, Xian-Zhu; Sun, Rong; Huang, Weixin; Wong, Ching-Ping

2018-07-15

Monodisperse hollow mesoporous PdCo alloy nanospheres are prepared via a simple galvanic replacement reaction. The as-prepared PdCo hollow nanospheres have small diameter, such as Pd 78 Co 22 nanospheres of diameter about 25 nm and mesoporous shells about 4-5 nm. The Pd 78 Co 22 hollow mesoporous nanospheres possess the largest electrochemical active surface areas (ECSA, 53.91 m 2  g -1 ), mass activity (1488 mA mg -1 ) and specific activity (2.76 mA cm -2 ) towards to methanol oxidation relative to the Pd 68 Co 32 , Pd 92 Co 8 hollow mesoporous nanospheres and commercial Pd/C catalysts. Moreover, the activity of Pd 78 Co 22 after long-term stability tests is still the best and even better than those of fresh Pd 68 Co 32 and commercial Pd/C catalysts. The PdCo catalysts not only effectively reduce the Pd usage by forming hollow structure, but also fully realize the Pd-Co alloying effects for enhancing the methanol oxidation catalytic performance. Copyright © 2018 Elsevier Inc. All rights reserved.

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

PubMed

Saha, Dipendu; Barakat, Soukaina; Van Bramer, Scott E; Nelson, Karl A; Hensley, Dale K; Chen, Jihua

2016-12-14

In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SO x . SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m 2 /g with total pore volume of 0.71-2.3 cm 3 /g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl 2 ), lead (as Pb(NO 3 ) 2 ), cadmium (as CdCl 2 ), and nickel (as NiCl 2 ) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO 4 , 14% and 2% of Pb was converted to PbSO 4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO 4 . Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

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

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

PubMed

Finocchio, Elisabetta; Gonzalez-Prior, Jonatan; Gutierrez-Ortiz, Jose Ignacio; Lopez-Fonseca, Ruben; Busca, Guido; de Rivas, Beatriz

2018-05-29

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

Controlled Embedding of Metal Oxide Nanoparticles in ZSM-5 Zeolites through Preencapsulation and Timed Release.

PubMed

Lai, Yungchieh; Rutigliano, Michael N; Veser, Götz

2015-09-29

We report a straightforward and transferrable synthesis strategy to encapsulate metal oxide nanoparticles (NPs) in mesoporous ZSM-5 via the encapsulation of NPs into silica followed by conversion of the NP@silica precursor to NP@ZSM-5. The systematic bottom-up approach allows for straightforward, precise control of both the metal weight loading and size of the embedded NP and yields uniform NP@ZSM-5 microspheres composed of stacked ZSM-5 nanorods with substantial mesoporosity. Key to the synthesis is the timed release of the embedded NPs during dissolution of the silica matrix in the hydrothermal conversion step, which finely balances the rate of NP release with the rate of SiO2 dissolution and the subsequent nucleation of aluminosilicate. The synthesis approach is demonstrated for Zn, Fe, and Ni oxide encapsulation in ZSM-5 but can be expected to be broadly transferrable for the encapsulation of metal and metal oxide nanoparticles into other zeolite structures.

Metal-nitrogen doping of mesoporous carbon/graphene nanosheets by self-templating for oxygen reduction electrocatalysts.

PubMed

Li, Shuang; Wu, Dongqing; Liang, Haiwei; Wang, Jinzuan; Zhuang, Xiaodong; Mai, Yiyong; Su, Yuezeng; Feng, Xinliang

2014-11-01

We demonstrate a general and efficient self-templating strategy towards transition metal-nitrogen containing mesoporous carbon/graphene nanosheets with a unique two-dimensional (2D) morphology and tunable mesoscale porosity. Owing to the well-defined 2D morphology, nanometer-scale thickness, high specific surface area, and the simultaneous doping of the metal-nitrogen compounds, the as-prepared catalysts exhibits excellent electrocatalytic activity and stability towards the oxygen reduction reaction (ORR) in both alkaline and acidic media. More importantly, such a self-templating approach towards two-dimensional porous carbon hybrids with diverse metal-nitrogen doping opens up new avenues to mesoporous heteroatom-doped carbon materials as electrochemical catalysts for oxygen reduction and hydrogen evolution, with promising applications in fuel cell and battery technologies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous silica wrapped with graphene oxide-conducting PANI nanowires as a novel hybrid electrode for supercapacitor

NASA Astrophysics Data System (ADS)

Javed, Mohsin; Abbas, Syed Mustansar; Siddiq, Mohammad; Han, Dongxue; Niu, Li

2018-02-01

A high charge-carrier transport is an important aim in the synthesis of nanostructures for an effective supercapacitor. This article describes a methodology to prepare mesoporous silica nanoparticles (MSNs) wrapped with graphene oxide (GO) together with conducting polyaniline (PANI) wires. The morphology and chemical structure of the prepared samples have been tested by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and X-ray diffraction (XRD), whereas the stability and electrostatic interaction of the structures have been verified by thermogravimetric analysis (TGA) and Fourier-transform infrared (FT-IR) spectroscopy, respectively. The supercapacitive behaviour of these nanocomposites has been analysed by cyclic voltammetry (CV), charge-discharge tests, and electrochemical impedance spectroscopy (EIS). Compared with pristine MSNs and PANI, the 20%-GO@MSNs/PANI nanocomposite had the highest specific capacitance, reaching 412 F g-1. The nanocomposite structure maximizes the synergy between mesoporous metal oxide, conducting PANI, and GO, yielding a significantly enhanced specific capacitance, rapid charge-discharge rates, and good cycling stability of the resulting device. The wrapping with GO prevents the structural breakdown and acts as a highly conductive pathway by bridging the individual particles, whereas the MSNs nanoparticles greatly enlarge the specific surface area to facilitate ion transport and charge transfer throughout the cycling performance of supercapacitor. The approach adopted in this article can be applied for preparing similar novel functional materials in future for electrochemical applications.

Enantioselective recognition at mesoporous chiral metal surfaces.

PubMed

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.

Assessment of surface acidity in mesoporous materials containing aluminum and titanium

NASA Astrophysics Data System (ADS)

Araújo, Rinaldo S.; Maia, Débora A. S.; Azevedo, Diana C. S.; Cavalcante, Célio L., Jr.; Rodríguez-Castellón, E.; Jimenez-Lopez, A.

2009-04-01

The surface acidity of mesoporous molecular sieves of aluminum and titanium was evaluated using four different techniques: n-butylamine volumetry, cyclohexylamine thermodesorption, temperature-programmed desorption of ammonia and adsorption of pyridine. The nature, strength and concentration of the acid sites were determined and correlated to the results of a probe reaction of anthracene oxidation to 9,10-anthraquinone (in liquid phase). In general, the surface acidity was highly influenced by the nature, location and coordination of the metal species (Al and Ti) in the mesoporous samples. Moderate to strong Brönsted acid sites were identified for the Al-MCM-41 sample in a large temperature range. For mesoporous materials containing Ti, the acidity was represented by a combination of weak to moderate Brönsted and Lewis acid sites. The Ti-HMS sample exhibits a higher acidity of moderate strength together with a well-balanced concentration of Brönsted and Lewis acid sites, which enhanced both conversion and selectivity in the oxidation reaction of anthracene.

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

PubMed

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Preparation of Mesoporous Ceramics from Polymer Nanotubes

NASA Astrophysics Data System (ADS)

Chen, Dian; Park, Soojin; Chen, Jiun-Tai; Redston, Emily; Russell, Thomas

2009-03-01

Poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) nanotubes were prepared by placing polymer solution into the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. The PS-b-P4VP nanotubes within the AAO membranes were exposed to tetrahydrofuran vapor to produce uniform spherical micelles along the tube. The tubes were removed from the membranes, then suspended in ethylene glycol, a preferential solvent for P4VP. At 95^ oC, near the glass transition temperature (Tg) of PS, nanotubes with uniform nanopores were obtained by a reconstruction of the nanotubes. As the temperature was increased, mesoporous polymer structures were obtained. Tetraethyl orthosilicate or titanium tetraethoxide, ceramic precursors, were introduced into the 4VP microdomains. After exposure to an oxygen plasma or high temperature, the copolymer was removed and the precursor converted to a mesoporous ceramic. This process offers a simple route for the fabrication of tunable mesoporous ceramic or metallic structures by changing molecular weight of copolymers.

Functional, mesoporous, superparamagnetic colloidal sorbents for efficient removal of toxic metals.

PubMed

Sinha, Arjyabaran; Jana, Nikhil R

2012-09-25

γ-Fe(2)O(3) incorporated mesoporous silica particles of 50-100 nm size have been synthesized which are functionalized with chelating agents of metal ions. These particles are water dispersible but aggregate in response to the external magnetic field and have been used for high performance and selective removal of Cd, Pb, Hg and As.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Mesoporous MnCeO x 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 Mn 0.5Ce 0.5O x 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 Mn 0.5Ce 0.5O xmore » solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

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.

Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

PubMed

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

2014-12-19

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.

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

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.

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. PMID:28344241

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids.

PubMed

Pal, Nabanita; Bhaumik, Asim

2013-03-01

With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous materials started and in the 21st century this area of scientific investigation have extended into numerous branches, many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical research. As a consequence thousands of publications came out in large varieties of national and international journals. In this review, we have tried to summarize the published works on various synthetic pathways and formation mechanisms of different mesoporous materials viz. inorganic, organic-inorganic hybrid and purely organic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires participation of organic template (more specifically surfactants and their supramolecular assemblies) called structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition metal oxides, mixed oxides, metallophosphates, organic-inorganic hybrids as well as purely organic mesoporous materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper. Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their functionality, composition and surface properties are discussed at the appropriate places. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon

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 amore » 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.« less

Preparation of hollow mesoporous carbon spheres and their performances for electrochemical applications

NASA Astrophysics Data System (ADS)

Ariyanto, T.; Zhang, G. R.; Kern, A.; Etzold, B. J. M.

2018-03-01

Hollow carbon materials have received intensive attention for energy storage/conversion applications due to their attractive properties of high conductivity, high surface area, large void and short diffusion pathway. In this work, a novel hollow mesoporous material based on carbide-derived carbon (CDC) is presented. CDC is a new class of carbon material synthesized by the selective extraction of metals from metal carbides. With a two-stage extraction procedure of carbides with chlorine, firstly hybrid core-shell carbon particles were synthesized, i.e. mesoporous/graphitic carbon shells covering microporous/amorphous carbon cores. The amorphous cores were then selectively removed from particles by a careful oxidative treatment utilizing its low thermal characters while the more stable carbon shells remained, thus resulting hollow particles. The characterization methods (e.g. N2 sorption, Raman spectroscopy, temperature-programmed oxidation and SEM) proved the successful synthesis of the aspired material. In electric double-layer capacitor (EDLC) testing, this novel hollow core material showed a remarkable enhancement of EDLC’s rate handling ability (75% at a high scan rate) with respect to an entirely solid-mesoporous material. Furthermore, as a fuel cell catalyst support the material showed higher Pt mass activity (a factor of 1.8) compared to a conventional carbon support for methanol oxidation without noticeably decreasing activity in a long-term testing. Therefore, this carbon nanostructure shows great promises as efficient electrode materials for energy storage and conversion systems.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 nervemore » 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.« less

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.

Ordered mesoporous crystalline gamma-Al2O3 with variable architecture and porosity from a single hard template.

PubMed

Wu, Zhangxiong; Li, Qiang; Feng, Dan; Webley, Paul A; Zhao, Dongyuan

2010-09-01

-to-synthesize mesoporous metal oxides, such as magnesium oxide. We believe that the fundamentals in this research will provide new insights for rational synthesis of ordered mesoporous materials.

A Novel Conductive Mesoporous Layer with a Dynamic Two-Step Deposition Strategy Boosts Efficiency of Perovskite Solar Cells to 20.

PubMed

Sun, Haoxuan; Deng, Kaimo; Zhu, Yayun; Liao, Min; Xiong, Jie; Li, Yanrong; Li, Liang

2018-05-22

Lead halide perovskite solar cells (PSCs) with the high power conversion efficiency (PCE) typically use mesoporous metal oxide nanoparticles as the scaffold and electron-transport layers. However, the traditional mesoporous layer suffers from low electron conductivity and severe carrier recombination. Here, antimony-doped tin oxide nanorod arrays are proposed as novel transparent conductive mesoporous layers in PSCs. Such a mesoporous layer improves the electron transport as well as light utilization. To resolve the common problem of uneven growth of perovskite on rough surface, the dynamic two-step spin coating strategy is proposed to prepare highly smooth, dense, and crystallized perovskite films with micrometer-scale grains, largely reducing the carrier recombination ratio. The conductive mesoporous layer and high-quality perovskite film eventually render the PSC with a remarkable PCE of 20.1% with excellent reproducibility. These findings provide a new avenue to further design high-efficiency PSCs from the aspect of carrier transport and recombination. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and Characterization of Mesoporous Nickel derived from Liquid crystalline Template and Evaluation of its Electro catalytic activity towards Methanol Oxidation

NASA Astrophysics Data System (ADS)

Mohanapriya, S.; Renuka devi, R.; Raj, V.

2018-02-01

Mesoporous Nickel has been prepared by electrodeposition using non-ionic surfactant based liquid crystalline template under optimized processing conditions. Physico-chemical properties of mesoporous nickel is systematically characterized through XRD, SEM and AFM analyses. Comparison of electrocatalytic activity of mesoporous nickel with smooth nickel was interrogated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) analyses. Distinctly enhanced electrocatalytic activity with improved surface poisoning resistance related to mesoporous nickel electrode towards methanol oxidation stems from unique mesoporous morphology. This mesoporous morphology with high surface to volume ratio is highly beneficial to promote active catalytic centers to offer readily accessible Pt catalytic sites for MOR, through facilitating mass and electron transports.

Tailored Mesoporous Silicas: From Confinement Effects to Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buchanan III, A C; Kidder, Michelle

2010-01-01

Ordered mesoporous silicas continue to find widespread use as supports for diverse applications such as catalysis, separations, and sensors. They provide a versatile platform for these studies because of their high surface area and the ability to control pore size, topology, and surface properties over wide ranges. Furthermore, there is a diverse array of synthetic methodologies for tailoring the pore surface with organic, organometallic, and inorganic functional groups. In this paper, we will discuss two examples of tailored mesoporous silicas and the resultant impact on chemical reactivity. First, we explore the impact of pore confinement on the thermochemical reactivity ofmore » phenethyl phenyl ether (PhCH2CH2OPh, PPE), which is a model of the dominant {beta}-aryl ether linkage present in lignin derived from woody biomass. The influence of PPE surface immobilization, grafting density, silica pore diameter, and presence of a second surface-grafted inert 'spacer' molecule on the product selectivity has been examined. We will show that the product selectivity can be substantially altered compared with the inherent gas-phase selectivity. Second, we have recently initiated an investigation of mesoporous silica supported, heterobimetallic oxide materials for photocatalytic conversion of carbon dioxide. Through surface organometallic chemistry, isolated M-O-M species can be generated on mesoporous silicas that, upon irradiation, form metal to metal charge transfer bands capable of converting CO{sub 2} into CO. Initial results from studies of Ti(IV)-O-Sn(II) on SBA-15 will be presented.« less

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.

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

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

Pair distribution function (PDF) analysis of mesoporous α-Fe2O3 and Cr2O3.

PubMed

Hill, Adrian H; Allieta, Mattia

2013-06-14

We have measured atomic pair distribution functions of novel mesoporous metal oxides, α-Fe2O3 and Cr2O3. These have an ordered pore mosaic as well as crystalline structure within the pore walls, making them an interesting class of materials to characterise. Comparison of "bulk" and mesoporous data sets has allowed an estimate of long range structural coherence to be derived; ≈125 Å and ≈290 Å for α-Fe2O3 and Cr2O3 respectively. Further "box-car" analysis has shown that above ≈40 Å both mesoporous samples deviate greatly from their bulk counterparts. This is attributed to the pores of the mesoporous structure creating voids in the pair-correlations, disrupting long range order.

Nanosized iron and chromium oxides supported on mesoporous CeO2 and SBA-15 silica: Physicochemical and catalytic study

NASA Astrophysics Data System (ADS)

Tsoncheva, Tanya; Roggenbuck, Jan; Paneva, Daniela; Dimitrov, Momtchil; Mitov, Ivan; Fröba, Michael

2010-11-01

Mesoporous ceria and SBA-15 silica were modified with iron and chromium oxide nanoparticles and characterized by XRD, N2-physisorption, FTIR, UV-vis, Moessbauer spectroscopy and TPR-TG in hydrogen. Their catalytic behaviour in methanol decomposition to CO and hydrogen was also studied. Stabilization of mono- and bi-chromate species, FeOx patches or isolated iron ions as well as Fe2O3 and Cr2O3 nanoparticles in different ratio depending on the nature of the porous matrix was observed. The simultaneous presence of iron and chromium oxides lead to change in their dispersion, providing easier reducibility, higher catalytic activity and stability of the obtained materials in comparison with the corresponding mono-component ones. The "intimate contact" at the interface of both loaded metal oxide nanoparticles and the support was discussed with respect to explain the differences in the state of the active ingredient and its specific catalytic behaviour.

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.

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.

Mesoporous nickel oxide nanowires: hydrothermal synthesis, characterisation and applications for lithium-ion batteries and supercapacitors with superior performance.

PubMed

Su, Dawei; Kim, Hyun-Soo; Kim, Woo-Seong; Wang, Guoxiu

2012-06-25

Mesoporous nickel oxide nanowires were synthesized by a hydrothermal reaction and subsequent annealing at 400 °C. The porous one-dimensional nanostructures were analysed by field-emission SEM, high-resolution TEM and N(2) adsorption/desorption isotherm measurements. When applied as the anode material in lithium-ion batteries, the as-prepared mesoporous nickel oxide nanowires demonstrated outstanding electrochemical performance with high lithium storage capacity, satisfactory cyclability and an excellent rate capacity. They also exhibited a high specific capacitance of 348 F g(-1) as electrodes in supercapacitors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template-assisted electrostatic spray deposition as a new route to mesoporous, macroporous, and hierarchically porous oxide films.

PubMed

Sokolov, S; Paul, B; Ortel, E; Fischer, A; Kraehnert, R

2011-03-01

A novel film coating technique, template-assisted electrostatic spray deposition (TAESD), was developed for the synthesis of porous metal oxide films and tested on TiO(2). Organic templates are codeposited with the titania precursor by electrostatic spray deposition and then removed during calcination. Resultant films are highly porous with pores casted by uniformly sized templates, which introduced a new level of control over the pore morphology for the ESD method. Employing the amphiphilic block copolymer Pluronic P123, PMMA latex spheres, or a combination of the two, mesoporous, macroporous, and hierarchically porous TiO(2) films are obtained. Decoupled from other coating parameters, film thickness can be controlled by deposition time or depositing multiple layers while maintaining the coating's structure and integrity.

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

PubMed

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

Photochemical metal organic deposition of metal oxides

NASA Astrophysics Data System (ADS)

Law, Wai Lung (Simon)

This thesis pertains to the study of the deposition of metal oxide thin films via the process of Photochemical Metal Organic Deposition (PMOD). In this process, an amorphous metal organic precursor thin film is subjected to irradiation under ambient conditions. Fragmentation of the metal precursor results from the photoreaction, leading to the formation of metal oxide thin films in the presence of oxygen. The advantage of PMOD lies in its ability to perform lithography of metal oxide thin film without the application of photoresist. The metal organic precursor can be imaged directly by photolysis through a lithography mask under ambient conditions. Thus the PMOD process provides an attractive alternative to the conventional VLSI fabrication process. Metal carboxylates and metal acetylacetonates complexes were used as the precursors for PMOD process in this thesis. Transition metal carboxylate and metal acetylacetonate complexes have shown previously that when deposited as amorphous thin films, they will undergo fragmentation upon photolysis, leading to the formation of metal oxide thin films under ambient conditions. In this thesis, the formation of main group metal oxides of aluminum, indium and tin, as well as the formation of rare-earth metal oxides of cerium and europium by PMOD from its corresponding metal organic precursor will be presented. The nature of the photoreactions as well as the properties of the thin films deposited by PMOD will be investigated. Doped metal oxide thin films can also be prepared using the PMOD process. By mixing the metal precursors prior to deposition in the desired ratio, precursor films containing more than one metal precursor can be obtained. Mixed metal oxide thin films corresponding to the original metal ratio, in the precursor mixture, can be obtained upon photolysis under ambient conditions. In this thesis, the properties of doped metal oxide thin films of europium doped aluminum oxide as well as tin doped indium oxide thin

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sol-gel synthesis and adsorption properties of mesoporous manganese oxide

NASA Astrophysics Data System (ADS)

Ivanets, A. I.; Kuznetsova, T. F.; Prozorovich, V. G.

2015-03-01

Sol-gel synthesis of mesoporous xerogels of manganese oxide with different phase compositions has been performed. The manganese oxide sols were obtained by redox reactions of potassium permanganate with hydrogen peroxide or manganese(II) chloride in aqueous solutions. The isotherms of the low-temperature adsorption-desorption of nitrogen with manganese oxide xerogels treated at 80, 200, 400, and 600°C were measured. The samples were studied by electron microscopy and thermal and XRD analysis. The phase transformation and the changes in the adsorption and capillary-condensation properties of manganese oxide were shown to depend on the sol synthesis conditions and the temperature of the thermal treatment of the gel. The X-ray amorphous samples heated at 80°C were shown to have low values of the specific surface; at higher temperatures, the xerogel crystallized into mixed phases with various compositions and its surface area increased at 200-400°C and decreased at 600°C.

Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Malgras, Victor; Li, Cuiling; Tang, Jing; Kim, Jung Ho; Yamauchi, Yusuke

2015-09-14

A facile method for the fabrication of well-dispersed mesoporous Pt nanospheres involves the use of a polymeric micelle assembly. A core-shell-corona type triblock copolymer [poly(styrene-b-2-vinylpyridine-b-ethylene oxide), PS-b-P2VP-b-PEO] is employed as the pore-directing agent. Negatively charged PtCl4 (2-) ions preferably interact with the protonated P2VP(+) blocks while the free PEO chains prevent the aggregation of the Pt nanospheres. The size of the mesopores can be finely tuned by varying the length of the PS chain. Furthermore, it is demonstrated that the metallic mesoporous nanospheres thus obtained are promising candidates for applications in electrochemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential of hybrid functionalized meso-porous materials for the separation and immobilization of radionuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luca, V.

2013-07-01

Functionalized meso-porous materials are a class of hybrid organic-inorganic material in which a meso-porous metal oxide framework is functionalized with multifunctional organic molecules. These molecules may contain one or more anchor groups that form strong bonds to the pore surfaces of the metal oxide framework and free functional groups that can impart and or modify the functionality of the material such as for binding metal ions in solution. Such materials have been extensively studied over the past decade and are of particular interest in absorption applications because of the tremendous versatility in choosing the composition and architecture of the metalmore » oxide framework and the nature of the functional organic molecule as well as the efficient mass transfer that can occur through a well-designed hierarchically porous network. A sorbent for nuclear applications would have to be highly selective for particular radio nuclides, it would need to be hydrolytically and radiolytically stable, and it would have to possess reasonable capacity and fast kinetics. The sorbent would also have to be available in a form suitable for use in a column. Finally, it would also be desirable if once saturated with radio nuclides, the sorbent could be recycled or converted directly into a ceramic or glass waste form suitable for direct repository disposal or even converted directly into a material that could be used as a transmutation target. Such a cradle-to- grave strategy could have many benefits in so far as process efficiency and the generation of secondary wastes are concerned.This paper will provide an overview of work done on all of the above mentioned aspects of the development of functionalized meso-porous adsorbent materials for the selective separation of lanthanides and actinides and discuss the prospects for future implementation of a cradle-to-grave strategy with such materials. (author)« less

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

PubMed

Chu, Wei-Cheng; Bastakoti, Bishnu Prasad; Kaneti, Yusuf Valentino; Li, Jheng-Guang; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Kuo, Shiao-Wei

2017-10-04

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO 2 adsorption capacity (6.72 mmol g -1 at 0 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2013 Elsevier Inc. All rights reserved.

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

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.

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.

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.

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.

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.

TiO2-coated mesoporous carbon: conventional vs. microwave-annealing process.

PubMed

Coromelci-Pastravanu, Cristina; Ignat, Maria; Popovici, Evelini; Harabagiu, Valeria

2014-08-15

The study of coating mesoporous carbon materials with titanium oxide nanoparticles is now becoming a promising and challenging area of research. To optimize the use of carbon materials in various applications, it is necessary to attach functional groups or other nanostructures to their surface. The combination of the distinctive properties of mesoporous carbon materials and titanium oxide is expected to be applied in field emission displays, nanoelectronic devices, novel catalysts, and polymer or ceramic reinforcement. But, their synthesis is still largely based on conventional techniques, such as wet impregnation followed by chemical reduction of the metal nanoparticle precursors, which takes time and money. The thermal heating based techniques are time consuming and often lack control of particle size and morphology. Hence, since there is a growing interest in microwave technology, an alternative way of power input into chemical reactions through dielectric heating is the use of microwaves. This work is focused on the advantages of microwave-assisted synthesis of TiO2-coated mesoporous carbon over conventional thermal heating method. The reviewed studies showed that the microwave-assisted synthesis of such composites allows processes to be completed within a shorter reaction time allowing the nanoparticles formation with superior properties than that obtained by conventional method. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

PubMed

Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

2017-07-03

Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

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 activemore » 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.« less

Tunneled Mesoporous Carbon Nanofibers with Embedded ZnO Nanoparticles for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Lee, Do-Young; Ahn, Hyo-Jin

2017-04-12

Carbon and metal oxide composites have received considerable attention as anode materials for Li-ion batteries (LIBs) owing to their excellent cycling stability and high specific capacity based on the chemical and physical stability of carbon and the high theoretical specific capacity of metal oxides. However, efforts to obtain ultrafast cycling stability in carbon and metal oxide composites at high current density for practical applications still face important challenges because of the longer Li-ion diffusion pathway, which leads to poor ultrafast performance during cycling. Here, tunneled mesoporous carbon nanofibers with embedded ZnO nanoparticles (TMCNF/ZnO) are synthesized by electrospinning, carbonization, and postcalcination. The optimized TMCNF/ZnO shows improved electrochemical performance, delivering outstanding ultrafast cycling stability, indicating a higher specific capacity than previously reported ZnO-based anode materials in LIBs. Therefore, the unique architecture of TMCNF/ZnO has potential for use as an anode material in ultrafast LIBs.

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}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xinbo; Wang, Danjun; College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000

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 catalystmore » 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}.« less

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hard template synthesis of metal nanowires

NASA Astrophysics Data System (ADS)

Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

2014-11-01

Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed.

Hard template synthesis of metal nanowires.

PubMed

Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

2014-01-01

Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance, and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed.

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.

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

PubMed

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

Amorphous ZnO Quantum Dot/Mesoporous Carbon Bubble Composites for a High-Performance Lithium-Ion Battery Anode.

PubMed

Tu, Zhiming; Yang, Gongzheng; Song, Huawei; Wang, Chengxin

2017-01-11

Due to its high theoretical capacity (978 mA h g -1 ), natural abundance, environmental friendliness, and low cost, zinc oxide is regarded as one of the most promising anode materials for lithium-ion batteries (LIBs). A lot of research has been done in the past few years on this topic. However, hardly any research on amorphous ZnO for LIB anodes has been reported despite the fact that the amorphous type could have superior electrochemical performance due to its isotropic nature, abundant active sites, better buffer effect, and different electrochemical reaction details. In this work, we develop a simple route to prepare an amorphous ZnO quantum dot (QDs)/mesoporous carbon bubble composite. The composite consists of two parts: mesoporous carbon bubbles as a flexible skeleton and monodisperse amorphous zinc oxide QDs (smaller than 3 nm) encapsulated in an amorphous carbon matrix as a continuous coating tightly anchored on the surface of mesoporous carbon bubbles. With the benefits of abundant active sites, amorphous nature, high specific surface area, buffer effect, hierarchical pores, stable interconnected conductive network, and multidimensional electron transport pathways, the amorphous ZnO QD/mesoporous carbon bubble composite delivers a high reversible capacity of nearly 930 mA h g -1 (at current density of 100 mA g -1 ) with almost 90% retention for 85 cycles and possesses a good rate performance. This work opens the possibility to fabricate high-performance electrode materials for LIBs, especially for amorphous metal oxide-based materials.

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.

Hierarchically Mesoporous o-Hydroxyazobenzene Polymers: Synthesis and Their Applications in CO2 Capture and Conversion.

PubMed

Ji, Guipeng; Yang, Zhenzhen; Zhang, Hongye; Zhao, Yanfei; Yu, Bo; Ma, Zhishuang; Liu, Zhimin

2016-08-08

The synthesis of hierarchically mesoporous polymers with multiple functionalities is challenging. Herein we reported a template-free strategy for synthesis of phenolic azo-polymers with hierarchical porous structures based on diazo-coupling reaction in aqueous solution under mild conditions. The resultant polymers have surface areas up to 593 m(2)  g(-1) with the mesopore ratio of >80 %, and a good ability to complex with metal ions, such as Cu(2+) , Zn(2+) ,Ni(2+) , achieving a metal loading up to 26.24 wt %. Moreover, the polymers complexed with Zn showed excellent performance for catalyzing the reaction of CO2 with epoxide, affording a TOF of 2570 h(-1) in the presence of tetrabutyl ammonium bromide (7.2 mol %). The polymer complexed with Cu could catalyze the oxidation of alcohol with high efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Mesoporous Phosphate Heterostructures: Synthesis and Application on Adsorption and Catalysis

NASA Astrophysics Data System (ADS)

Moreno-Tost, Ramón; Jiménez-Jiménez, José; Infantes-Molina, Antonia; Cavalcante, Celio L.; Azevedo, Diana C. S.; Soriano, María Dolores; López Nieto, José Manuel; Jiménez-López, Antonio; Rodríguez-Castellón, Enrique

Porous phosphate heterostructures (PPHs) are solids formed by a layered metal(IV) phosphate expanded with silica galleries obtained by combining the two main strategies for obtaining mesoporous materials [pillared layered structures (PLS') and MCM-41]. The different synthetic pathways for obtaining mesoporous phosphate structures with silica galleries with Zr- or Ti-doped silica, the study of their structural, textural and acid properties, its functionalisation with different organic substances such as propionitrile, 3-aminopropyl triethoxysilane, (3-mercaptopropyl)trimethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane and 3-(triethoxysilyl)propionitrile are discussed. The preparation of metal-supported catalysts and their application in gas separation, adsorption and catalysis are reviewed. Specifically, the use of Cu- and Fe-exchanged PPH for the adsorption of benzothiophene and the separation of propane/propene is the main application as adsorbent. The hydrotreating of aromatic hydrocarbons using ruthenium-impregnated catalysts via hydrogenation and hydrogenolysis/hydrocracking for the production of clean diesel fuels, the selective catalytic reduction of NO from stationary and mobile sources by using Cu-PPH with 1, 3 and 7 wt% of Cu and the selective oxidation of hydrogen sulphide to sulphur with vanadium-containing PPH are the three catalytic reactions of environmental interest studied.

Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

2015-01-15

Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was moremore » beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.« less

Cubic mesoporous Ag@CN: a high performance humidity sensor.

PubMed

Tomer, Vijay K; Thangaraj, Nishanthi; Gahlot, Sweta; Kailasam, Kamalakannan

2016-12-01

The fabrication of highly responsive, rapid response/recovery and durable relative humidity (%RH) sensors that can precisely monitor humidity levels still remains a considerable challenge for realizing the next generation humidity sensing applications. Herein, we report a remarkably sensitive and rapid %RH sensor having a reversible response using a nanocasting route for synthesizing mesoporous g-CN (commonly known as g-C 3 N 4 ). The 3D replicated cubic mesostructure provides a high surface area thereby increasing the adsorption, transmission of charge carriers and desorption of water molecules across the sensor surfaces. Owing to its unique structure, the mesoporous g-CN functionalized with well dispersed catalytic Ag nanoparticles exhibits excellent sensitivity in the 11-98% RH range while retaining high stability, negligible hysteresis and superior real time %RH detection performances. Compared to conventional resistive sensors based on metal oxides, a rapid response time (3 s) and recovery time (1.4 s) were observed in the 11-98% RH range. Such impressive features originate from the planar morphology of g-CN as well as unique physical affinity and favourable electronic band positions of this material that facilitate water adsorption and charge transportation. Mesoporous g-CN with Ag nanoparticles is demonstrated to provide an effective strategy in designing high performance %RH sensors and show great promise for utilization of mesoporous 2D layered materials in the Internet of Things and next generation humidity sensing applications.

Highly Loaded Mesoporous Silica/Nanoparticle Composites and Patterned Mesoporous Silica Films

NASA Astrophysics Data System (ADS)

Kothari, Rohit; Hendricks, Nicholas R.; Wang, Xinyu; Watkins, James J.

2014-03-01

Novel approaches for the preparation of highly filled mesoporous silica/nanoparticle (MS/NP) composites and for the fabrication of patterned MS films are described. The incorporation of iron platinum NPs within the walls of MS is achieved at high NP loadings by doping amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (Pluronic®) copolymer templates via selective hydrogen bonding between the pre-synthesized NPs and the hydrophilic portion of the block copolymer. The MS is then synthesized by means of phase selective condensation of tetraethylorthosilicate (TEOS) within the NP loaded block copolymer templates dilated with supercritical carbon dioxide (scCO2) followed by calcination. For patterned films, microphase separated block copolymer/small molecule additive blends are patterned using UV-assisted nanoimprint lithography. Infusion and condensation of a TEOS within template films using ScCO2 as a processing medium followed by calcination yields the patterned MS films. Scanning electron microscopy is used characterize pattern fidelity and transmission electron microscopy analysis confirms the presence of the mesopores. Long range order in nanocomposites is confirmed by low angle x-ray diffraction.

Hard template synthesis of metal nanowires

PubMed Central

Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

2014-01-01

Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance, and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed. PMID:25453031

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.

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

PubMed

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

TiO2-Containing Carbon Derived from a Metal-Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization.

PubMed

Bhadra, Biswa Nath; Song, Ji Yoon; Khan, Nazmul Abedin; Jhung, Sung Hwa

2017-09-13

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H 2 N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H 2 N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO 2 nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO 2 nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO 2 , and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO 2 content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO 2 might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.

Nitrogen and Phosphorus Codoped Mesoporous Carbon Derived from Polypyrrole as Superior Metal-Free Electrocatalyst toward the Oxygen Reduction Reaction.

PubMed

Zhang, Zhengping; Sun, Junting; Dou, Meiling; Ji, Jing; Wang, Feng

2017-05-17

To replace high-cost platinum group metal (PGM) electrocatalysts for oxygen reduction reaction (ORR) that is the crucial cathode reaction in fuel cell technology and metal-air battery, the development of low-cost and high-efficiency non-PGM catalysts for ORR has attracted much attention during the past decades. As one of the promising candidates, N-doped carbon is highly desirable for its strong designability and outstanding catalytic activity and stability. In this work, a facile and rational strategy is demonstrated for preparation of N,P-codoped mesoporous carbon (N,P-MC) for ORR by the direct pyrolysis treatment of polypyrrole with phytic acid as P-dopant and polystyrene sphere as template. The resultant N,P-MC exhibits a mesoporous structure with the optimized ORR active sites originating from the N,P-codoping. Owing to these features, N,P-MC exhibits excellent ORR activity, remarkable electrochemical stability, and superior methanol tolerance, comparable or even better than that of commercial Pt/C catalyst. The origin of enhanced ORR performance can be attributed to both the increased active sites and the mesoporous structure, which is expected to guide the future preparation of more capable carbon-based electrocatalysts for oxygen reduction and other electrocatalytic application.

Synthesis and structural characterization of ZnO-and CuO-NPs supported mesoporous silica materials (hexagonal SBA-15 and lamellar-SiO2)

NASA Astrophysics Data System (ADS)

El-Nahhal, Issa M.; Salem, Jamil K.; Tabasi, Nihal S.; Hempelmann, Rolf; Kodeh, Fawzi S.

2018-01-01

Two different mesoporous silica structures (hexagonal and lamellar) were synthesized via sol-gel method using a series of triblock copolymer (Pluronic) surfactants. L81, L61 & L31 surfactants form lamellar structure whereas P123 surfactant forms a hexagonal structure. CuO and ZnO nanoparticles (NPs) supported mesoporous silica were synthesized using impregnation method. The structural properties of these materials were investigated using several characterization techniques such as FTIR, XRD, SAXS, TEM and TGA. SAXS and TEM confirmed that the obtained mesoporous silica is based on the EO/PO ratio of Pluronic surfactants. They proved that the mesoporosity of silica is well maintained even after they loaded with metal oxide nanoparticles.

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.

Hierarchical Mesoporous Zinc-Nickel-Cobalt Ternary Oxide Nanowire Arrays on Nickel Foam as High-Performance Electrodes for Supercapacitors.

PubMed

Wu, Chun; Cai, Junjie; Zhang, Qiaobao; Zhou, Xiang; Zhu, Ying; Shen, Pei Kang; Zhang, Kaili

2015-12-09

Nickel foam supported hierarchical mesoporous Zn-Ni-Co ternary oxide (ZNCO) nanowire arrays are synthesized by a simple two-step approach including a hydrothermal method and subsequent calcination process and directly utilized for supercapacitive investigation for the first time. The nickel foam supported hierarchical mesoporous ZNCO nanowire arrays possess an ultrahigh specific capacitance value of 2481.8 F g(-1) at 1 A g(-1) and excellent rate capability of about 91.9% capacitance retention at 5 A g(-1). More importantly, an asymmetric supercapacitor with a high energy density (35.6 Wh kg(-1)) and remarkable cycle stability performance (94% capacitance retention over 3000 cycles) is assembled successfully by employing the ZNCO electrode as positive electrode and activated carbon as negative electrode. The remarkable electrochemical behaviors demonstrate that the nickel foam supported hierarchical mesoporous ZNCO nanowire array electrodes are highly desirable for application as advanced supercapacitor electrodes.

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.

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.

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.

Oxidation of refractory sulfur compounds over Ti-containing mesoporous molecular sieves prepared by using a fluorosilicon compound.

PubMed

Jeong, Kwang-Eun; Cho, Chin-Soo; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong

2010-05-01

Titanium containing mesoporous molecular sieve (Ti-MMS) catalysts were studied for the oxidative desulfurization of refractory sulfur compounds. Ti-MMS catalysts were synthesized from fluorosilicon compounds and Ti with the hydrolysis reaction of H2SiF6 in an ammonia-surfactant mixed solution. The solid products were characterized by XRD, XRF, nitrogen adsorption, and diffuse reflectance UV-vis spectroscopy. Effects of Ti loading and oxidant/sulfur mole ratio, and sulfur species on ODS activity were investigated.

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.

Mesoporous ZnO microcube derived from a metal-organic framework as photocatalyst for the degradation of organic dyes

NASA Astrophysics Data System (ADS)

Ban, Jin-jin; Xu, Guan-cheng; Zhang, Li; Lin, He; Sun, Zhi-peng; Lv, Yan; Jia, Dian-zeng

2017-12-01

A cube-like porous ZnO architecture was synthesized by direct two-step thermolysis of a zinc-based metal-organic framework [(CH3)2NH2][Zn(HCOO)3]. The obtained ZnO microcube was characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption and desorption isotherms. The mesoporous ZnO microcube was comprised by many nanoparticles, and inherited the cube shape from [(CH3)2NH2][Zn(HCOO)3] precursor. With large surface area and mesoporous structure, the ZnO microcube exhibits excellent photocatalytic activities against methyl orange (MO) and rhodamine B (RhB) under UV irradiation, and the degradation rates reached 99.7% and 98.1% within 120 min, respectively.

Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

NASA Astrophysics Data System (ADS)

Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-04-01

The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

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.

Amino-functionalized silica nanoparticles with center-radially hierarchical mesopores as ideal catalyst carriers

NASA Astrophysics Data System (ADS)

Du, Xin; He, Junhui

2012-01-01

Our previously fabricated amino-functionalized silica nanoparticles (NPs) with center-radially hierarchical mesopores (NH2-HMSNs) were purified by a filtration membrane and used as catalyst carriers in the current article. Noble metal NPs (Au, Pd, Pt and Au & Pt) with small sizes (3-8 nm) were successfully immobilized into the NH2-HMSNs via the deposition-precipitation method. These noble metal NPs with readily adjusted small sizes have high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Among them, Au-NH2-HMSNs were investigated as the composite catalyst in the catalytic reduction of 2-nitroaniline (2-NA) as a model reaction and exhibited excellent catalytic activity and stability. The presence of center-radially large mesopores in the NH2-HMSNs may favor the loading of noble metal NPs with high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Metal-NH2-HMSNs may be more promising composite catalysts due to their superstructure of center-radially hierarchical mesopores that maybe significantly enhance and harmonize the diffusion of guest molecules of different sizes through the porous matrices.Our previously fabricated amino-functionalized silica nanoparticles (NPs) with center-radially hierarchical mesopores (NH2-HMSNs) were purified by a filtration membrane and used as catalyst carriers in the current article. Noble metal NPs (Au, Pd, Pt and Au & Pt) with small sizes (3-8 nm) were successfully immobilized into the NH2-HMSNs via the deposition-precipitation method. These noble metal NPs with readily adjusted small sizes have high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Among them, Au-NH2-HMSNs were investigated as the composite catalyst in the catalytic reduction of 2-nitroaniline (2-NA) as a model reaction and exhibited excellent catalytic activity and stability. The presence of center-radially large mesopores in the NH2-HMSNs may favor

Calcium oxide-modified mesoporous silica loaded onto ferriferrous oxide core: Magnetically responsive mesoporous solid strong base.

PubMed

Li, Tian-Tian; Liu, Yu; Qi, Shi-Chao; Liu, Xiao-Qin; Huang, Li; Sun, Lin-Bing

2018-05-03

The design of new type of solid strong base with ideal activity, stability, and reusability is strongly urged by the growing demand of green chemistry and sustainable development. In this study, a new type of mesoporous solid strong base, denoted as CaO/mSiO 2 /Fe 3 O 4 , is successfully fabricated by successively coating SiO 2 onto Fe 3 O 4 magnetic nanoparticles and loading CaO into the mesoporous SiO 2 . Compared with a series of other typical solid bases, the CaO/mSiO 2 /Fe 3 O 4 exhibits higher activity towards the synthesis of dimethyl carbonate by the transesterification of ethylene carbonate and methanol. The activity of the CaO/mSiO 2 /Fe 3 O 4 is not observed to decrease obviously even after sextic catalyst recirculation, and in particular, the recovery of the catalyst without quality loss is very convenient due to the good magnetic responsiveness of the Fe 3 O 4 cores. Copyright © 2018. Published by Elsevier Inc.

Method for plating with metal oxides

DOEpatents

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.

General facile approach to transition-metal oxides with highly uniform mesoporosity and their application as adsorbents for heavy-metal-ion sequestration.

PubMed

Seisenbaeva, Gulaim A; Daniel, Geoffrey; Kessler, Vadim G; Nedelec, Jean-Marie

2014-08-18

Mesoporous powders of transition-metal oxides, TiO2, ZrO2, HfO2, Nb2O5, and Ta2O5, pure from organic impurities were produced by a rapid single-step thermohydrolytic approach. The obtained materials display an impressively large active surface area and sharp pore-size distribution, being composed of partially coalesced uniform nanoparticles with crystalline cores and amorphous shells. They reveal extremely high adsorption capacity in removal of Cr(VI) anions from solutions (25.8 for TiO2, 73.0 for ZrO2, and 74.7 mg g(-1) for Nb2O5 in relation to the Cr2O7(2-) anion), making them very attractive as adsorbents in water remediation applications. The difference in adsorption capacities for the studied oxides may be explained by variation in surface hydration and surface-charge distribution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported mesoporous carbon ultrafiltration membrane and process for making the same

DOEpatents

Strano, Michael; Foley, Henry C.; Agarwal, Hans

2004-04-13

A novel supported mesoporous carbon ultrafiltration membrane and process for producing the same. The membranes comprise a mesoporous carbon layer that exists both within and external to the porous support. A liquid polymer precursor composition comprising both carbonizing and noncarbonizing templating polymers is deposited on the porous metal support. The coated support is then heated in an inert-gas atmosphere to pyrolyze the polymeric precursor and form a mesoporous carbon layer on and within the support. The pore-size of the membranes is dependent on the molecular weight of the noncarbonizing templating polymer precursor. The mesoporous carbon layer is stable and can withstand high temperatures and exposure to organic chemicals. Additionally, the porous metal support provides excellent strength properties. The composite structure of the membrane provides novel structural properties and allows for increased operating pressures allowing for greater membrane flow rates. The invention also relates to the use of the novel ultrafiltration membrane to separate macromolecules from solution. An example is shown separating bovine serum albumin from water. The membrane functions by separating and by selective adsorption. Because of the membrane's porous metal support, it is well suited to industrial applications. The unique properties of the supported mesoporous carbon membrane also allow the membrane to be used in transient pressure or temperature swing separations processes. Such processes were not previously possible with existing mesoporous membranes. The present invention, however, possesses the requisite physical properties to perform such novel ultrafiltration processes.

Synthesis and structural characterization of ZnO and CuO nanoparticles supported mesoporous silica SBA-15

NASA Astrophysics Data System (ADS)

El-Nahhal, Issa M.; Salem, Jamil K.; Selmane, Mohamed; Kodeh, Fawzi S.; Ebtihan, Heba A.

2017-01-01

Zinc oxide (ZnO) and copper oxide (CuO) nanoparticles were loaded into mesoporous silica SBA-15 by post-synthesis and direct methods. The structural properties were characterized using wide and small angle X-ray diffraction (WXRD & SXRD), X-ray photoelectron spectroscopy (XPS) and N2-adsorption desorption (BET). The WXRD showed that, the loaded zinc and copper oxides were present in crystalline forms (impregnation). The mesoporosity properties of SBA-15 silica were well maintained even after the introduction of metal oxide nanoparticles. BET analysis indicate that the impregnated and condensed ZnO and CuO supported SBA-15 nanocomposites have a lower surface area than that of its parent SBA-15.

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

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.

Oxide film on metal substrate reduced to form metal-oxide-metal layer structure

NASA Technical Reports Server (NTRS)

Youngdahl, C. A.

1967-01-01

Electrically conductive layer of zirconium on a zirconium-oxide film residing on a zirconium substrate is formed by reducing the oxide in a sodium-calcium solution. The reduced metal remains on the oxide surface as an adherent layer and seems to form a barrier that inhibits further reaction.

Metal oxide nanorod arrays on monolithic substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can includemore » a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.« less

Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

PubMed

Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

2014-01-01

Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

A Review on the Synthesis and Applications of Mesostructured Transition Metal Phosphates

PubMed Central

Lin, Ronghe; Ding, Yunjie

2013-01-01

Considerable efforts have been devoted to extending the range of the elemental composition of mesoporous materials since the pioneering work of the M41S family of ordered mesoporous silica by Mobil researchers. The synthesis of transition metal-containing mesostructured materials with large surface area and high porosity has drawn great attention for its potential applications in acid and redox catalysis, photocatalysis, proton conducting devices, environmental restoration and so on. Thus, various transition metals-containing mesoporous materials, including transition metal-substituted mesoporous silicates, mesostructured transition metal oxides and transition metal phosphates (TMP), have been documented in the literature. Among these, mesostructured TMP materials are less studied, but possess some unique features, partly because of the easy and facile functionalization of PO4 and/or P–OH groups, rendering them interesting functional materials. This review first introduced the general synthesis strategies for manufacturing mesostructured TMP materials, as well as advantages and disadvantages of the respective method; then, we surveyed the ongoing developments of fabrication and application of the TMP materials in three groups on the basis of their components and application fields. Future perspectives on existing problems related to the present synthesis routes and further modifying of the functional groups for the purpose of tailoring special physical-chemical properties to meet wide application requirements were also provided in the last part. PMID:28809304

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.

One-pot synthesis of transition metal ion-chelating ordered mesoporous carbon/carbon nanotube composites for active and durable fuel cell catalysts

NASA Astrophysics Data System (ADS)

Dombrovskis, Johanna K.; Palmqvist, Anders E. C.

2017-07-01

Development of non-precious metal catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells with high activity and durability and with optimal water management properties is of outmost technological importance and highly challenging. Here we study the possibilities offered through judicious selection of small molecular precursors used for the formation of ordered mesoporous carbon-based non-precious metal ORR catalysts. By combining two complementary precursors, we present a one-pot synthesis that leads to a composite material consisting of transition metal ion-chelating ordered mesoporous carbon and multi-walled carbon nanotubes (TM-OMC/CNT). The resulting composite materials show high specific surface areas and a carbon structure that exhibits graphitic signatures. The synthesis procedure allows for tuning of the carbon structure, the surface area, the pore volume and the ratio of the two components of the composite. The TM-OMC/CNT composites were processed into membrane electrode assemblies and evaluated in single cell fuel cell measurements where they showed a combination of good ORR activity and very high durability.

Metals and lipid oxidation. Contemporary issues.

PubMed

Schaich, K M

1992-03-01

Lipid oxidation is now recognized to be a critically important reaction in physiological and toxicological processes as well as in food products. This provides compelling reasons to understand what causes lipid oxidation in order to be able to prevent or control the reactions. Redox-active metals are major factors catalyzing lipid oxidation in biological systems. Classical mechanisms of direct electron transfer to double bonds by higher valence metals and of reduction of hydroperoxides by lower valence metals do not always account for patterns of metal catalysis of lipid oxidation in multiphasic or compartmentalized biological systems. To explain why oxidation kinetics, mechanisms, and products in molecular environments which are both chemically and physically complex often do not follow classical patterns predicted by model system studies, increased consideration must be given to five contemporary issues regarding metal catalysis of lipid oxidation: hypervalent non-heme iron or iron-oxygen complexes, heme catalysis mechanism(s), compartmentalization of reactions and lipid phase reactions of metals, effects of metals on product mixes, and factors affecting the mode of metal catalytic action.

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)

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, NH 3, 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 O 2 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 moleculemore » 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 O 2 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

N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Yang; Huo, Jiajie; Jia, Fan

Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH 3, 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 O 2 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 moleculemore » 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 O 2 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

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.

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO 2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H 2 plasma treatment makes TiO 2 films black, with broad-spectrum enhancementmore » of visible light absorption, and XPS analysis shows peak for Ti 3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO 2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO 2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO 2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO 2 is accompanied by significant hydrogen uptake and not just Ti 3+ generation or surface disordering.« less

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE PAGES

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj; ...

2017-10-26

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO 2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H 2 plasma treatment makes TiO 2 films black, with broad-spectrum enhancementmore » of visible light absorption, and XPS analysis shows peak for Ti 3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO 2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO 2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO 2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO 2 is accompanied by significant hydrogen uptake and not just Ti 3+ generation or surface disordering.« less

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj

2018-05-01

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H2 plasma treatment makes TiO2 films black, with broad-spectrum enhancement of visible lightmore » absorption, and XPS analysis shows peak for Ti3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO2 is accompanied by significant hydrogen uptake and not just Ti3+ generation or surface disordering.« less

Synergistic interaction between oxides of copper and iron for production of fatty alcohols from fatty acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kandel, Kapil; Chaudhary, Umesh; Nelson, Nicholas C.

2015-10-08

In this study, the selective hydrogenation of fatty acids to fatty alcohols can be achieved under moderate conditions (180 °C, 30 bar H 2) by simultaneously supporting copper and iron oxides on mesoporous silica nanoparticles. The activity of the cosupported oxides is significantly higher than that of each supported metal oxide and of a physical mixture of both individually supported metal oxides. A strong interaction between both metal oxides is evident from dispersion, XRD, TPR, and acetic acid TPD measurements, which is likely responsible for the synergistic behavior of the catalyst. Copper oxide is reduced in situ to its metallicmore » form and thereby activates hydrogen.« less

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.

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.

Solar hydrogen and solar electricity using mesoporous materials

NASA Astrophysics Data System (ADS)

Mahoney, Luther

The development of cost-effective materials for effective utilization of solar energy is a major challenge for solving the energy problems that face the world. This thesis work relates to the development of mesoporous materials for solar energy applications in the areas of photocatalytic water splitting and the generation of electricity. Mesoporous materials were employed throughout the studies because of their favorable physico-chemical properties such as high surface areas and large porosities. The first project was related to the use of a cubic periodic mesoporous material, MCM-48. The studies showed that chromium loading directly affected the phase of mesoporous silica formed. Furthermore, within the cubic MCM-48 structure, the loading of polychromate species determined the concentration of solar hydrogen produced. In an effort to determine the potential of mesoporous materials, titanium dioxide was prepared using the Evaporation-Induced Self-Assembly (EISA) synthetic method. The aging period directly determined the amount of various phases of titanium dioxide. This method was extended for the preparation of cobalt doped titanium dioxide for solar simulated hydrogen evolution. In another study, metal doped systems were synthesized using the EISA procedure and rhodamine B (RhB) dye sensitized and metal doped titania mesoporous materials were evaluated for visible light hydrogen evolution. The final study employed various mesoporous titanium dioxide materials for N719 dye sensitized solar cell (DSSC) materials for photovoltaic applications. The materials were extensively characterized using powder X-ray diffraction (XRD), nitrogen physisorption, diffuse reflectance spectroscopy (DRS), UV-Vis spectroscopy, Fourier-Transform-Infrared Spectroscopy (FT-IR), Raman spectroscopy, chemisorption, photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). In addition, photoelectrochemical measurements were completed using

Ordered mesoporous ferrosilicate materials with highly dispersed iron oxide nanoparticles and investigation of their unique magnetic properties.

PubMed

Srinivasu, Pavuluri; Suresh, Koppoju; Datt, Gopal; Abhayankar, Ashutosh C; Rao, Pothuraju Nageswara; Lakshmi Kantam, Mannepalli; Bhargava, Suresh K; Tang, Jing; Yamauchi, Yusuke

2014-11-07

Ordered mesoporous ferrosilicate materials with highly dispersed iron oxide nanoparticles are directly synthesized through a hydrothermal approach under acidic conditions. The obtained samples possess a high surface area (up to 1236 m(2) g(-1)) and a large pore volume (up to 1.1 cm(3) g(-1)). By changing the amount of iron content, the magnetic properties can be tuned.

Method for producing metal oxide nanoparticles

DOEpatents

Phillips, Jonathan [Santa Fe, NM; Mendoza, Daniel [Santa Fe, NM; Chen, Chun-Ku [Albuquerque, NM

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.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

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.

The adsorption of gold, palladium and platinum from acidic chloride solutions on mesoporous carbons.

DOE PAGES

Zalupski, Peter R.; McDowell, Rocklan; Dutech, Guy

2014-08-05

Studies on the adsorption characteristics of gold, palladium and platinum on mesoporous carbon (CMK-3) and sulfur-impregnated mesoporous carbon (CMK-3/S) evaluated the benefits/drawbacks of the presence of a layer of elemental sulfur inside mesoporous carbon structures. Adsorption isotherms collected for Au(III), Pd(II) and Pt(IV) on those materials suggest that sulfur does enhance the adsorption of those metal ions in mildly acidic environment (pH 3). The isotherms collected in 1 M HCl show that the benefit of sulfur disappears due to the competing influence of large concentration of hydrogen ions on the ion-exchanging mechanism of metal ions sorption on mesoporous carbon surfaces.more » The collected acid dependencies illustrate similar adsorption characteristics for CMK-3 and CMK-3/S in 1-5 M HCl concentration range. Sorption of metal ions from diluted aqueous acidic mixtures of actual leached electronic waste demonstrated the feasibility of recovery of gold from such liquors.« less

Reactive metal-oxide interfaces: A microscopic view

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

2016-03-01

Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

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.

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.

Method of making controlled morphology metal-oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 tomore » metal oxide nanoparticles having the preselected morphology or to a metal oxide nanosheet including conjoined nanoparticles having the preselected morphology.« less

Regeneration of mesoporous silica aerogel for hydrocarbon adsorption and recovery.

PubMed

Zhang, Chengzhao; Dai, Chong; Zhang, Huaqin; Peng, Shitao; Wei, Xin; Hu, Yandi

2017-09-15

Silica aerogel, with mesoporous structure and high hydrophobicity, is a promising adsorbent for oil spill clean-up. To make it economic and environmental-friendly, hydrocarbon desorption and silica aerogel regeneration were investigated. After hydrocarbon desorption at 80°C, silica aerogel maintained its hydrophobicity. After toluene, petrol, and diesel desorption, shrinkage of mesopores (from 19.9 to 16.8, 13.5, and 13.4nm) of silica aerogels occurred, causing decreased adsorption capacities (from 12.4, 11.2, and 13.6 to 12.0, 6.5, and 2.3g/g). Low surface tension of petrol caused high stress on mesopores during its desorption, resulting in significant pore shrinkage. For diesel, its incomplete desorption and oxidation further hindered the regeneration. Therefore, diesel desorption was also conducted at 200°C. Severe diesel oxidation occurred under aerobic condition and destroyed the mesopores. Under anaerobic condition, no diesel oxidation occurred and the decreases in pore size (to 13.2nm) and adsorption efficiency (to 10.0g/g) of regenerated silica aerogels were much less, compared with under aerobic condition. This study provided new insights on silica aerogel regeneration for oil spill clean-up. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants.

PubMed

Min, Sa Hoon; Bae, Joonwon; Jang, Jyongsik; Lee, Kyung Jin

2013-06-28

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant.

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants

NASA Astrophysics Data System (ADS)

Min, Sa Hoon; Bae, Joonwon; Jang, Jyongsik; Lee, Kyung Jin

2013-06-01

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant.

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.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Mesoporous Silicate Materials in Sensing

PubMed Central

Melde, Brian J.; Johnson, Brandy J.; Charles, Paul T.

2008-01-01

Mesoporous silicas, especially those exhibiting ordered pore systems and uniform pore diameters, have shown great potential for sensing applications in recent years. Morphological control grants them versatility in the method of deployment whether as bulk powders, monoliths, thin films, or embedded in coatings. High surface areas and pore sizes greater than 2 nm make them effective as adsorbent coatings for humidity sensors. The pore networks also provide the potential for immobilization of enzymes within the materials. Functionalization of materials by silane grafting or through co-condensation of silicate precursors can be used to provide mesoporous materials with a variety of fluorescent probes as well as surface properties that aid in selective detection of specific analytes. This review will illustrate how mesoporous silicas have been applied to sensing changes in relative humidity, changes in pH, metal cations, toxic industrial compounds, volatile organic compounds, small molecules and ions, nitroenergetic compounds, and biologically relevant molecules. PMID:27873810

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, L. H.; Deng, Z. X.; Xiao, J. X.; Yang, G. W.

2015-06-01

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

PubMed

Li, L H; Deng, Z X; Xiao, J X; Yang, G W

2015-01-26

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

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.

Electrocatalytic N-Doped Graphitic Nanofiber - Metal/Metal Oxide Nanoparticle Composites.

PubMed

Tang, Hongjie; Chen, Wei; Wang, Jiangyan; Dugger, Thomas; Cruz, Luz; Kisailus, David

2018-03-01

Carbon-based nanocomposites have shown promising results in replacing commercial Pt/C as high-performance, low cost, nonprecious metal-based oxygen reduction reaction (ORR) catalysts. Developing unique nanostructures of active components (e.g., metal oxides) and carbon materials is essential for their application in next generation electrode materials for fuel cells and metal-air batteries. Herein, a general approach for the production of 1D porous nitrogen-doped graphitic carbon fibers embedded with active ORR components, (M/MO x , i.e., metal or metal oxide nanoparticles) using a facile two-step electrospinning and annealing process is reported. Metal nanoparticles/nanoclusters nucleate within the polymer nanofibers and subsequently catalyze graphitization of the surrounding polymer matrix and following oxidation, create an interconnected graphite-metal oxide framework with large pore channels, considerable active sites, and high specific surface area. The metal/metal oxide@N-doped graphitic carbon fibers, especially Co 3 O 4 , exhibit comparable ORR catalytic activity but superior stability and methanol tolerance versus Pt in alkaline solutions, which can be ascribed to the synergistic chemical coupling effects between Co 3 O 4 and robust 1D porous structures composed of interconnected N-doped graphitic nanocarbon rings. This finding provides a novel insight into the design of functional electrocatalysts using electrospun carbon nanomaterials for their application in energy storage and conversion fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Cross dehydrogenative coupling of N-aryltetrahydroisoquinolines (sp3 C–H) with indoles (sp2 C–H) using a heterogeneous mesoporous manganese oxide catalyst

DOE PAGES

Dutta, B.; Sharma, Vinit K.; Sassu, N.; ...

2017-09-01

We disclose a novel, heterogeneous catalytic approach for selective coupling of C1 of N-aryltetrahydroisoquinolines with C3 of indoles in the presence of mesoporous manganese oxides. Our work involves a detailed mechanistic investigation of the reaction on the catalyst surface, backed by DFT computational studies, to understand the superior catalytic activity of manganese oxides.

Bio-inspired immobilization of metal oxides on monolithic microreactor for continuous Knoevenagel reaction.

PubMed

Song, Wentong; Shi, Da; Tao, Shengyang; Li, Zhaoliang; Wang, Yuchao; Yu, Yongxian; Qiu, Jieshan; Ji, Min; Wang, Xinkui

2016-11-01

A facile method is reported to construct monolithic microreactor with high catalytic performance for Knoevenagel reaction. The microreactor is based on hierarchically porous silica (HPS) which has interconnected macro- and mesopores. Then the HPS is surface modified by pyrogallol (PG) polymer. Al(NO3)3 and Mg(NO3)2 are loaded on the surface of HPS through coordination with -OH groups of PG. After thermal treatment, Al(NO3)3 and Mg(NO3)2 are converted Al2O3 and MgO. The as-synthesized catalytic microreactor shows a high and stable performance in Knoevenagel reaction. The microreactor possess large surface area and interconnected pore structures which are beneficial for reactions. Moreover, this economic, facile and eco-friendly surface modification method can be used in loading more metal oxides for more reactions. Copyright © 2016 Elsevier Inc. All rights reserved.

Systematic study of metal-insulator-metal diodes with a native oxide

NASA Astrophysics Data System (ADS)

Donchev, E.; Gammon, P. M.; Pang, J. S.; Petrov, P. K.; Alford, N. McN.

2014-10-01

In this paper, a systematic analysis of native oxides within a Metal-Insulator-Metal (MIM) diode is carried out, with the goal of determining their practicality for incorporation into a nanoscale Rectenna (Rectifying Antenna). The requirement of having a sub-10nm oxide scale is met by using the native oxide, which forms on most metals exposed to an oxygen containing environment. This, therefore, provides a simplified MIM fabrication process as the complex, controlled oxide deposition step is omitted. We shall present the results of an investigation into the current-voltage characteristics of various MIM combinations that incorporate a native oxide, in order to establish whether the native oxide is of sufficient quality for good diode operation. The thin native oxide layers are formed by room temperature oxidation of the first metal layer, deposited by magnetron sputtering. This is done in-situ, within the deposition chamber before depositing the second metal electrode. Using these structures, we study the established trend where the bigger the difference in metal workfunctions, the better the rectification properties of MIM structures, and hence the selection of the second metal is key to controlling the device's rectifying properties. We show how leakage current paths through the non-optimised native oxide control the net current-voltage response of the MIM devices. Furthermore, we will present the so-called diode figures of merit (asymmetry, non-linearity and responsivity) for each of the best performing structures.

Recent advances of mesoporous materials in sample preparation.

PubMed

Zhao, Liang; Qin, Hongqiang; Wu, Ren'an; Zou, Hanfa

2012-03-09

Sample preparation has been playing an important role in the analysis of complex samples. Mesoporous materials as the promising adsorbents have gained increasing research interest in sample preparation due to their desirable characteristics of high surface area, large pore volume, tunable mesoporous channels with well defined pore-size distribution, controllable wall composition, as well as modifiable surface properties. The aim of this paper is to review the recent advances of mesoporous materials in sample preparation with emphases on extraction of metal ions, adsorption of organic compounds, size selective enrichment of peptides/proteins, specific capture of post-translational peptides/proteins and enzymatic reactor for protein digestion. Copyright © 2011 Elsevier B.V. All rights reserved.

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Oxidized film structure and method of making epitaxial metal oxide structure

DOEpatents

Gan, Shupan [Richland, WA; Liang, Yong [Richland, WA

2003-02-25

A stable oxidized structure and an improved method of making such a structure, including an improved method of making an interfacial template for growing a crystalline metal oxide structure, are disclosed. The improved method comprises the steps of providing a substrate with a clean surface and depositing a metal on the surface at a high temperature under a vacuum to form a metal-substrate compound layer on the surface with a thickness of less than one monolayer. The compound layer is then oxidized by exposing the compound layer to essentially oxygen at a low partial pressure and low temperature. The method may further comprise the step of annealing the surface while under a vacuum to further stabilize the oxidized film structure. A crystalline metal oxide structure may be subsequently epitaxially grown by using the oxidized film structure as an interfacial template and depositing on the interfacial template at least one layer of a crystalline metal oxide.

One-pot hydrothermal synthesis of mesoporous Zn(x)Cd(1-x)S/reduced graphene oxide hybrid material and its enhanced photocatalytic activity.

PubMed

Wang, Xinwei; Tian, Hongwei; Cui, Xiaoqiang; Zheng, Weitao; Liu, Yichun

2014-09-14

We successfully synthesized mesoporous Zn(x)Cd(1-x)S/reduced graphene oxide (Z(x)CSG) hybrid materials as photocatalysts using a facile one-pot hydrothermal reaction, in which graphene oxide (GO) was easily reduced (RGO), and simultaneously Zn(x)Cd(1-x)S (Z(x)CS) nanoparticles (NPs) with a mesoporous structure were uniformly dispersed on the RGO sheets. By well tuning the band gap from 3.42 to 2.21 eV by changing the molar ratio of Zn/Cd (or Zn content), Z(x)CSG with an optimal zinc content has been found to have a significant absorption in the visible light (VL) region. In addition, under VL irradiation (λ > 420 nm), Z(x)CSG also showed zinc content-dependent photocatalytic efficiencies for the degradation of methylene blue (MB). Our findings are that, among Z(x)CSG, Z(0.4)CSG displayed not only a superior photodegradation efficiency of MB (98%), but also good removal efficiency of total organic carbon (TOC) (67%). Furthermore, Z(0.4)CSG had a high photocatalytic stability, and could be used repeatedly. The enhanced photocatalytic activity for Z(0.4)CSG could be attributed to a synergistic effect between mesoporous Z(x)CS NPs and RGO, including the optimal band gap and the moderate conduction band position for ZxCS (compared to CdS), efficient separation and transfer ability of photogenerated electron/hole pairs in the presence of RGO sheets, and relatively high surface area for both mesoporous Z(x)CS NPs and RGO.

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

NASA Astrophysics Data System (ADS)

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-03-01

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions

Facile chemical routes to mesoporous silver substrates for SERS analysis

PubMed Central

Tastekova, Elina A; Polyakov, Alexander Yu; Goldt, Anastasia E; Sidorov, Alexander V; Oshmyanskaya, Alexandra A; Sukhorukova, Irina V; Shtansky, Dmitry V; Grünert, Wolgang

2018-01-01

Mesoporous silver nanoparticles were easily synthesized through the bulk reduction of crystalline silver(I) oxide and used for the preparation of highly porous surface-enhanced Raman scattering (SERS)-active substrates. An analogous procedure was successfully performed for the production of mesoporous silver films by chemical reduction of oxidized silver films. The sponge-like silver blocks with high surface area and the in-situ-prepared mesoporous silver films are efficient as both analyte adsorbents and Raman signal enhancement mediators. The efficiency of silver reduction was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The developed substrates were applied for SERS detection of rhodamine 6G (enhancement factor of about 1–5 × 105) and an anti-ischemic mildronate drug (meldonium; enhancement factor of ≈102) that is known for its ability to increase the endurance performance of athletes. PMID:29600149

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.

Conducting metal oxide and metal nitride nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst supportmore » in a fuel cell.« less

Mesoporous silicon oxide films and their uses as templates in obtaining nanostructured conductive polymers

NASA Astrophysics Data System (ADS)

Salgado, R.; Arteaga, G. C.; Arias, J. M.

2018-04-01

Obtaining conductive polymers (CPs) for the manufacture of OLEDs, solar cells, electrochromic devices, sensors, etc., has been possible through the use of electrochemical techniques that allow obtaining films of controlled thickness with positive results in different applications. Current trends point towards the manufacture of nanomaterials, and therefore it is necessary to develop methods that allow obtaining CPs with nanostructured morphology. This is possible by using a porous template to allow the growth of the polymeric materials. However, prior and subsequent treatments are required to separate the material from the template so that it can be evaluated in the applications mentioned above. This is why mesoporous silicon oxide films (template) are essential for the synthesis of nanostructured polymers since both the template and the polymer are obtained on the electrode surface, and therefore it is not necessary to separate the material from the template. Thus, the material can be evaluated directly in the applications mentioned above. The dimensions of the resulting nanostructures will depend on the power, time and technique used for electropolymerization as well as the monomer and the surfactant of the mesoporous film.

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.

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.

Interactions of Plutonium and Lanthanides with Ordered Mesoporous Materials

NASA Astrophysics Data System (ADS)

Parsons-Moss, Tashi

Ordered mesoporous materials are porous solids with a regular, patterned structure composed of pores between 2 and 50 nm wide. Such materials have attracted much attention in the past twenty years because the chemistry of their synthesis allows control of their unique physicochemical properties, which can be tuned for a variety of applications. Generally, ordered mesoporous materials have very high specific surface areas and pore volumes, and offer unique structures that are neither crystalline nor amorphous. The large tunable interface provided by ordered mesoporous solids may be advantageous in applications involving sequestration, separation, or detection of actinides and lanthanides in solution. However, the fundamental chemical interactions of actinides and lanthanides must be understood before applications can be implemented. This dissertation focuses primarily on the fundamental interactions of plutonium with organically modified mesoporous silica, as well as several different porous carbon materials, both untreated and chemically oxidized. A method for functionalizing mesoporous silica by self assembly and molecular grafting of functional organosilane ligands was optimized for the 2D-hexagonal ordered mesoporous silica known as SBA-15 (Santa Barbara amorphous silica). Four different organically-modified silica materials were synthesized and characterized with several techniques. To confirm that covalent bonds were formed between the silane anchor of the ligand and the silica substrate, functionalized silica samples were analyzed with 29Si nuclear magnetic resonance spectroscopy. Infrared spectroscopy was used in combination with 13C and 31P nuclear magnetic resonance spectroscopy to verify the molecular structures of the ligands after they were synthesized and grafted to the silica. The densities of the functional silane ligands on the silica surface were estimated using thermogravimetric analysis. Batch sorption experiments were conducted with solutions of

Mesoporous titanium phosphate molecular sieves with ion-exchange capacity.

PubMed

Bhaumik, A; Inagaki, S

2001-01-31

Novel open framework molecular sieves, titanium(IV) phosphates named, i.e., TCM-7 and -8 (Toyota Composite Materials, numbers 7 and 8), with new mesoporous cationic framework topologies obtained by using both cationic and anionic surfactants are reported. The (31)P MAS NMR, UV-visible absorption, and XANES data suggest the tetrahedral state of P and Ti, and stabilization of the tetrahedral state of Ti in TCM-7/8 is due to the incorporation of phosphorus (at Ti/P = 1:1) vis-à-vis the most stable octahedral state of Ti in the pure mesoporous TiO(2). Mesoporous TCM-7 and -8 show anion exchange capacity due to the framework phosphonium cation and cation exchange capacity due to defective P-OH groups. The high catalytic activity in the liquid-phase partial oxidation of cyclohexene with a dilute H(2)O(2) oxidant supports the tetrahedral coordination of Ti in these materials.

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.

High surface area, electrically conductive nanocarbon-supported metal oxide

DOEpatents

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.

Mesoporous xEr 2O 3·CoTiO 3 composite oxide catalysts for low temperature dehydrogenation of ethylbenzene to styrene using CO 2 as a soft oxidant

DOE PAGES

Yue, Yanfeng; Zhang, Li; Chen, Jihua; ...

2016-01-01

A series of mesoporous xEr 2O 3·CoTiO 3 composite oxide catalysts have been prepared using template method and tested as a new type of catalyst for the oxidative dehydrogenation of ethylbenzene to styrene by using CO 2 as a soft oxidant. Among the catalysts tested, the 0.25Er 2O 3 CoTiO 3 sample with a ratio of 1:4:4 content and calcined at 600 oC exhibited the highest ethylbenzene conversion (58%) and remarkable styrene selectivity (95%) at low temperature (450 °C).

Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

DOEpatents

Poston, J.A.

1997-12-02

Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

DOEpatents

Poston, James A.

1997-01-01

Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

Influence of metal electrodes on the response of humidity sensors coated with mesoporous silica

NASA Astrophysics Data System (ADS)

Bearzotti, Andrea

2008-01-01

Interesting effects of different metal electrodes on the behaviour of mesoporous based humidity sensors have been observed and studied by chemical characterization and electric measurements. The devices were prepared on passivated silicon slices utilizing an interdigitated structure as contacts. For comparison, the response of a device implemented on an alumina substrate has been reported. A block copolymer Pluronic F-127 has been used as the organic template and has been partially removed from the films by thermal calcination. A thin film mesoporous membrane has been deposited by dip-coating on the substrates in a sol-gel solution containing non-ionic block copolymers. Silica mesostructured films have been produced using an evaporation induced self-assembling process. The films were calcined at 150 °C to obtain the best performances in terms of stability, hysteresis and reproducibility of the response. The performance of the sensor has been found to be dependent on the film preparation method, the used electrodes and the substrate when exposed to different contents of relative humidity. Electrical characterization was performed under vacuum and dark conditions to investigate the properties of the materials in the absence of interfering chemicals, while the sensory properties were obtained in a controlled environment.

Synthesis of Nitrogen-Doped Mesoporous Carbon for the Catalytic Oxidation of Ethylbenzene

NASA Astrophysics Data System (ADS)

Wang, Ruicong; Yu, Yifeng; Zhang, Yue; Lv, Haijun; Chen, Aibing

2017-06-01

Nitrogen-doped ordered mesoporous carbon (NOMC) was fabricated via a simple hard-template method by functionalized ionic liquids as carbon and nitrogen source, SBA-15 as a hard-template. The obtained NOMC materials have a high nitrogen content of 5.55 %, a high surface area of 446.2 m2 g-1, and an excellent performance in catalysing oxidation of ethylbenzene. The conversion rate of ethylbenzene can be up to 84.5% and the yield of acetophenone can be up to 69.9%, the results indicated that the NOMC materials have a faster catalytic rate and a higher production of acetophenone than catalyst-free and CMK-3, due to their uniform pore size, high surface area and rich active sites in the carbon pore walls.

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

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters

DOE PAGES

Fernando, Amendra; Weerawardene, K. L. Dimuthu M.; Karimova, Natalia V.; ...

2015-04-21

Here, metal, metal oxide, and metal chalcogenide materials have a wide variety of applications. For example, many metal clusters and nanoparticles are used as catalysts for reactions varying from the oxidation of carbon monoxide to the reduction of protons to hydrogen gas. Noble metal nanoparticles have unique optical properties such as a surface plasmon resonance for large nanoparticles that yield applications in sensing and photonics. In addition, a number of transition metal clusters are magnetic. Metal oxide clusters and surfaces are commonly used as catalysts for reactions such as water splitting. Both metal oxide and metal chalcogenide materials can bemore » semiconducting, which leads to applications in sensors, electronics, and solar cells. Many researchers have been interested in studying nanoparticles and/or small clusters of these materials. Some of the system sizes under investigation have been experimentally synthesized, which enables direct theory–experiment comparison. Other clusters that have been examined theoretically are of interest as models of larger systems or surfaces. Often, the size-dependence of their properties such as their HOMO–LUMO gap, magnetic properties, optical properties, etc., is of interest.« less

Carboxyl-functionalized nanoparticles with magnetic core and mesopore carbon shell as adsorbents for the removal of heavy metal ions from aqueous solution.

PubMed

Wang, Hui; Yu, Yi-Fei; Chen, Qian-Wang; Cheng, Kai

2011-01-21

This communication demonstrates superparamagnetic nanosized particles with a magnetic core and a porous carbon shell (thickness of 11 nm), which can remove 97% of Pb(2+) ions from an acidic aqueous solution at a Pb(2+) ion concentration of 100 mg L(-1). It is suggested that a weak electrostatic force of attraction between the heavy metal ions and the nanoparticles and the heavy metal ions adsorption on the mesopore carbon shell contribute most to the superior removal property.

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

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 P-96-19...

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 P-96-19...

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...

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

2017-07-05

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 H 2 W 12 O 42 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 (H 2 O 2 , 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. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of nitrogen- and sulfur-codoped 3D cubic-ordered mesoporous carbon with superior performance in supercapacitors.

PubMed

Zhang, Deyi; Zheng, Liweng; Ma, Ying; Lei, Longyan; Li, Qinglin; Li, Yan; Luo, Heming; Feng, Huixia; Hao, Yuan

2014-02-26

In this contribution, nitrogen- and sulfur-codoped 3D cubic-ordered mesoporous carbon (KNOMC) materials with controlled dopant content (10.0-4.6 atom % for nitrogen and 0.94-0.75 atom % for sulfur) are presented, using KIT-6 as the template and pyrrole as the precursor, and its supercapacitive behavior is also investigated. The presented materials exhibit excellent supercapacitive performance by combining electrical double-layer capacitance and pseudocapacitance as well as the enhanced wettability and improved conductivity generated from the incorporation of nitrogen and sulfur into the framework of carbon materials. The specific capacitance of the presented materials reaches 320 F g(-1) at a current density of 1 A g(-1), which is significantly larger than that of the pristine-ordered mesoporous carbon reported in the literature and can even compete with some metal oxides and conducting polymers.

Mesoporous ZnS–NiS Nanocomposites for Nonenzymatic Electrochemical Glucose Sensors

PubMed Central

Wei, Chengzhen; Cheng, Cheng; Zhao, Junhong; Wang, Zhangtao; Wu, Haipeng; Gu, Kaiyue; Du, Weimin; Pang, Huan

2015-01-01

Mesoporous ZnS–NiS composites are prepared via ion- exchange reactions using ZnS as the precursor. The prepared mesoporous ZnS–NiS composite materials have large surface areas (137.9 m2 g−1) compared with the ZnS precursor. More importantly, the application of these mesoporous ZnS–NiS composites as nonenzymatic glucose sensors was successfully explored. Electrochemical sensors based on mesoporous ZnS–NiS composites exhibit a high selectivity and a low detection limit (0.125 μm) toward the oxidation of glucose, which can mainly be attributed to the morphological characteristics of the mesoporous structure with high specific surface area and a rational composition of the two constituents. In addition, the mesoporous ZnS–NiS composites coated on the surface of electrodes can be used to modify the mass transport regime, and this alteration can, in favorable circumstances, facilitate the amperometric discrimination between species. These results suggest that such mesoporous ZnS–NiS composites are promising materials for nonenzymatic glucose sensors. PMID:25861568

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.

Synthesis of Mesoporous Co2+-Doped TiO2 Nanodisks Derived from Metal Organic Frameworks with Improved Sodium Storage Performance.

PubMed

Hong, Zhensheng; Kang, Meiling; Chen, Xiaohui; Zhou, Kaiqiang; Huang, Zhigao; Wei, Mingdeng

2017-09-20

TiO 2 is a most promising anode candidate for rechargeable Na-ion batteries (NIBs) because of its appropriate working voltage, low cost, and superior structural stability during chage/discharge process. Nevertheless, it suffers from intrinsically low electrical conductivity. Herein, we report an in situ synthesis of Co 2+ -doped TiO 2 through the thermal treatment of metal organic frameworks precursors of MIL-125(Ti)-Co as a superior anode material for NIBs. The Co 2+ -doped TiO 2 possesses uniform nanodisk morphology, a large surface area and mesoporous structure with narrow pore distribution. The reversible capacity, Coulombic efficiency (CE) and rate capability can be improved by Co 2+ doping in mesoporous TiO 2 anode. Co 2+ -doped mesoporous TiO 2 nanodisks exhibited a high reversible capacity of 232 mAhg -1 at 0.1 Ag 1- , good rate capability and cycling stability with a stable capacity of about 140 mAhg -1 at 0.5 Ag 1- after 500 cycles. The enhanced Na-ion storage performance could be due to the increased electrical conductivity revealed by Kelvin probe force microscopy measurements.

Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

PubMed

Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

2017-01-03

Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Study of Horseradish Peroxidase Fixed on Mesoporous Materials as a Chemical Reaction Catalyst

NASA Astrophysics Data System (ADS)

Gao, Mengdan; Dai, Rongji

2017-12-01

Nanostructured mesoporous materials is a new type of porous materials, which has been widely used. It has excellent capability in enzymes immobilization, but modification on the chemical bonds of the enzyme reduce the enzymatic activity and rarely used in chemical reactions. The horseradish peroxidase was immobilized on the mesoporous materials with appropriate aperture and its activity and stability was evaluated when catalyzing the nitration reaction of amines and oxidation reaction of thiourea. The optimum mesoporous material to fix the horseradish peroxidase can be obtained by mixing polyoxyethylene - polyoxypropylene-pol, yoxyethylene(P123), 1,3,5-trimethylbenzene(TMB), and tetramethoxysilane (TMOS) at a ratio of 10:1:1, whose surface area and pore volume and pore diameter calculated by BET and BJH model were 402.903m2/g, 1.084cm2/g, 1.084cm2/g respectively. The horseradish peroxidase, immobilized on the mesoporous materials, was applied for catalyzing the nitration reaction of anilines and oxidation reaction of thiourea, produced a high product yield and can be recycled. Thus, it is a strong candidate as a catalysts for oxidation reactions, to be produced at industral scale, due to its high efficiency and low cost.

Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

NASA Astrophysics Data System (ADS)

Garces Trujillo, Hector Fabian

This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulvio, Pasquale F; Dai, Sheng; Guo, Bingkun

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol formaldehyde as a carbon precursor in the presence of triblock ethylene oxide propylene oxide ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from 0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m2 g 1 after fluorination as calculated from nitrogen adsorption isotherms at 196more » C. Furthermore, the materials exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CFx batteries.« less

Controllable synthesis of mesoporous multi-shelled ZnO microspheres as efficient photocatalysts for NO oxidation

NASA Astrophysics Data System (ADS)

Chen, Xiaolang; Zhang, Huiqiang; Zhang, Dieqing; Miao, Yingchun; Li, Guisheng

2018-03-01

The successful application of hierarchically porous structure in environmental treatment has provided new insights for solving environmental problems. Hierarchically structured semiconductor materials were considered as promising photocatalysts for NO oxidation in gas phase. Multi-shelled ZnO microspheres (MMSZ) were controllably shaped with hierarchically porous structures via a facile hydrothermal route using amino acid (N-Acetyl-D-Proline) as template and post-calcination treatment. Symmetric Ostwald ripening was used to explain the morphological evolution of hierarchical nanostructure. MMSZ was proved highly efficient for oxidizing NO (400 ppb) in gas phase under UV light irradiation with a much higher photocatalytic removal rate (77.3%) than that of the as-obtained ZnO crystals with other hierachically porous structures, owing to its higher photocurrent intensity. Such greatly enhanced photocatalytic activity can be assigned to the enhanced crystallinity of ZnO, mesopores and unique multi-shelled structure. Enhanced crystallinity promotes photogenerated charges under light irradiation. Mesoporous porosity can ensure enough light scattering between the shells. Multi-shelled structure endows ZnO with higher specific surface area and high frequency of multiple light reflection, resulting in more exposed active sites, higher light utilization efficiency, and fast separation efficiency of photogenerated charge carriers. The experimental results demonstrated that the photogenerated holes (h+) are the main active species. Hierarchically structured ZnO is not only contributed to directly use solar energy to solving various problems caused by atmospheric pollution, but also has potential applications in energy converse and storage including solar cells, lithium batteries, water-splitting, etc.

Unified computational model of transport in metal-insulating oxide-metal systems

NASA Astrophysics Data System (ADS)

Tierney, B. D.; Hjalmarson, H. P.; Jacobs-Gedrim, R. B.; Agarwal, Sapan; James, C. D.; Marinella, M. J.

2018-04-01

A unified physics-based model of electron transport in metal-insulator-metal (MIM) systems is presented. In this model, transport through metal-oxide interfaces occurs by electron tunneling between the metal electrodes and oxide defect states. Transport in the oxide bulk is dominated by hopping, modeled as a series of tunneling events that alter the electron occupancy of defect states. Electron transport in the oxide conduction band is treated by the drift-diffusion formalism and defect chemistry reactions link all the various transport mechanisms. It is shown that the current-limiting effect of the interface band offsets is a function of the defect vacancy concentration. These results provide insight into the underlying physical mechanisms of leakage currents in oxide-based capacitors and steady-state electron transport in resistive random access memory (ReRAM) MIM devices. Finally, an explanation of ReRAM bipolar switching behavior based on these results is proposed.

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.

Synthesis of mesoporous TS-1 using a hybrid SiO{sub 2}–TiO{sub 2} xerogel for catalytic oxidative desulfurization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Seung-Tae; Jeong, Kwang-Eun; Jeong, Soon-Yong

2012-12-15

Graphical abstract: Display Omitted Highlights: ► Meso-TS-1 catalyst was synthesized using a SiO{sub 2}–TiO{sub 2} xerogel with an organosilane precursor. ► Hierarchical pore structure was confirmed by characterization of the materials. ► Catalytic activity was tested using oxidative desulfurization of the model sulfur compounds. ► Meso-TS-1 demonstrated significantly improved catalytic activity than TS-1. -- Abstract: Mesoporous TS-1 (M-TS-1) was synthesized using a hybrid SiO{sub 2}–TiO{sub 2} xerogel combined with an organosilane precursor. Prepared samples were characterized by XRD, UV–vis spectroscopy, SEM, and N{sub 2} adsorption–desorption measurement. M-TS-1, prepared in 2 days, showed high crystallinity and the best textural properties amongmore » the samples. The N{sub 2} adsorption–desorption isotherms of M-TS-1 exhibited a hysteresis loop at pressure higher than P/P{sub 0} = 0.4, clearly indicating the existence of mesopores. M-TS-1 has significantly larger mesopore volume (0.48 cm{sup 3}/g) than that of conventional TS-1 (0.07 cm{sup 3}/g), and showed a narrow peak centered at ca. 6.3 nm. In the oxidative desulfurization reaction, M-TS-1 was more active than conventional TS-1 at the same Ti-loading; M-TS-1 produced a dibenzothiophene (DBT) conversion of 96%, whereas conventional TS-1 produced a final DBT conversion of 5.6% after a reaction time of 180 min. Oxidative desulfurization over TS-1 was influenced both by electron density and steric hindrance in the sulfur compounds tested.« less

Interfacial Metal-Oxide Interactions in Resistive Switching Memories.

PubMed

Cho, Deok-Yong; Luebben, Michael; Wiefels, Stefan; Lee, Kug-Seung; Valov, Ilia

2017-06-07

Metal oxides are commonly used as electrolytes for redox-based resistive switching memories. In most cases, non-noble metals are directly deposited as ohmic electrodes. We demonstrate that irrespective of bulk thermodynamics predictions an intermediate oxide film a few nanometers in thickness is always formed at the metal/insulator interface, and this layer significantly contributes to the development of reliable switching characteristics. We have tested metal electrodes and metal oxides mostly used for memristive devices, that is, Ta, Hf, and Ti and Ta 2 O 5 , HfO 2 , and SiO 2 . Intermediate oxide layers are always formed at the interfaces, whereas only the rate of the electrode oxidation depends on the oxygen affinity of the metal and the chemical stability of the oxide matrix. Device failure is associated with complete transition of short-range order to a more disordered main matrix structure.

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

PubMed

Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

2013-04-05

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Mesoporous nanocrystalline film architecture for capacitive storage devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

The MSFC complementary metal oxide semiconductor (including multilevel interconnect metallization) process handbook

NASA Technical Reports Server (NTRS)

Bouldin, D. L.; Eastes, R. W.; Feltner, W. R.; Hollis, B. R.; Routh, D. E.

1979-01-01

The fabrication techniques for creation of complementary metal oxide semiconductor integrated circuits at George C. Marshall Space Flight Center are described. Examples of C-MOS integrated circuits manufactured at MSFC are presented with functional descriptions of each. Typical electrical characteristics of both p-channel metal oxide semiconductor and n-channel metal oxide semiconductor discrete devices under given conditions are provided. Procedures design, mask making, packaging, and testing are included.

Oxidized template-synthesized mesoporous carbon with pH-dependent adsorption activity: A promising adsorbent for removal of hydrophilic ionic liquid

NASA Astrophysics Data System (ADS)

Zhang, Ling; Cao, Wugang; Alvarez, Pedro J. J.; Qu, Xiaolei; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

2018-05-01

Aiming to remove ionic liquid pollutants from water, an ordered mesoporous carbon CMK-3 (OMC) was prepared and modified by oxidation with nitric acid. A commercial microporous activated carbon adsorbent, Filtrasorb-300 (AC), was used as benchmark. Boehm titration showed that oxidized OMC had a substantially higher oxygen content than oxidized AC. Adsorption of the hydrophilic imidazolium-based ionic liquid 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl) on OMC and AC was well-described by the Freundlich isotherm model. Surface oxidation markedly enhanced [Bmim]Cl adsorption by both OMC and AC. Nevertheless, [Bmim]Cl adsorption was much higher on oxidized OMC than on oxidized AC. Increasing pH had negligible influence on [Bmim]Cl adsorption on pristine OMC, but enhanced adsorption on oxidized OMC. Regeneration tests showed stable performance of oxidized OMC over five adsorption-desorption cycles. Thus, oxidized OMC can be a highly effective adsorbent for the removal of hydrophilic ionic liquids from water.

Mesoporous carbon materials

DOEpatents

Dai, Sheng; Fulvio, Pasquale Fernando; Mayes, Richard T.; Wang, Xiqing; Sun, Xiao-Guang; Guo, Bingkun

2014-09-09

A conductive mesoporous carbon composite comprising conductive carbon nanoparticles contained within a mesoporous carbon matrix, wherein the conductive mesoporous carbon composite possesses at least a portion of mesopores having a pore size of at least 10 nm and up to 50 nm, and wherein the mesopores are either within the mesoporous carbon matrix, or are spacings delineated by surfaces of said conductive carbon nanoparticles when said conductive carbon nanoparticles are fused with each other, or both. Methods for producing the above-described composite, devices incorporating them (e.g., lithium batteries), and methods of using them, are also described.

Synthesis of Oxides Containing Transition Metals

DTIC Science & Technology

1990-07-09

metal oxide single crystals by the electrolysis of molten salts containing mixtures of the appropriate oxides. Andreiux and Bozon (33-34) were able to...examples of unusual transition metal oxides which can be prepared (usually as single crystals) by electrolysis of fused salts . Summary The methods of...ferrites with the composition MFe 204 involved the thermal decomposition of oxalate (3) or pyridinate salts (1). The synthesis of ferrites from mixed

Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica

DOEpatents

Pham, Hien N.; Datye, Abhaya K.

2003-04-15

The present invention relates to catalysts in mesoporous structures. In a preferred embodiment, the invention comprises a method for encapsulating a dispersed insoluble compound in a mesoporous structure comprising combining a soluble oxide precursor, a solvent, and a surfactant to form a mixture; dispersing an insoluble compound in the mixture; spray-drying the mixture to produce dry powder; and calcining the powder to yield a porous structure comprising the dispersed insoluble compound.

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 P-98-0002...

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 P-99-511...

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 P-98-0002...

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 P-99-511...

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 P-98-0002...

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 P-98-0002...

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 P-99-511...

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 P-98-0002...

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 P-99-511...

Synthesis and characterization of mesoporous hydrocracking catalysts

NASA Astrophysics Data System (ADS)

Munir, D.; Usman, M. R.

2016-08-01

Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

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) is...

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) is...

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) is...

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) is...

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) is...

Immobilization of mesoporous silica particles on stainless steel plates

NASA Astrophysics Data System (ADS)

Pasqua, Luigi; Morra, Marco

2017-03-01

A preliminary study aimed to the nano-engineering of stainless steel surface is presented. Aminopropyl-functionalized mesoporous silica is covalently and electrostatically anchored on the surface of stainless steel plates. The anchoring is carried out through the use of a nanometric spacer, and two different spacers are proposed (both below 2 nm in size). The first sample is obtained by anchoring to the stainless steel amino functionalized, a glutaryl dichloride spacer. This specie forms an amide linkage with the amino group while the unreacted acyl groups undergo hydrolysis giving a free carboxylic group. The so-obtained functionalized stainless steel plate is used as substrate for anchoring derivatized mesoporous silica particles. The second sample is prepared using 2-bromo-methyl propionic acid as spacer (BMPA). Successively, the carboxylic group of propionic acid is condensed to the aminopropyl derivatization on the external surface of the mesoporous silica particle through covalent bond. In both cases, a continuous deposition (coating thickness is around 10 μm) is obtained, in fact, XPS data do not reveal the metal elements constituting the plate. The nano-engineering of metal surfaces can represent an intriguing opportunity for producing long-term drug release or biomimetic surface.

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.

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control.

PubMed

Park, Sung Soo; Ha, Chang-Sik

2006-01-01

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc. c) 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Dextran templating for the synthesis of metallic and metal oxide sponges

NASA Astrophysics Data System (ADS)

Walsh, Dominic; Arcelli, Laura; Ikoma, Toshiyuki; Tanaka, Junzo; Mann, Stephen

2003-06-01

Silver or gold-containing porous frameworks have been used extensively in catalysis, electrochemistry, heat dissipation and biofiltration. These materials are often prepared by thermal reduction of metal-ion-impregnated porous insoluble supports (such as alumina and pumice), and have surface areas of about 1 m2 g-1, which is typically higher than that obtained for pure metal powders or foils prepared electrolytically or by infiltration and thermal decomposition of insoluble cellulose supports. Starch gels have been used in association with zeolite nanoparticles to produce porous inorganic materials with structural hierarchy, but the use of soft sacrificial templates in the synthesis of metallic sponges has not been investigated. Here we demonstrate that self-supporting macroporous frameworks of silver, gold and copper oxide, as well as composites of silver/copper oxide or silver/titania can be routinely prepared by heating metal-salt-containing pastes of the polysaccharide, dextran, to temperatures between 500 and 900 °C. Magnetic sponges were similarly prepared by replacing the metal salt precursor with preformed iron oxide (magnetite) nanoparticles. The use of dextran as a sacrificial template for the fabrication of metallic and metal oxide sponges should have significant benefits over existing technologies because the method is facile, inexpensive, environmentally benign, and amenable to scale-up and processing.

Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.

PubMed

Chen, Po-Chiang; Shen, Guozhen; Shi, Yi; Chen, Haitian; Zhou, Chongwu

2010-08-24

In the work described in this paper, we have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on transition-metal-oxide nanowire/single-walled carbon nanotube (SWNT) hybrid thin-film electrodes. These hybrid nanostructured films, with advantages of mechanical flexibility, uniform layered structures, and mesoporous surface morphology, were produced by using a filtration method. Here, manganese dioxide nanowire/SWNT hybrid films worked as the positive electrode, and indium oxide nanowire/SWNT hybrid films served as the negative electrode in a designed ASC. In our design, charges can be stored not only via electrochemical double-layer capacitance from SWNT films but also through a reversible faradic process from transition-metal-oxide nanowires. In addition, to obtain stable electrochemical behavior during charging/discharging cycles in a 2 V potential window, the mass balance between two electrodes has been optimized. Our optimized hybrid nanostructured ASCs exhibited a superior device performance with specific capacitance of 184 F/g, energy density of 25.5 Wh/kg, and columbic efficiency of approximately 90%. In addition, our ASCs exhibited a power density of 50.3 kW/kg, which is 10-fold higher than obtained in early reported ASC work. The high-performance hybrid nanostructured ASCs can find applications in conformal electrics, portable electronics, and electrical vehicles.

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.

CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1990-01-01

Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Mesoporous Nickel Oxide (NiO) Nanopetals for Ultrasensitive Glucose Sensing

NASA Astrophysics Data System (ADS)

Mishra, Suryakant; Yogi, Priyanka; Sagdeo, P. R.; Kumar, Rajesh

2018-01-01

Glucose sensing properties of mesoporous well-aligned, dense nickel oxide (NiO) nanostructures (NSs) in nanopetals (NPs) shape grown hydrothermally on the FTO-coated glass substrate has been demonstrated. The structural study based investigations of NiO-NPs has been carried out by X-ray diffraction (XRD), electron and atomic force microscopies, energy dispersive X-ray (EDX), and X-ray photospectroscopy (XPS). Brunauer-Emmett-Teller (BET) measurements, employed for surface analysis, suggest NiO's suitability for surface activity based glucose sensing applications. The glucose sensor, which immobilized glucose on NiO-NPs@FTO electrode, shows detection of wide range of glucose concentrations with good linearity and high sensitivity of 3.9 μA/μM/cm2 at 0.5 V operating potential. Detection limit of as low as 1 μΜ and a fast response time of less than 1 s was observed. The glucose sensor electrode possesses good anti-interference ability, stability, repeatability & reproducibility and shows inert behavior toward ascorbic acid (AA), uric acid (UA) and dopamine acid (DA) making it a perfect non-enzymatic glucose sensor.

Synthesis and applications of nanoporous perovskite metal oxides

PubMed Central

Huang, Xiubing; Zhao, Guixia

2018-01-01

Perovskite-type metal oxides have been widely investigated and applied in various fields in the past several decades due to their extraordinary variability of compositions and structures with targeted physical and chemical properties (e.g., redox behaviour, oxygen mobility, electronic and ionic conductivity). Recently, nanoporous perovskite metal oxides have attracted extensive attention because of their special morphology and properties, as well as superior performance. This minireview aims at summarizing and reviewing the different synthesis methods of nanoporous perovskite metal oxides and their various applications comprehensively. The correlations between the nanoporous structures and the specific performance of perovskite oxides are summarized and highlighted. The future research directions of nanoporous perovskite metal oxides are also prospected. PMID:29862001

Versatile NiO/mesoporous carbon nanodisks: controlled synthesis from hexagon shaped heterobimetallic metal-organic frameworks.

PubMed

Zeng, Dehong; Yang, Ying; Yang, Feng; Guo, Fangmin; Yang, Senjie; Liu, Baijun; Hao, Shijie; Ren, Yang

2017-08-24

Hexagonal NiO/mesoporous carbon nanodisks (NiO/MCN) are facilely and controllably synthesized via constructing nickel-zinc trimesic acid heterobimetallic metal-organic framework (HMOF) disks before pyrolysis at 910 °C. Tailoring the Ni/(Zn + Ni) feed ratio and the reaction time during the HMOF synthesis creates a well-defined hexagonal carbon nanodisk with properly populated NiO nanocrystals while maintaining high porosity and conductivity. Such an elaborately fabricated NiO/MCN is highly stable, and exhibits the largest specific capacitance of 261 F g -1 and the highest specific activity factor of 1.93 s -1 g -1 of any composite nanodisk during the capacitive test and 4-nitrophenol reduction, respectively.

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.

Increased photocatalytic activity of TiO 2 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 TiO 2 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 TiO 2 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 bothmore » 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 TiO 2 was significantly enhanced relative to (N) TiO 2.« less

Highly improved sensibility and selectivity ethanol sensor of mesoporous Fe-doped NiO nanowires

NASA Astrophysics Data System (ADS)

Li, X. Q.; Wei, J. Q.; Xu, J. C.; Jin, H. X.; Jin, D. F.; Peng, X. L.; Hong, B.; Li, J.; Yang, Y. T.; Ge, H. L.; Wang, Xinqing

2017-12-01

In this paper, nickel oxides (NiO) and iron (Fe)-doped NiO nanowires (NWs) with the various doping content (from 1 to 9 at%) were synthesized by using SBA-15 templates with the nanocasting method. All samples were synthesized in the same conditions and exhibited the same mesoporous-structures, uniform diameter, and defects. Mesoporous-structures with high surface area created more active sites for the adsorption of oxygen on the surface of all samples, resulting in the smaller surface resistance in air. The impurity energy levels from the donor Fe-doping provided electrons to neutralize the holes of p-type Fe-doped NiO NWs, which greatly enhanced the total resistance. The comparative gas-sensing study between NiO NWs and Fe-doped NiO NWs indicated that the high-valence donor Fe-doping obviously improved the ethanol sensitivity and selectivity for Fe-doped NiO NWs. And Ni0.94Fe0.06O1.03 NWs sensor presented the highest sensitivity of 14.30 toward ethanol gas at 320 °C for the high-valence metal-doping.

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

PubMed

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

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 (MF x ) 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 (NH 4 F) for the preparation of anhydrous MF x (CuF 2 , FeF 3 , and CoF 2 )/mesoporous carbon (MSU-F-C) nanocomposites, whereby a series of metal precursor nanoparticles preconfined in mesoporous carbon were readily converted to anhydrous MF x through simple heat treatment with NH 4 F 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 MF x /MSU-F-C prepared in this study exhibited superior electrochemical performances, through conversion reactions, as the cathode for LIBs. In particular, FeF 3 /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 MF x for use in energy storage and other applications.

Metal/oxide interfacial effects on the selective oxidation of primary alcohols

PubMed Central

Zhao, Guofeng; Yang, Fan; Chen, Zongjia; Liu, Qingfei; Ji, Yongjun; Zhang, Yi; Niu, Zhiqiang; Mao, Junjie; Bao, Xinhe; Hu, Peijun; Li, Yadong

2017-01-01

A main obstacle in the rational development of heterogeneous catalysts is the difficulty in identifying active sites. Here we show metal/oxide interfacial sites are highly active for the oxidation of benzyl alcohol and other industrially important primary alcohols on a range of metals and oxides combinations. Scanning tunnelling microscopy together with density functional theory calculations on FeO/Pt(111) reveals that benzyl alcohol enriches preferentially at the oxygen-terminated FeO/Pt(111) interface and undergoes readily O–H and C–H dissociations with the aid of interfacial oxygen, which is also validated in the model study of Cu2O/Ag(111). We demonstrate that the interfacial effects are independent of metal or oxide sizes and the way by which the interfaces were constructed. It inspires us to inversely support nano-oxides on micro-metals to make the structure more stable against sintering while the number of active sites is not sacrificed. The catalyst lifetime, by taking the inverse design, is thereby significantly prolonged. PMID:28098146

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts.

PubMed

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-04-14

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the "I(+)X(-)S(+)" mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.

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.

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.

Recent applications of liquid metals featuring nanoscale surface oxides

NASA Astrophysics Data System (ADS)

Neumann, Taylor V.; Dickey, Michael D.

2016-05-01

This proceeding describes recent efforts from our group to control the shape and actuation of liquid metal. The liquid metal is an alloy of gallium and indium which is non-toxic, has negligible vapor pressure, and develops a thin, passivating surface oxide layer. The surface oxide allows the liquid metal to be patterned and shaped into structures that do not minimize interfacial energy. The surface oxide can be selectively removed by changes in pH or by applying a voltage. The surface oxide allows the liquid metal to be 3D printed to form free-standing structures. It also allows for the liquid metal to be injected into microfluidic channels and to maintain its shape within the channels. The selective removal of the oxide results in drastic changes in surface tension that can be used to control the flow behavior of the liquid metal. The metal can also wet thin, solid films of metal that accelerates droplets of the liquid along the metal traces .Here we discuss the properties and applications of liquid metal to make soft, reconfigurable electronics.

Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

NASA Astrophysics Data System (ADS)

Renaud, Gilles

Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having

Lithium metal oxide electrodes for lithium batteries

DOEpatents

Thackeray, Michael M [Naperville, IL; Kim, Jeom-Soo [Naperville, IL; Johnson, Christopher S [Naperville, IL

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.

Mesoporous anatase TiO{sub 2}/reduced graphene oxide nanocomposites: A simple template-free synthesis and their high photocatalytic performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Qi; Zhong, Yong-Hui; Laboratory of Nanomaterials and Environmental Detection, Hefei Institute of Physical Sciences, Chinese Academy of Sciences, Hefei 230031

2014-03-01

Graphical abstract: - Highlights: • Mesoporous TiO{sub 2} nanoparticles with anatase phase were assembled on reduced graphene oxide via a template-free one-step hydrothermal method. • The TiO{sub 2}/rGO nanocomposites have better adsorption capacity and photocatalytic degradation efficiency for dyes removal. • Improved dye adsorption and photogenerated charge separation are responsible for enhanced activity. - Abstract: Mesoporous anatase phase TiO{sub 2} was assembled on reduced graphene oxide (rGO) using a template-free one-step hydrothermal process. The nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Brunauer–Emmett–Teller (BET) surface area.more » Morphology of TiO{sub 2} was related to the content of graphene oxide. TiO{sub 2}/rGO nanocomposites exhibited excellent photocatalytic activity for the photo-degradation of methyl orange. The degradation rate was 4.5 times greater than that of pure TiO{sub 2} nanoparticles. This difference was attributed to the thin two-dimensional graphene sheet. The graphene sheet had a large surface area, high adsorption capacity, and acted as a good electron acceptor for the transfer of photo-generated electrons from the conduction band of TiO{sub 2}. The enhanced surface adsorption characteristics and excellent charge transport separation were independent properties of the photocatalytic degradation process.« less

Metal-oxide-based energetic materials and synthesis thereof

DOEpatents

Tillotson, Thomas M. , Simpson; Randall, L [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2006-01-17

A method of preparing energetic metal-oxide-based energetic materials using sol-gel chemistry has been invented. The wet chemical sol-gel processing provides an improvement in both safety and performance. Essentially, a metal-oxide oxidizer skeletal structure is prepared from hydrolyzable metals (metal salts or metal alkoxides) with fuel added to the sol prior to gelation or synthesized within the porosity metal-oxide gel matrix. With metal salt precursors a proton scavenger is used to destabilize the sol and induce gelation. With metal alkoxide precursors standard well-known sol-gel hydrolysis and condensation reactions are used. Drying is done by standard sol-gel practices, either by a slow evaporation of the liquid residing within the pores to produce a high density solid nanocomposite, or by supercritical extraction to produce a lower density, high porous nanocomposite. Other ingredients may be added to this basic nanostructure to change physical and chemical properties, which include organic constituents for binders or gas generators during reactions, burn rate modifiers, or spectral emitters.

Aerosol chemical vapor deposition of metal oxide films

DOEpatents

Ott, K.C.; Kodas, T.T.

1994-01-11

A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said substrate.

Transition metal-catalyzed oxidation of sulfur(IV) oxides. Atmospheric-relevant processes and mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brandt, C.; Eldik, R. van

1995-01-01

The transition metal-catalyzed oxidation of sulfur(IV) oxides has been known for more than 100 years. There is a significant lack of information on the actual role of the transition metal-catalyzed reactions, and much of the earlier work was performed without a detailed knowledge of the chemical system. For this reason attention is focused on the role of transition metal ions in the oxidation of sulfur(IV) oxides in terms of the coordination chemistry involved, as well as the stability and chemical behavior of the various participating species. The oxidation process of sulfur(IV) oxides plays an important role in atmospheric chemistry (e.g.more » acid rain formation) as well as industrial processes (e.g. desulfurization of plume gases and ore). The present report deals with the mechanism of the transition metal-catalyzed oxidation of sulfur(IV) oxides with the aim to discuss this in terms of atmospheric and chemical processes. In addition, the authors would like to emphasize the key role of oxygen in these processes. 1,076 refs.« less

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.

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

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.

Solder for oxide layer-building metals and alloys

DOEpatents

Kronberg, James W.

1992-01-01

A low temperature solder and method for soldering an oxide layer-building metal such as aluminum, titanium, tantalum or stainless steel. The comosition comprises tin and zinc; germanium as a wetting agent; preferably small amounts of copper and antimony; and a grit, such as silicon carbide. The grit abrades any oxide layer formed on the surface of the metal as the germanium penetrates beneath and loosens the oxide layer to provide good metal-to-metal contact. The germanium comprises less than aproximatley 10% by weight of the solder composition so that it provides sufficient wetting action but does not result in a melting temperature above approximately 300.degree. C. The method comprises the steps rubbing the solder against the metal surface so the grit in the solder abrades the surface while heating the surface until the solder begins to melt and the germanium penetrates the oxide layer, then brushing aside any oxide layer loosened by the solder.

Solder for oxide layer-building metals and alloys

DOEpatents

Kronberg, J.W.

1992-09-15

A low temperature solder and method for soldering an oxide layer-building metal such as aluminum, titanium, tantalum or stainless steel is disclosed. The composition comprises tin and zinc; germanium as a wetting agent; preferably small amounts of copper and antimony; and a grit, such as silicon carbide. The grit abrades any oxide layer formed on the surface of the metal as the germanium penetrates beneath and loosens the oxide layer to provide good metal-to-metal contact. The germanium comprises less than approximately 10% by weight of the solder composition so that it provides sufficient wetting action but does not result in a melting temperature above approximately 300 C. The method comprises the steps rubbing the solder against the metal surface so the grit in the solder abrades the surface while heating the surface until the solder begins to melt and the germanium penetrates the oxide layer, then brushing aside any oxide layer loosened by the solder.

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.

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.

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.

Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

PubMed

Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

2017-07-12

The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N 2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO 2 -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO 2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO 2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO 2 adsorption indicated the stronger interactions between the surfaces and CO 2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO 2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO 2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

Aerosol chemical vapor deposition of metal oxide films

DOEpatents

Ott, Kevin C.; Kodas, Toivo T.

1994-01-01

A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

Compositional effects in Ru, Pd, Pt, and Rh-doped mesoporous tantalum oxide catalysts for ammonia synthesis.

PubMed

Yue, Chaoyang; Qiu, Longhui; Trudeau, Michel; Antonelli, David

2007-06-11

A series of early metal-promoted Ru-, Pd-, Pt-, and Rh-doped mesoporous tantalum oxide catalysts were synthesized using a variety of dopant ratios and dopant precursors, and the effects of these parameters on the catalytic activity of NH3 synthesis from H2 and N2 were explored. Previous studies on this system supported an unprecedented mechanism in which N-N cleavage occurred at the Ta sites rather than on Ru. The results of the present study showed, for all systems, that Ba is a better promoter than Cs or La and that the nitrate is a superior precursor for Ba than the isopropoxide or the hydroxide. 15N-labeling studies showed that residual nitrate functions as the major ammonia source in the first hour but that it does not account for the ammonia produced after the nitrate is completely consumed. Ru3(CO)12 proved to be a better Ru precursor than RuCl(3).3H2O, and an almost linear increase in activity with increasing Ru loading level was observed at 350 degrees C (623 K). However, at 175 degrees C (448 K), the increase in Ru had no effect on the reaction rate. Pd functioned with comparable rates to Ru, while Pt and Rh functioned far less efficiently. The surprising activities for the Pd-doped catalysts, coupled with XPS evidence for low-valent Ta in this catalyst system, support a mechanism in which cleavage of the N-N triple bond occurs on Ta rather than the precious metal because the Ea value for N-N cleavage on Pd is 2.5 times greater than that for Ru, and the 9.3 kJ mol-1 Ea value measured previously for the Ru system suggests that N-N cleavage cannot occur at the Ru surface.

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

Internal zone growth method for producing metal oxide metal eutectic composites

DOEpatents

Clark, Grady W.; Holder, John D.; Pasto, Arvid E.

1980-01-01

An improved method for preparing a cermet comprises preparing a compact having about 85 to 95 percent theoretical density from a mixture of metal and metal oxide powders from a system containing a eutectic composition, and inductively heating the compact in a radiofrequency field to cause the formation of an internal molten zone. The metal oxide particles in the powder mixture are effectively sized relative to the metal particles to permit direct inductive heating of the compact by radiofrequency from room temperature. Surface melting is prevented by external cooling or by effectively sizing the particles in the powder mixture.

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

PubMed

Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

2015-11-16

Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photoelectrochemical activity in all-oxide heterojunction devices based on correlated "metallic" oxides.

PubMed

Apgar, Brent A; Lee, Sungki; Schroeder, Lauren E; Martin, Lane W

2013-11-20

n-n Schottky, n-n ohmic, and p-n Schottky heterojunctions based on TiO2 /correlated "metallic" oxide couples exhibit strong solar-light absorption driven by the unique electronic structure of the "metallic" oxides. Photovoltaic and photocatalytic responses are driven by hot electron injection from the "metallic" oxide into the TiO2 , enabling new modalities of operation for energy systems. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 new...

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 new...

Assembling metal oxide nanocrystals into dense, hollow, porous nanoparticles for lithium-ion and lithium-oxygen battery application.

PubMed

Ming, Jun; Wu, Yingqiang; Park, Jin-Bum; Lee, Joong Kee; Zhao, Fengyu; Sun, Yang-Kook

2013-11-07

New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP nanoparticles preserve the intriguing properties of nanocrystals and possess desirable surface area and pore volume that enhance the active surface, which ultimately benefits applications such as lithium-ion batteries. The DHP Co3O4 nanoparticles demonstrated an enhanced capacity of 1168 mA h g(-1) at 100 mA g(-1)vs. 590 mA h g(-1) of powders and stable cycling performance greater than 250 cycles when used as an anode material. Most importantly, the electrochemical performance of DHP Co3O4 nanoparticles in a lithium-O2 battery was also investigated for the first time. A low charge potential of ∼4.0 V, a high discharge voltage near 2.74 V and a long cycle ability greater than 100 cycles at a delivered capacity of 2000 mA h g(-1) (current density, 200 mA g(-1)) were observed. The performances were considerably improved compared to recent results of mesoporous Co3O4, Co3O4 nanoparticles and a composite of Co3O4/RGO and Co3O4/Pd. Therefore, it would be promising to investigate such properties of DHP nanoparticles or other hollow metal (oxide) particles for the popular lithium-air battery.

Facile Synthesis of Self-Assembled Flower-Like Mesoporous Zinc Oxide Nanoflakes for Energy Applications

NASA Astrophysics Data System (ADS)

Saranya, P. E.; Selladurai, S.

Flower-shaped self-assembled zinc oxide (ZnO) nanoflakes were successfully synthesized via a temperature-controlled hydrothermal method. The crystallinity and phase formation of the compound were determined from powder X-ray diffraction (PXRD) result. Surface morphology investigations reveal the self-assembled ZnO nanoflakes to form a spherical flower-like structure. In addition, the particle size was determined from high-resolution transmission electron microscope measurement as 18nm which is in accord with XRD and UV results. X-ray photo electron spectroscopy studies reveal the chemical composition and oxidation state of the ZnO nanoparticle. The specific surface area was calculated, and mesoporous nature was confirmed using Brunauer-Emmett-Teller analysis. Results support the superior interaction between the electrode and electrolyte ions through surface pores. Capacitive performance of the ZnO electrode material was determined using cyclic voltammetry and galvanostatic charge/discharge studies, and a maximum specific capacitance of 322F/g was obtained at 5mV/sec. Electrochemical impedance spectrum reveals the materials fast charge transfer kinetics.

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.

Application of a mixed metal oxide catalyst to a metallic substrate

NASA Technical Reports Server (NTRS)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

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.

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

DOE PAGES

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.; ...

2017-08-08

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 in this paper, 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 (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » 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 WO x–NbO x 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.« less

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.

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 in this paper, 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 (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » 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 WO x–NbO x 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.« less

Oxidation stress evolution and relaxation of oxide film/metal substrate system

NASA Astrophysics Data System (ADS)

Dong, Xuelin; Feng, Xue; Hwang, Keh-Chih

2012-07-01

Stresses in the oxide film/metal substrate system are crucial to the reliability of the system at high temperature. Two models for predicting the stress evolution during isothermal oxidation are proposed. The deformation of the system is depicted by the curvature for single surface oxidation. The creep strain of the oxide and metal, and the lateral growth strain of the oxide are considered. The proposed models are compared with the experimental results in literature, which demonstrates that the elastic model only considering for elastic strain gives an overestimated stress in magnitude, but the creep model is consistent with the experimental data and captures the stress relaxation phenomenon during oxidation. The effects of the parameter for the lateral growth strain rate are also analyzed.

Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuila, Debasish; Ilias, Shamsuddin

2013-02-13

In steam reforming reactions (SRRs) of alkanes and alcohols to produce H 2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N 2 adsorption, and Transmission electronmore » microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m 2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean Transportation Fuels�

Solid state microwave synthesis of highly crystalline ordered mesoporous hausmannite Mn 3 O 4 films

DOE PAGES

Xia, Yanfeng; Qiang, Zhe; Lee, Byeongdu; ...

2017-06-23

Microwave calcination of ordered micelle templated manganese carbonate films leads to highly crystalline, ordered mesoporous manganese oxide, while similar temperatures in a furnace lead to disordered, amorphous manganese oxide.

Mesoporous Aluminosilicates as a Host and Reactor for Preparation of Ordered Metal Nanowires

NASA Astrophysics Data System (ADS)

Eliseev, A. A.; Napolskii, K. S.; Kolesnik, I. V.; Kolenko, Yu. V.; Lukashin, A. V.; Gornert, P.; Tretyakov, Yu. D.

The creation of functional nanomaterials with the controlled properties is emerging as a new area of great technological and scientific interest, in particular, it is a key technology for developing novel high-density data storage devices. Today, no other technology can compete with magnetic carriers in information storage density and access rate. However, usually very small (10-1000 nm3) magnetic nanoparticles shows para- or superparamagnetic properties, with very low blocking temperatures and no coercitivity at normal conditions. One possible solution of this problem is preparation of highly anisotropic nanostructures. From the other hand, the use of purely nanocrystalline systems is limited because of their low stability and tendency to form aggregates. These problems could be solved by encapsulation of nanoparticles to a chemically inert matrix. One of the promising matrices for preparation of highly anisotropic magnetic nanoparticles is mesoporous silica or mesoporous aluminosilicates. Mesoporous silica is an amorphous SiO2 with a highly ordered uniform pore structure (the pore diameter can be controllably varied from 2 to 50 nm). This pore system is a perfect reactor for synthesis of nanocomposites due to the limitation of reaction zone by the pore walls. One could expect that size and shape of nanoparticles incorporated into mesoporous silica to be consistent with the dimensions of the porous framework.

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.

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...21 l 7 3 ..... l DTIC NSPECT I" ’I cCPY INSECE( METAL OXIDE SOLUBILITY AND MOLTEN SALT CORROSION I. INTRODUCTION Molten ...discussed in terms of its importance to the understanding of molten salt corrosion . II. PROTECTIVE COATINGS Since most structural metals and alloys are

SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

PubMed

Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

2014-09-01

The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid fabrication of mesoporous TiO2 thin films by pulsed fibre laser for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Hadi, Aseel; Alhabradi, Mansour; Chen, Qian; Liu, Hong; Guo, Wei; Curioni, Michele; Cernik, Robert; Liu, Zhu

2018-01-01

In this paper we demonstrate for the first time that a fibre laser with a wavelength of 1070 nm and a pulse width of milliseconds can be applied to generate mesoporous nanocrystalline (nc) TiO2 thin films on ITO coated glass in ambient atmosphere, by complete vaporisation of organic binder and inter-connection of TiO2 nanoparticles, without thermally damaging the ITO layer and the glass substrate. The fabrication of the mesoporous TiO2 thin films was achieved by stationary laser beam irradiation of 1 min. The dye sensitized solar cell (DSSC) with the laser-sintered TiO2 photoanode reached higher power conversion efficiency (PCE) of 3.20% for the TiO2 film thickness of 6 μm compared with 2.99% for the furnace-sintered. Electrochemical impedance spectroscopy studies revealed that the laser sintering under the optimised condition effectively decreased charge transfer resistance and increased electron lifetime of the TiO2 thin films. The use of the fibre laser with over 40% wall-plug efficiency offers an economically-feasible, industrial viable solution to the major challenge of rapid fabrication of large scale, mass production of mesoporous metal oxide thin film based solar energy systems, potentially for perovskite and monolithic tandem solar cells, in the future.

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.

Multiscale Interfacial Strategy to Engineer Mixed Metal-Oxide Anodes toward Enhanced Cycling Efficiency.

PubMed

Ma, Yue; Tai, Cheuk-Wai; Li, Shaowen; Edström, Kristina; Wei, Bingqing

2018-06-13

Interconnected macro/mesoporous structures of mixed metal oxide (MMO) are developed on nickel foam as freestanding anodes for Li-ion batteries. The sustainable production is realized via a wet chemical etching process with bio-friendly chemicals. By means of divalent iron doping during an in situ recrystallization process, the as-developed MMO anodes exhibit enhanced levels of cycling efficiency. Furthermore, this atomic-scale modification coherently synergizes with the encapsulation layer across a micrometer scale. During this step, we develop a quasi-gel-state tri-copolymer, i.e., F127-resorcinol-melamine, as the N-doped carbon source to regulate the interfacial chemistry of the MMO electrodes. Electrochemical tests of the modified Fe x Ni 1- x O@NC-NiF anode in both half-cell and full-cell configurations unravel the favorable suppression of the irreversible capacity loss and satisfactory cyclability at the high rates. This study highlights a proof-of-concept modification strategy across multiple scales to govern the interfacial chemical process of the electrodes toward better reversibility.

Facile synthesis and application of a carbon foam with large mesopores.

PubMed

Fu, Liling; Qi, Genggeng; Sahore, Ritu; Sougrat, Rachid; DiSalvo, Francis J; Giannelis, Emmanuel P

2013-11-28

By combining elements of hard- and soft-templating, a facile synthesis method for carbon foams with large mesopores has been demonstrated. A commercial Pluronic surfactant was used as the structure-directing agent as well as the carbon precursor. No micelle swelling agent or post treatment is necessary to enlarge mesopores. As such this method requires fewer synthesis steps and is highly scalable. The as-synthesized meso-carbons showed potential applications in the fields of carbon oxide capture and lithium-sulfur batteries.

A universal cooperative assembly-directed method for coating of mesoporous TiO2 nanoshells with enhanced lithium storage properties

PubMed Central

Guan, Bu Yuan; Yu, Le; Li, Ju; Lou, Xiong Wen (David)

2016-01-01

TiO2 is exceptionally useful, but it remains a great challenge to develop a universal method to coat TiO2 nanoshells on different functional materials. We report a one-pot, low-temperature, and facile method that can rapidly form mesoporous TiO2 shells on various inorganic, organic, and inorganic-organic composite materials, including silica-based, metal, metal oxide, organic polymer, carbon-based, and metal-organic framework nanomaterials via a cooperative assembly-directed strategy. In constructing hollow, core-shell, and yolk-shell geometries, both amorphous and crystalline TiO2 nanoshells are demonstrated with excellent control. When used as electrode materials for lithium ion batteries, these crystalline TiO2 nanoshells composed of very small nanocrystals exhibit remarkably long-term cycling stability over 1000 cycles. The electrochemical properties demonstrate that these TiO2 nanoshells are promising anode materials. PMID:26973879

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

Electrochromic device containing metal oxide nanoparticles and ultraviolet blocking material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia, Guillermo; Koo, Bonil; Gregoratto, Ivano

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant. The electrochromic device also includes nanoparticles containing one or more transparent conducting oxide (TCO), a solid state electrolyte, a counter electrode, and at least one protective layer to prevent degradation of the one or more nanostructured transition metal oxide bronze. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) and visible radiation as a function of an applied voltage to the device.

Multitasking mesoporous nanomaterials for biorefinery applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kandel, Kapil

2013-01-01

Mesoporous silica nanoparticles (MSNs) have attracted great interest for last two decades due to their unique and advantageous structural properties, such as high surface area, pore volume, stable mesostructure, tunable pore size and controllable particle morphology. The robust silica framework provides sites for organic modifications, making MSNs ideal platforms for adsorbents and supported organocatalysts. In addition, the pores of MSNs provide cavities/ channels for incorporation of metal and metal oxide nanoparticle catalysts. These supported metal nanoparticle catalysts benefit from confined local environments to enhance their activity and selectivity for various reactions. Biomass is considered as a sustainable feedstock with potentialmore » to replace diminishing fossil fuels for the production of biofuels. Among several strategies, one of the promising methods of biofuel production from biomass is to reduce the oxygen content of the feedstock in order to improve the energy density. This can be achieved by creating C-C bonds between biomass derived intermediates to increase the molecular weight of the final hydrocarbon molecules. In this context, pore size and organic functionality of MSNs are varied to obtain the ideal catalyst for a C-C bond forming reaction: the aldol condensation. The mechanistic aspects of this reaction in supported heterogeneous catalysts are explored. The modification of supported organocatalyst and the effect of solvent on the reaction are rationalized. The significance of two functional surfaces of MSNs is exploited by enzyme immobilization on the external surface and organo catalyst functionalization on the internal surface. Using this bifunctional catalyst, the tandem conversion of small chain alcohols into longer chain hydrocarbon molecules is demonstrated. The ability to incorporate metal and metal oxide nanoparticles in the pores and subsequent functionalization led to develop organic modified magnetic MSNs (OM-MSNs) for

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.

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.

Conductive metal oxide film and method of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Windisch, C.F. Jr.; Exarhos, G.J.

1999-11-23

The present invention is a method for reducing a dopant in a film of a metal oxide wherein the dopant is reduced and the first metal oxide is substantially not reduced. The method of the present invention relies upon exposing the film to reducing conditions for a predetermined time and reducing a valence of the metal from a positive valence to a zero valence and maintaining atoms with a zero valence in an atomic configuration within the lattice structure of the metal oxide. According to the present invention, exposure to reducing conditions may be achieved electrochemically or achieved in anmore » elevated temperature gas phase.« less

Conductive metal oxide film and method of making

DOEpatents

Windisch, Jr., Charles F.; Exarhos, Gregory J.

1999-01-01

The present invention is a method for reducing a dopant in a film of a metal oxide wherein the dopant is reduced and the first metal oxide is substantially not reduced. The method of the present invention relies upon exposing the film to reducing conditions for a predetermined time and reducing a valence of the metal from a positive valence to a zero valence and maintaining atoms with a zero valence in an atomic configuration within the lattice structure of the metal oxide. According to the present invention, exposure to reducing conditions may be achieved electrochemically or achieved in an elevated temperature gas phase.

Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

DOEpatents

Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

2010-04-27

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

Mesoporous silica-based bioactive glasses for antibiotic-free antibacterial applications.

PubMed

Kaya, Seray; Cresswell, Mark; Boccaccini, Aldo R

2018-02-01

Bioactive glasses (BGs) are being used in several biomedical applications, one of them being as antibacterial materials. BGs can be produced via melt-quenching technique or sol-gel method. Bactericidal silver-doped sol-gel derived mesoporous silica-based bioactive glasses were reported for the first time in 2000, having the composition 76SiO 2 -19CaO-2P 2 O 5 -3Ag 2 O (wt%) and a mean pore diameter of 28nm. This review paper discusses studies carried out exploring the potential antibacterial applications of drug-free mesoporous silica-based BGs. Bioactive glasses doped with metallic elements such as silver, copper, zinc, cerium and gallium are the point of interest of this review, in which SiO 2 , SiO 2 -CaO and SiO 2 -CaO-P 2 O 5 systems are included as the parent glass compositions. Key findings are that silica-based mesoporous BGs offer a potential alternative to the systemic delivery of antibiotics for prevention against infections. The composition dependent dissolution rate and the concentration of the doped elements affect the antibacterial efficacy of BGs. A balance between antibacterial activity and biocompatibility is required, since a high dose of metallic ion addition can cause cytotoxicity. Typical applications of mesoporous BGs doped with antibacterial ions include bone tissue regeneration, multifunctional ceramic coatings for orthopedic devices and orbital implants, scaffolds with enhanced angiogenesis potential, osteostimulation and antibacterial properties for the treatment of large bone defects as well as in wound healing. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

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.

Method of producing solution-derived metal oxide thin films

DOEpatents

Boyle, Timothy J.; Ingersoll, David

2000-01-01

A method of preparing metal oxide thin films by a solution method. A .beta.-metal .beta.-diketonate or carboxylate compound, where the metal is selected from groups 8, 9, 10, 11, and 12 of the Periodic Table, is solubilized in a strong Lewis base to form a homogeneous solution. This precursor solution forms within minutes and can be deposited on a substrate in a single layer or a multiple layers to form a metal oxide thin film. The substrate with the deposited thin film is heated to change the film from an amorphous phase to a ceramic metal oxide and cooled.

Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

DOEpatents

Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

2017-02-07

A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons

PubMed Central

Takahashi, Masaki; Koizumi, Hiromu; Chun, Wang-Jae; Kori, Makoto; Imaoka, Takane; Yamamoto, Kimihisa

2017-01-01

The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time. PMID:28782020

A new nano-sorbent for fast and efficient removal of heavy metals from aqueous solutions based on modification of magnetic mesoporous silica nanospheres

NASA Astrophysics Data System (ADS)

Vojoudi, Hossein; Badiei, Alireza; Bahar, Shahriyar; Mohammadi Ziarani, Ghodsi; Faridbod, Farnoush; Ganjali, Mohammad Reza

2017-11-01

In the present study, a new and efficient nanosorbent for the fast removal of heavy metal ions was prepared. The proposed nanosorbent was fabricated using Fe3O4 magnetic core shelled by mesoporous silica, and cetyltrimethylammonium bromide (CTAB) as surfactant template through a sol-gel process. The magnetic nanomaterial was further modified with bis(3-triethoxysilylpropyl)tetrasulfide (MSCMNPs-S4). The final nanosphers were characterized by FT-IR, XRD, TGA, BET, SEM, TEM, DLS, VSM, EDX, and UV-Vis. The potential of the resultant mesoporous magnetite nanomaterials was investigated as a convenient and effective adsorbent for the removal of toxic heavy metal ions from aqueous solutions in a batch system. The effect of essential parameters on the removal efficiency including initial pH of sample solution, adsorbent amount, metal ion concentration, contact time and type and quantity of the eluent on the adsorption characteristics of the MSCMNPs-S4 were studied. Under the optimized conditions, the proposed nanosorbent exhibited high adsorption capacity of 303.03, 256.41 and 270.27 mg g-1 and maximum removal percentages of 98.8%, 96.4%, 95.7% for Hg(II), Pd(II) and Pb(II) ions, respectively. The mechanism of the adsorbtion was found to be in good agreement with the Langmuir isotherm model. Furthermore, the reusability investigation indicated that the MSCMNPs-S4 could be used frequently at least for five cycles without any significant loss in its performance.

Periodically Arranged Arrays of Dendritic Pt Nanospheres Using Cage-Type Mesoporous Silica as a Hard Template.

PubMed

Kani, Kenya; Malgras, Victor; Jiang, Bo; Hossain, Md Shahriar A; Alshehri, Saad M; Ahamad, Tansir; Salunkhe, Rahul R; Huang, Zhenguo; Yamauchi, Yusuke

2018-01-04

Dendritic Pt nanospheres of 20 nm diameter are synthesized by using a highly concentrated surfactant assembly within the large-sized cage-type mesopores of mesoporous silica (LP-FDU-12). After diluting the surfactant solution with ethanol, the lower viscosity leads to an improved penetration inside the mesopores. After Pt deposition followed by template removal, the arrangement of the Pt nanospheres is a replication from that of the mesopores in the original LP-FDU-12 template. Although it is well known that ordered LLCs can form on flat substrates, the confined space inside the mesopores hinders surfactant self-organization. Therefore, the Pt nanospheres possess a dendritic porous structure over the entire area. The distortion observed in some nanospheres is attributed to the close proximity existing between neighboring cage-type mesopores. This new type of nanoporous metal with a hierarchical architecture holds potential to enhance substance diffusivity/accessibility for further improvement of catalytic activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of producing adherent metal oxide coatings on metallic surfaces

DOEpatents

Lane, Michael H.; Varrin, Jr., Robert D.

2001-01-01

Provided is a process of producing an adherent synthetic corrosion product (sludge) coating on metallic surfaces. The method involves a chemical reaction between a dry solid powder mixture of at least one reactive metal oxide with orthophosphoric acid to produce a coating in which the particles are bound together and the matrix is adherent to the metallic surface.

Metal Oxide/Graphene Composites for Supercapacitive Electrode Materials.

PubMed

Jeong, Gyoung Hwa; Baek, Seungmin; Lee, Seungyeol; Kim, Sang-Wook

2016-04-05

Graphene composites with metal or metal oxide nanoparticles have been extensively investigated owing to their potential applications in the fields of fuel cells, batteries, sensing, solar cells, and catalysis. Among them, much research has focused on supercapacitor applications and have come close to realization. Composites include monometal oxides of cobalt, nickel, manganese, and iron, as well as their binary and ternary oxides. In addition, their morphological control and hybrid systems of carbon nanotubes have also been investigated. This review presents the current trends in research on metal oxide/graphene composites for supercapacitors. Furthermore, methods are suggested to improve the properties of electrochemical capacitor electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

PubMed Central

Robbins, Spencer W.; Beaucage, Peter A.; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G.; Sethna, James P.; DiSalvo, Francis J.; Gruner, Sol M.; Van Dover, Robert B.; Wiesner, Ulrich

2016-01-01

Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly–directed sol-gel–derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (Tc) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (Jc) of 440 A cm−2 at 100 Oe and 2.5 K. We expect block copolymer self-assembly–directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies. PMID:27152327

Block copolymer self-assembly-directed synthesis of mesoporous gyroidal superconductors.

PubMed

Robbins, Spencer W; Beaucage, Peter A; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G; Sethna, James P; DiSalvo, Francis J; Gruner, Sol M; Van Dover, Robert B; Wiesner, Ulrich

2016-01-01

Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly-directed sol-gel-derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (T c) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (J c) of 440 A cm(-2) at 100 Oe and 2.5 K. We expect block copolymer self-assembly-directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1991-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Removal of Congo Red by magnetic mesoporous titanium dioxide-graphene oxide core-shell microspheres for water purification.

PubMed

Li, Leilei; Li, Xiangjun; Duan, Huimin; Wang, Xiaojiao; Luo, Chuannan

2014-06-14

Magnetic mesoporous titanium dioxide-graphene oxide (Fe3O4@mTiO2@GO) with a large surface area and a good magnetic responsiveness was synthesized by immobilizing a mesoporous titanium dioxide (mTiO2) shell on the surface of magnetic Fe3O4 nanoparticles prior to binding with graphene oxide (GO). It showed a tunable pore structure and surface properties, and was mechanically strong. The characteristic results of a Fourier transform infrared spectrometer (FTIR), a scanning electron microscope (SEM), a vibrating sample magnetometer (VSM) and X-ray diffraction (XRD) indicated that Fe3O4@mTiO2@GO has been prepared. Fe3O4@mTiO2@GO was used as an adsorbent for the removal of Congo Red (CR) from simulated wastewater with a fast solid-liquid separation in the presence of an external magnetic field. Batch adsorption experiments were performed to evaluate the adsorption conditions and reusability. The results showed that the maximum adsorption capacity was 89.95 mg g(-1), which is much higher than the previously reported values of other absorbent materials. Moreover, the Fe3O4@mTiO2@GO could be repeatedly used via simple treatment without any obvious structure and performance degradation. The adsorption kinetic data were best described by a pseudo-second-order model and the equilibrium adsorptions were well-described by the Freundlich isotherm model. The Fe3O4@mTiO2@GO may be suitable materials for use in CR pollution cleanup if synthesized on a large scale and at a low price in the near future.

Ultrahigh–current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF 3 framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hansen; Lin, Dingchang; Liu, Yayuan

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/Al 4Li 9-LiF nanocomposite (LAFN) through an “overlithiation” process of a mesoporous AlF 3 framework, which can simultaneously mitigate the abovementioned problems. Reaction-produced Al 4Li 9-LiF nanoparticles serve as the ideal skeleton for Li metal infusion, helping to achieve a near-zeromore » 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. 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

Ultrahigh–current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF 3 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/Al 4Li 9-LiF nanocomposite (LAFN) through an “overlithiation” process of a mesoporous AlF 3 framework, which can simultaneously mitigate the abovementioned problems. Reaction-produced Al 4Li 9-LiF nanoparticles serve as the ideal skeleton for Li metal infusion, helping to achieve a near-zeromore » 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. 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

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.

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.

40 CFR 721.5315 - Nickel, cobalt 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 Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for the...

40 CFR 721.5315 - Nickel, cobalt 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 Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for the...

40 CFR 721.5315 - Nickel, cobalt 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 Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for the...

40 CFR 721.5315 - Nickel, cobalt 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 Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for the...

Mesoporous zirconium titanium oxides. Part 2: Synthesis, porosity, and adsorption properties of beads.

PubMed

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

2008-11-04

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 m2/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.

A facile one-pot self-assembly approach to incorporate SnOx nanoparticles in ordered mesoporous carbon with soft templating for fuel cells

NASA Astrophysics Data System (ADS)

Huang, Yingqiang; Zhai, Zhicheng; Luo, Zhigang; Liu, Yingju; Liang, Zhurong; Fang, Yueping

2014-04-01

Unique SnOx (x = 1,2)/ordered mesoporous carbon nanocomposites (denoted as SnOx/OMC) are firstly synthesized through a ‘one-pot’ synthesis together with the soft template self-assembly approach. The obtained SnOx/OMC nanocomposites with various SnOx contents exhibit uniform pore sizes between 3.9 and 4.2 nm, high specific surface areas between 497 and 595 m2 g-1, and high pore volumes between 0.39 and 0.48 cm3 g-1. With loading of Pt, Pt-SnOx/OMC with relatively low SnOx content exhibits superior electrocatalytic performance, long-term durability, and resistance to CO poisoning for methanol oxidation, as compared to Pt/OMC, PtRu/C and Pt-SnOx/C, which may be attributed not only to the synergetic effect of embedded SnOx, but also to the highly ordered mesostructure with high specific surface areas and large pore volumes affording plenty of surface area for support of Pt nanoparticles. This work supplies an efficient way to synthesize novel ordered mesoporous carbon self-supported metallic oxide as catalyst support and its further potential application to reduce the cost of catalysts in direct methanol fuel cells.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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