Xenon capture on silver-loaded zeolites: characterization of very strong adsorption sites

International Nuclear Information System (INIS)

Daniel, Cecile; Elbaraoui, Adnane; Aguado, Sonia; Schuurman, Yves; Farrusseng, David; Springuel-Huet, Marie-Anne; Nossov, Andrei; Fontaine, Jean-Pierre; Topin, Sylvain; Taffary, Thomas; Deliere, Ludovic

2013-01-01

The number and strength of adsorption sites for Xe in silver-modified zeolites are estimated from isotherm measurements at various temperatures over a broad range of pressure (from 1 ppm to atmospheric pressure). Fully and partially exchanged silver zeolites were synthesized starting from Na-ZSM-5(25), Na-ZSM-5(40), Na-Beta, NaX, and NaY. We have discovered that silver-modified zeolites may present one or two distinct adsorption sites depending on the nature of the material and silver loadings. The strongest adsorption sites are characterized by isosteric heat of adsorption in the order of -40 to -50 kJ.mol -1 . For Pentasil-type zeolites, we observe a linear 2:1 correlation between the total amount of silver and the number of strong sites. The highest concentration of strong sites is found for fully silver exchanged ZSM-5 (5.7 * 10 -4 mol/g), which presents the largest silver content for Pentasil-type zeolite. The equilibrium constant of Ag-ZSM-5 at low pressure is about 50 times larger than that of AgX. Qualitative correlations were established between Xe adsorption isotherms and Xe NMR signals. We show that Xe NMR could be used as a quantitative method for the characterization of the strength and of the number of strong Xe adsorption sites on silver-exchanged zeolites. The numbers of strong adsorption sites responsible for the Xe adsorption at 10-1000 ppm can be determined by the length of the plateau observed at low Xe uptake. In practice, our findings give guidelines for the discovery and optimization of silver-loaded zeolites for the capture of Xe at ppm levels. It appears that the amount of silver is a key parameter. Silver-modified ZSM-5 shows adsorption capacities 2-3 orders of magnitude larger than currently applied adsorbents for atmospheric Xe capture. (authors)

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

NARCIS (Netherlands)

Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Hofmann, Jan P.|info:eu-repo/dai/nl/355351110; De Cremer, Gert; Kubarev, Alexey V.; Rohnke, Marcus; Meirer, Florian; Hofkens, Johan; Roeffaers, Maarten B. J.; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2015-01-01

Optimizing the number, distribution, and accessibility of Bronsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by

The nature of cationic adsorption sites in alkaline zeolites-single, dual and multiple cation sites

Czech Academy of Sciences Publication Activity Database

Nachtigall, P.; Delgado, M. R.; Nachtigallová, Dana; Arean, C. O.

2012-01-01

Roč. 14, č. 5 (2012), s. 1552-1569 ISSN 1463-9076 R&D Projects: GA ČR GA203/09/0143 Institutional research plan: CEZ:AV0Z40550506 Keywords : exchanged ZSM-5 zeolites * carbon-monoxide adsorption * low-temperature CO * solid-state NMR * high-silica zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

Science.gov (United States)

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.

Science.gov (United States)

Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

2014-04-16

Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

Performance Evaluations of Ion Exchanged Zeolite Membranes on Alumina Supports

Energy Technology Data Exchange (ETDEWEB)

Bhave, Ramesh R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jubin, Robert Thomas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Spencer, Barry B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nair, Sankar [Georgia Inst. of Technology, Atlanta, GA (United States)

2017-08-27

This report describes the synthesis and evaluation of molecular sieve zeolite membranes to separate and concentrate tritiated water (HTO) from dilute HTO-bearing aqueous streams. In the first phase of this effort, several monovalent and divalent cation-exchanged silico alumino phosphate (SAPO-34) molecular sieve zeolite membranes were synthesized on disk supports and characterized with gas and vapor permeation measurements. In the second phase, Linde Type A (LTA) zeolite membranes were synthesized in disk and tubular supports. The pervaporation process performance was evaluated for the separation and concentration of tritiated water.

Halloysite nanotube-based electrospun ceramic nanofibre mat: a novel support for zeolite membranes

Science.gov (United States)

Chen, Zhuwen; Zeng, Jiaying; Lv, Dong; Gao, Jinqiang; Zhang, Jian; Bai, Shan; Li, Ruili; Hong, Mei; Wu, Jingshen

2016-12-01

Some key parameters of supports such as porosity, pore shape and size are of great importance for fabrication and performance of zeolite membranes. In this study, we fabricated millimetre-thick, self-standing electrospun ceramic nanofibre mats and employed them as a novel support for zeolite membranes. The nanofibre mats were prepared by electrospinning a halloysite nanotubes/polyvinyl pyrrolidone composite followed by a programmed sintering process. The interwoven nanofibre mats possess up to 80% porosity, narrow pore size distribution, low pore tortuosity and highly interconnected pore structure. Compared with the commercial α-Al2O3 supports prepared by powder compaction and sintering, the halloysite nanotube-based mats (HNMs) show higher flux, better adsorption of zeolite seeds, adhesion of zeolite membranes and lower Al leaching. Four types of zeolite membranes supported on HNMs have been successfully synthesized with either in situ crystallization or a secondary growth method, demonstrating good universality of HNMs for supporting zeolite membranes.

Comparative study of the active sites in zeolites by different probe molecules

Directory of Open Access Journals (Sweden)

ALINE AUROUX

2005-03-01

Full Text Available This review summarizes some of the recently published results concerning the acid sites in the zeolites ZSM-5 and Y studied by temperature-programmed desorption (TPD and adsorption calorimetry using different probe molecules NH3, CO, N2O and n-hexane. For the first time it has been shown that the acid sites in hydrated zeolites are accessible for n-hexane adsorption

Adsorption structure of dimethyl ether on silicalite-1 zeolite determined using single-crystal X-ray diffraction

International Nuclear Information System (INIS)

Fujiyama, Shinjiro; Seino, Shintaro; Kamiya, Natsumi; Nishi, Koji; Yokomori, Yoshinobu

2014-01-01

The most stable sorption site of dimethyl ether on silicalite-1 is the sinusoidal channel. The configuration of guest molecules (linear or bent) plays an important role in determining where the stable sorption site is situated. The adsorption structures of dimethyl ether (DME) on silicalite-1 zeolite (MFI-type) are determined using single-crystal X-ray diffraction. The structure of low-loaded DME-silicalite-1 indicates that all DME molecules are located in the sinusoidal channel, which is the most stable sorption site based on the van der Waals interaction between DME and the framework. The configuration of guest molecules (linear or bent) plays an important role in determining where the stable sorption site is in the pore system of MFI-type zeolites. Bent molecules favor the sinusoidal channel, while linear molecules favor the straight channel. The contribution of DME–DME interactions is considerable in the high-loaded DME-silicalite-1 structure

A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

Directory of Open Access Journals (Sweden)

Maria Michela Dell’Anna

2010-05-01

Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

Crystallization and melting behavior of isotactic polypropylene composites filled by zeolite supported β-nucleator

International Nuclear Information System (INIS)

Jiang, Juan; Li, Gu; Tan, Nanshu; Ding, Qian; Mai, Kancheng

2012-01-01

Highlights: ► The supported calcium pimelate β-zeolite was prepared. ► The β-nucleation of zeolite was enhanced dramatically through reaction. ► High β-phase content iPP composites were obtained by introducing the β-zeolite into iPP. - Abstract: In order to prepare the zeolite filled β-iPP composites, the calcium pimelate as β-nucleator supported on the surface of zeolite (β-zeolite) was prepared by the interaction between calcified zeolite and pimelic acid. The β-nucleation, crystallization behavior and melting characteristic of zeolite, calcified zeolite and β-zeolite filled iPP composites were investigated by differential scanning calorimetry and wide-angle X-ray diffractometer. The results indicated that addition of the zeolite and calcified zeolite as well as β-zeolite increased the crystallization temperature of iPP. The zeolite and calcified zeolite filled iPP composites mainly crystallized in the α-crystal form and the strong β-heterogeneous nucleation of β-zeolite results in the formation of only β-crystal in β-zeolite filled iPP composites. The zeolite filled β-iPP composites with high β-crystal contents (above 0.90) can be easily obtained by adding β-zeolite into iPP matrix.

Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts

Science.gov (United States)

Anis, Shaheen Fatima; Hashaikeh, Raed

2018-02-01

Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50-150 nm range) and micro-zeolite Y (500-800 nm range) were loaded with WO3, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO3 were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO3 loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO3. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO3, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.

Application of zeolite-based catalyst to hydrocracking of coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Sato, T.; Yoshimura, Y.; Hinata, A.; Yoshitomi, S.; Castillo Mares, A.; Nishijima, A. (National Chemical Laboratory for Industry, Tsukuba (Japan))

1990-06-01

Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template

KAUST Repository

Zhu, Jie

2014-02-12

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules. © 2014 American Chemical Society.

Mesoporous zeolite and zeotype single crystals synthesized in fluoride media

DEFF Research Database (Denmark)

Egeblad, Kresten; Kustova, Marina; Klitgaard, Søren Kegnæs

2007-01-01

We report the synthesis and characterization of a series of new mesoporous zeolite and zeotype materials made available by combining new and improved procedures for directly introducing carbon into reaction mixtures with the fluoride route for conventional zeolite synthesis. The mesoporous...... materials were all prepared by hydrothermal crystallization of gels adsorbed on carbon matrices which were subsequently removed by combustion. The procedures presented here resulted in mesoporous zeolite and zeotypes materials with MFI, MEL, BEA, AFI and CHA framework structures. All samples were...... characterized by XRPD, SEM, TEM and N-2 physisorption measurements. For the zeolite materials it A as found that mesoporous MFI and MEL structured single crystals could indeed be crystallized from fluoride media using an improved carbon-templating approach. More importantly, it was found that mesoporous BEA...

Hydroformylation and kinetics of 1-hexene over ruthenium, cobalt and rhodium zerolite catalysts

International Nuclear Information System (INIS)

Wang, C.; Wei, W.

1989-01-01

In this paper, six kinds of catalysts were prepared by cation exchange with rhodium, ruthenium and cobalt chloropentaamino dichoride and zeolites. Effects such as support materials, PPH 3 to metal ratio, reaction temperature, total pressure, H 2 /CO ratio, reaction time and solvents have been investigated in an autoclave. The most favorable results of 1-hexene hydroformylation were obtained in the temperature range 100-150 degrees C at a pressure of 5.0MPa (H 2 /CO=1:1) and the addition of free PPh 3 . The bimetallic catalysts showed high catalytic activing for hydroformylation because of the synergistic effect of bimetallic systems. This paper reports the results of experiments and catalysts characterization by means of IR and XRD spectroscopy

Hydrogen Separation by Natural Zeolite Composite Membranes: Single and Multicomponent Gas Transport.

Science.gov (United States)

Farjoo, Afrooz; Kuznicki, Steve M; Sadrzadeh, Mohtada

2017-10-06

Single and multicomponent gas permeation tests were used to evaluate the performance of metal-supported clinoptilolite membranes. The efficiency of hydrogen separation from lower hydrocarbons (methane, ethane, and ethylene) was studied within the temperature and pressure ranges of 25-600 °C and 110-160 kPa, respectively. The hydrogen separation factor was found to reduce noticeably in the gas mixture compared with single gas experiments at 25 °C. The difference between the single and multicomponent gas results decreased as the temperature increased to higher than 300 °C, which is when the competitive adsorption-diffusion mechanism was replaced by Knudsen diffusion or activated diffusion mechanisms. To evaluate the effect of gas adsorption, the zeolite surface isotherms of each gas in the mixture were obtained from 25 °C to 600 °C. The results indicated negligible adsorption of individual gases at temperatures higher than 300 °C. Increasing the feed pressure resulted in a higher separation efficiency for the individual gases compared with the multicomponent mixture, due to the governing effect of the adsorptive mechanism. This study provides valuable insight into the application of natural zeolites for the separation of hydrogen from a mixture of hydrocarbons.

Rhodium self-powered neutron detector's lifetime for korean standard nuclear power plants

International Nuclear Information System (INIS)

Yoo, Choon Sung; Kim, Byoung Chul; Park, Jong Ho; Fero, Arnold H.; Anderson, S. L.

2005-01-01

A method to estimate the relative sensitivity of a self-powered rhodium detector for an upcoming cycle is developed by combining the rhodium depletion data from a nuclear design with the site measurement data. This method can be used both by nuclear power plant designers and by site staffs of Korean standard nuclear power plants for determining which rhodium detectors should be replaced during overhauls

Templating mesoporous zeolites

DEFF Research Database (Denmark)

Egeblad, Kresten; Christensen, Christina Hviid; Kustova, Marina

2008-01-01

The application of templating methods to produce zeolite materials with hierarchical bi- or trimodal pore size distributions is reviewed with emphasis on mesoporous materials. Hierarchical zeolite materials are categorized into three distinctly different types of materials: hierarchical zeolite...... crystals, nanosized zeolite crystals, and supported zeolite crystals. For the pure zeolite materials in the first two categories, the additional meso- or macroporosity can be classified as being either intracrystalline or intercrystalline, whereas for supported zeolite materials, the additional porosity...... originates almost exclusively from the support material. The methods for introducing mesopores into zeolite materials are discussed and categorized. In general, mesopores can be templated in zeolite materials by use of solid templating, supramolecular templating, or indirect templating...

Hydrogen Separation by Natural Zeolite Composite Membranes: Single and Multicomponent Gas Transport

Directory of Open Access Journals (Sweden)

Afrooz Farjoo

2017-10-01

Full Text Available Single and multicomponent gas permeation tests were used to evaluate the performance of metal-supported clinoptilolite membranes. The efficiency of hydrogen separation from lower hydrocarbons (methane, ethane, and ethylene was studied within the temperature and pressure ranges of 25–600 °C and 110–160 kPa, respectively. The hydrogen separation factor was found to reduce noticeably in the gas mixture compared with single gas experiments at 25 °C. The difference between the single and multicomponent gas results decreased as the temperature increased to higher than 300 °C, which is when the competitive adsorption–diffusion mechanism was replaced by Knudsen diffusion or activated diffusion mechanisms. To evaluate the effect of gas adsorption, the zeolite surface isotherms of each gas in the mixture were obtained from 25 °C to 600 °C. The results indicated negligible adsorption of individual gases at temperatures higher than 300 °C. Increasing the feed pressure resulted in a higher separation efficiency for the individual gases compared with the multicomponent mixture, due to the governing effect of the adsorptive mechanism. This study provides valuable insight into the application of natural zeolites for the separation of hydrogen from a mixture of hydrocarbons.

Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

NARCIS (Netherlands)

Koningsberger, D.C.; Martens, J.H.A.; Prins, R.

1989-01-01

An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

Reactivity of rhodium during co-deposition of rhodium and carbon

International Nuclear Information System (INIS)

Marot, Laurent; Steiner, Roland; De Temmerman, Gregory; Oelhafen, Peter

2009-01-01

The detailed characterizations of rhodium/carbon films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the carbon incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using XPS, reflectivity measurements, XRD and SEM. The incorporation of carbon changes the films' crystallinity and thus producing amorphous films. The reflectivity of the films decreases linearly as the rhodium concentration decreases. It is important to note that no chemical bonding was observed between rhodium and carbon whatever the deposition conditions, even at high deposition temperature. Concerning the reactivity of rhodium films with oxygen, after long term storage in air the rhodium surface is covered with a thin rhodium oxide (few nanometers). However, for these films no variation of the optical reflectivity was observed after long air storage.

Design and fabrication of zeolite macro- and micromembranes

Science.gov (United States)

Chau, Lik Hang Joseph

2001-07-01

The chemical nature of the support surface influences zeolite nucleation, crystal growth and elm adhesion. It had been demonstrated that chemical modification of support surface can significantly alter the zeolite film and has a good potential for large-scale applications for zeolite membrane production. The incorporation of titanium and vanadium metal ions into the structural framework of MFI zeolite imparts the material with catalytic properties. The effects of silica and metal (i.e., Ti and V) content, template concentration and temperature on the zeolite membrane growth and morphology were investigated. Single-gas permeation experiments were conducted for noble gases (He and Ar), inorganic gases (H2, N2, SF6) and hydrocarbons (methane, n-C4, i-C4) to determine the separation performance of these membranes. Using a new fabrication method based on microelectronic fabrication and zeolite thin film technologies, complex microchannel geometry and network (supported zeolite films. The zeolite micropatterns were stable even after repeated thermal cycling between 303 K and 873 K for prolonged periods of time. This work also demonstrates that zeolites (i.e., Sil-1, ZSM-5 and TS-1) can be employed as catalyst, membrane or structural materials in miniature chemical devices. Traditional semiconductor fabrication technology was employed in micromachining the device architecture. Four strategies for the manufacture of zeolite catalytic microreactors were discussed: zeolite powder coating, uniform zeolite film growth, localized zeolite growth, and etching of zeolite-silicon composite film growth inhibitors. Silicalite-1 was also prepared as free-standing membrane for zeolite membrane microseparators.

Rhodium(I) catalysis in olefin photoreactions

International Nuclear Information System (INIS)

Salomon, R.G.; El Sanadi, N.

1975-01-01

The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

Coordination Environment of Copper Sites in Cu-CHA Zeolite Investigated by Electron Paramagnetic Resonance

DEFF Research Database (Denmark)

Godiksen, Anita; Stappen, Frederick N.; Vennestrøm, Peter N. R.

2014-01-01

Cu-CHA combines high activity for the selective catalytic reduction (SCR) reaction with better hydrothermal stability and selectivity compared to other copper-substituted zeolites. At the same time Cu-CHA offers an opportunity for unraveling the coordination environment of the copper centers since...... the zeolite framework is very simple with only one crystallographically independent tetrahedral site (T-site). In this study the results of an X-band electron paramagnetic resonance (EPR) investigation of ion-exchanged Cu-CHA zeolite with a Si/Al ratio of 14 ± 1 is presented. Different dehydration treatments...... of the EPR silent monomeric Cu2+ in copper-substituted zeolites is suggested to be copper species with an approximate trigonal coordination sphere appearing during the dehydration. After complete dehydration at 250 °C the majority of the EPR silent Cu2+ is suggested to exist as Cu2+–OH– coordinated to two...

Rhodium thioacetate complexes

International Nuclear Information System (INIS)

Baranovskij, I.B.; Golubnichaya, M.A.; Mazo, G.Ya.

1976-01-01

Thioacetato-complexes of rhodium(II) were prepared by the reaction of thioacetic acid with rhodium(II) carboxylates. Diamagnetic compounds of the type Rh 2 (CH 3 COS) 4 2A, where A=H 2 O, Py, N 2 H 4 .HCl, Thio, KNCS, DMSO, CH 3 CN, CsCl, or CH 3 COSH, were isolated. Their infrared spectra were recorded, and the principal vibrational wavenumbers assigned. The X-ray electron spectra confirm that rhodium is divalent. The thioacetato-complexes are dimeric, with a metal-metal bond. [Rh(NH 3 ) 5 (CH 3 COS)]I 2 was prepared, and its properties studied. The significant decrease in the strength of the bonds formed by the axial ligands with rhodium is due to the strong trans-influence of the covalent rhodium-rhodium sigma-bond

Synthesis and characterization of alumina application in support of zeolite membrane

International Nuclear Information System (INIS)

Barbosa, A.S.; Rodrigues, M.G.F.

2012-01-01

Much interest has been aroused in process applications using zeolite membrane. The physicochemical properties of the support have a strong effect on the quality of zeolite membrane. This work is to synthesize and characterize alumina for use as a support for zeolite membrane. In this work was synthesized α-alumina: 40% alumina, 0.2% for PABA, 0.5% oleic acid and 59.3% ethyl alcohol. The mixture was ground in ball mill and placed in an oven for 24 hours at 60 °C, allowed to stand for 24h. The pressing was performed with 4 tons. The pressed material was subjected to sintering at 1400 °C/hour. The samples were characterized by EDX, XRD and SEM. The results for the media by XRD showed that they are crystalline and pure. By EDX was observed that the supports consist essentially of alumina. (author)

Catalytic Ozonation of Toluene Using Chilean Natural Zeolite: The Key Role of Brønsted and Lewis Acid Sites

Directory of Open Access Journals (Sweden)

Serguei Alejandro-Martín

2018-05-01

Full Text Available The influence of surface physical-chemical characteristics of Chilean natural zeolite on the catalytic ozonation of toluene is presented in this article. Surface characteristics of natural zeolite were modified by acid treatment with hydrochloric acid and ion-exchange with ammonium sulphate. Prior to catalytic ozonation assays, natural and chemically modified zeolite samples were thermally treated at 623 and 823 K in order to enhance Brønsted and Lewis acid sites formation, respectively. Natural and modified zeolite samples were characterised by N2 adsorption at 77 K, elemental analysis, X-ray fluorescence, and Fourier transform infrared (FTIR spectroscopy, using pyridine as a probe molecule. The highest values of the reaction rate of toluene oxidation were observed when NH4Z1 and 2NH4Z1 zeolite samples were used. Those samples registered the highest density values of Lewis acid sites compared to other samples used here. Results indicate that the presence of strong Lewis acid sites at the 2NH4Z1 zeolite surface causes an increase in the reaction rate of toluene oxidation, confirming the role of Lewis acid sites during the catalytic ozonation of toluene at room temperature. Lewis acid sites decompose gaseous ozone into atomic oxygen, which reacts with the adsorbed toluene at Brønsted acid sites. On the other hand, no significant contribution of Brønsted acid sites on the reaction rate was registered when NH4Z1 and 2NH4Z1 zeolite samples were used.

Physicochemical impact of zeolites as the support for photocatalytic hydrogen production using solar-activated TiO2-based nanoparticles

International Nuclear Information System (INIS)

Taheri Najafabadi, Amin; Taghipour, Fariborz

2014-01-01

Highlights: • Zeolite chemical properties are crucial to photocatalytic hydrogen production. • Basic zeolite, TiO 2 , heteropolyacid and cobalt together are active under visible light. • TiO 2 impregnation on zeolite causes band gap widening and band edges’ anodic shift. • Heteropolyacid enhances the visible light activity of the photocatalyst. • Zeolite’s basicity can overshadow the anodic shift, advancing hydrogen evolution. - Abstract: Silico-aluminates (zeolites) have been recently utilized promisingly as the support for photocatalytic hydrogen production using solar-activated TiO 2 -based nanoparticles. Aside from conventional advantages offered by the supports in photocatalysis, we demonstrate the unique physicochemical impact of zeolites on photocatalytic hydrogen production. Beside zeolites, our synthesized materials comprise titanium dioxide (TiO 2 ) as the semiconductor, cobalt ions as the hydrogen evolution sites, and heteropolyacids (HPAs) as the multifunctional solid acids with significant excitability under visible light. Four classes of zeolites (Na-Y, Na-mordenite, H-Y, and H-beta) with different Si/Al ratios and sodium contents were evaluated. Among the studied photocatalysts, Na-Y and Na-mordenite containing 10 wt% titania emerged as the potential candidates for the hydrogen evolution reaction, with corresponding rates of 250.8 and 187.2 μmol/g h, in comparison to 84.2 μmol/g h for Degussa P25; while these values for H-Y and H-beta were 96.8 and 100.1 μmol/g h, respectively. The higher photocatalytic activity of the first two classes is attributed to the basicity of the zeolite matrix, which is possibly due to the pH dependency of the TiO 2 band edges. The results indicate the importance of controlling the chemical properties of the zeolite as a photocatalyst support through the selection of suitable types. Furthermore, our analyses show that the precise pore size distribution of the zeolite framework rules over accommodating the

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support

DNA Mismatch Binding and Antiproliferative Activity of Rhodium Metalloinsertors

Science.gov (United States)

Ernst, Russell J.; Song, Hang; Barton, Jacqueline K.

2009-01-01

Deficiencies in mismatch repair (MMR) are associated with carcinogenesis. Rhodium metalloinsertors bind to DNA base mismatches with high specificity and inhibit cellular proliferation preferentially in MMR-deficient cells versus MMR-proficient cells. A family of chrysenequinone diimine complexes of rhodium with varying ancillary ligands that serve as DNA metalloinsertors has been synthesized, and both DNA mismatch binding affinities and antiproliferative activities against the human colorectal carcinoma cell lines HCT116N and HCT116O, an isogenic model system for MMR deficiency, have been determined. DNA photocleavage experiments reveal that all complexes bind to the mismatch sites with high specificities; DNA binding affinities to oligonucleotides containing single base CA and CC mismatches, obtained through photocleavage titration or competition, vary from 104 to 108 M−1 for the series of complexes. Significantly, binding affinities are found to be inversely related to ancillary ligand size and directly related to differential inhibition of the HCT116 cell lines. The observed trend in binding affinity is consistent with the metalloinsertion mode where the complex binds from the minor groove with ejection of mismatched base pairs. The correlation between binding affinity and targeting of the MMR-deficient cell line suggests that rhodium metalloinsertors exert their selective biological effects on MMR-deficient cells through mismatch binding in vivo. PMID:19175313

Direct activation of microcrystalline zeolites

NARCIS (Netherlands)

Ortiz-Iniesta, Maria Jesus; Heeres, Hero Jan; Melian-Cabrera, Ignacio

2013-01-01

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Bronsted sites directly; thus applying merely a single thermal

Szilard-Chalmers cation recoil studies in zeolites X and Y. Pt. 3. Recoils from locked to open sites

Energy Technology Data Exchange (ETDEWEB)

Lai, P P; Rees, L V.C. [Imperial Coll. of Science and Technology, London (UK)

1976-01-01

The Szilard-Chalmers recoil of the cations Rb/sup +/, Cs/sup +/, Ba/sup 2 +/, La/sup 3 +/, Co/sup 2 +/, Zn/sup 2 +/, Cu/sup 2 +/ and Na/sup +/ from the sodalite cage and hexagonal prism sites into the supercage sites of zeolites X and Y has been studied. This study is complementary to that described in Lai et al, JCS Faraday I; 72:181 (1976). It has been found that these cations recoil from the sodalite cage sites into the supercage sites with a probability of approximately 90% whereas the corresponding probability for these cations in the hexagonal prism sites (site I) is between 40 and 50% depending on the cation. It is thus possible to determine the preferences shown by these cations for these 'locked-in' sites as a function of temperature of calcination, Tsub(c), concentration and type of other cations contained in these sites. In these studies the cations present in the supercage sites before irradiation were usually NH/sub 4//sup +/ but Ba/sup 2 +/, Ca/sup 2 +/ and Na/sup +/ have also been used. When Tsub(c) > 400/sup 0/C, Rb/sup +/ and Cs/sup +/ began to populate site I. These ions populated this site in zeolite X at lower calcination temperatures than required for zeolite Y. When Tsub(c) was increased from 110 to 220/sup 0/C the occupancy of site I by Ba/sup 2 +/ was greatly enhanced and when Tsub(c) > 440/sup 0/C Ba/sup 2 +/ ions now occupied this site in preference to all other 'locked-in' sites. Barium exhibited a higher affinity for site I in zeolite X than in zeolite Y when Tsub(c) = 110/sup 0/C. If dehydrated La-Y was assumed to have 5 La/sup 3 +/ ions per u.c. in site I, the hydration of this material did not change the concentration of La/sup 3 +/ in site I. Co/sup 2 +/, Zn/sup 2 +/ and Cu/sup 2 +/ ions all exhibited similar affinities for the 'locked-in' sites of zeolites X and Y.

First-principles study of hydrogen diffusion in transition metal Rhodium

International Nuclear Information System (INIS)

Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

2015-01-01

In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

Enhanced photocatalytic activity of supported TiO{sub 2} by selective surface modification of zeolite Y

Energy Technology Data Exchange (ETDEWEB)

Guesh, Kiros [Chemistry-Department, Addis Ababa University, P.O. Box 1176, Addis Ababa (Ethiopia); Mizan-Tepi University, P.O. Box 260, Mizan-Teferi (Ethiopia); Márquez-Álvarez, Carlos [Instituto de Catálisis y Petroleoquímica, CSIC, c/Marie Curie 2, 28049 Madrid (Spain); Chebude, Yonas [Chemistry-Department, Addis Ababa University, P.O. Box 1176, Addis Ababa (Ethiopia); Díaz, Isabel, E-mail: idiaz@icp.csic.es [Chemistry-Department, Addis Ababa University, P.O. Box 1176, Addis Ababa (Ethiopia); Instituto de Catálisis y Petroleoquímica, CSIC, c/Marie Curie 2, 28049 Madrid (Spain)

2016-08-15

Highlights: • XPS analysis confirmed that 50% of the Al was removed from the surface of zeolite Y. • Loaded TiO{sub 2} on the treated zeolites showed 12 times higher TORm than the parent zeolite. • Supported TiO{sub 2} showed very low leaching of TiO{sub 2} nanoparticles than non supported. - Abstract: Zeolite Y was treated using ammonium acetate and ammonium fluoride sequentially. As a consequence the aluminum from the surface was selectively removed. Then, loading with TiO{sub 2} (20 wt%) led to a final photocatalyst. The samples were characterized by X-ray diffraction (XRD), elemental analysis (ICP-OES), N{sub 2} adsorption, diffuse reflectance UV–vis spectroscopy (DRS), photoluminescence spectroscopy (PL), and X-ray photoelectron spectroscopy (XPS). It was found that 50% of the Al atoms were removed from the surface of the zeolite without affecting the framework structure. The TiO{sub 2}/treated zeolite sample yielded 92% photocatalytic degradation of 10 ppm methyl orange (MO), a model pollutant, while the TiO{sub 2}/parent zeolite converted only 7.6%. The mass normalized turnover rate (TOR{sub m}) of the treated zeolite loaded with TiO{sub 2} was about 12 times higher than that of the parent zeolite loaded with the same amount of TiO{sub 2} precursor. This higher photocatalytic activity of the TiO{sub 2} supported on treated zeolite can be attributed to a more efficient interaction of the TiO{sub 2} with the zeolite leading to higher adsorption capacity. Reusability of the photocatalysts was assessed by performing three consecutive reaction cycles that showed no significant loss of photocatalytic activity.

Catalytic Pyrolysis of Chilean Oak: Influence of Brønsted Acid Sites of Chilean Natural Zeolite

Directory of Open Access Journals (Sweden)

Serguei Alejandro Martín

2017-11-01

Full Text Available This paper proposes the Chilean natural zeolite as catalyst on bio-oil upgrade processes. The aim of this study was to analyze chemical composition of bio-oil samples obtained from catalytic pyrolysis of Chilean native oak in order to increase bio-oil stability during storage. In order to identify chemical compounds before and after storage, biomass pyrolysis was carried out in a fixed bed reactor at 623 K and bio-oil samples were characterized by gas chromatography/mass spectrophotometry (GC/MS. A bio-oil fractionation method was successfully applied here. Results indicate that bio-oil viscosity decreases due to active sites on the zeolite framework. Active acids sites were associated with an increment of alcohols, aldehydes, and hydrocarbon content during storage. Higher composition on aldehydes and alcohols after storage could be attributed to the occurrence of carbonyl reduction reactions that promotes them. These reactions are influenced by zeolite surface characteristics and could be achieved via the direct contribution of Brønsted acid sites to Chilean natural zeolite.

Bronsted acid site number evaluation using isopropylamine decomposition on Y-zeolite contaminated with vanadium in a simultaneous DSC-TGA analyzer

International Nuclear Information System (INIS)

Osorio Perez, Yonnathan; Forero, Liliam Alexandra Palomeque; Torres, Diana Vanessa Cristiano; Trujillo, Carlos Alexander

2008-01-01

Acid-site catalyzed decomposition of isopropylamine was followed in a simultaneous DSC-TGA analyzer. USY zeolite samples with and without vanadium were studied. Results show that acid sites number decreases linearly with vanadium concentration in zeolite indicating that vanadium neutralizes acid sites on catalyst and the metal is able to move on the surface of the solid. The neutralizing species probably contain only one vanadium atom. The reaction enthalpy plus desorption heat of the products show that vanadium preferentially neutralizes the strongest acid sites on the zeolite. The application of the simultaneous DSC-TGA technique to quantify Bronsted acid sites on solids by this reaction is novel

Rhodium segregation in dilute silver-rhodium alloys

International Nuclear Information System (INIS)

Krolas, K.; Sternik, M.

1995-01-01

Segregation of Rh in Ag-based alloys has been studied using the perturbed angular correlation of γ-rays emitted in the nuclear decay of radioactive 111 In. The formation of impurity complexes, consisting of an 111 In probe atom and one or more Rh atoms, was observed as a function of annealing time and temperature. Rhodium atom aggregation starts at about 600 K. From the fraction of 111 In bound to isolated Rh atoms the solute rhodium atom concentration was determined. It increases with the nominal alloy concentration up to about 0.04 at.% and then it is essentially constant for the nominal Rh concentration varying between 0.1 and 0.5 at.%. The solute rhodium atom concentration is 3 times larger at the melting point than at 750 K

Well-defined single-site monohydride silica-supported zirconium from azazirconacyclopropane

KAUST Repository

Hamzaoui, Bilel

2015-01-13

The silica-supported azazirconacyclopropane ≡SiOZr(HNMe2)(η2-NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150°C) to the single-site monopodal monohydride silica-supported zirconium species ≡SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200°C revealed alkene hydrogenation.

Well-defined single-site monohydride silica-supported zirconium from azazirconacyclopropane

KAUST Repository

Hamzaoui, Bilel; El Eter, Mohamad; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Basset, Jean-Marie

2015-01-01

The silica-supported azazirconacyclopropane ≡SiOZr(HNMe2)(η2-NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150°C) to the single-site monopodal monohydride silica-supported zirconium species ≡SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200°C revealed alkene hydrogenation.

Rhodium trichloride as a homogeneous catalyst for isotopic hydrogen exchange. Comparison with heterogeneous rhodium in the deuteriation of aromatic compounds and alkanes

Energy Technology Data Exchange (ETDEWEB)

Blake, M R; Garnett, J L; Gregor, I K; Hannan, W; Hoa, K; Long, M A [New South Wales Univ., Kensington (Australia)

1975-12-03

The use of rhodium trichloride as a homogeneous catalyst for the exchange of aromatic compounds and alkanes is described; comparison of the results with corresponding data from heterogeneous rhodium metal and other homogeneous systems, e.g., platinum and iridium, supports the proposal that specific type of ..pi..-complex mechanisms are common to all such exchange systems.

Comparative study of activated carbon, natural zeolite, and green sand supports for CuOX and ZnO sites as ozone decomposition catalyst

Science.gov (United States)

Azhariyah, A. S.; Pradyasti, A.; Dianty, A. G.; Bismo, S.

2018-03-01

This research was based on ozone decomposition in industrial environment. Ozone is harmful to human. Therefore, catalysts were made as a mask filter to decompose ozone. Comparison studies of catalyst supports were done using Granular Activated Carbon (GAC), Natural Zeolite (NZ), and Green Sand (GS). GAC showed the highest catalytic activity compared to other supports with conversion of 98%. Meanwhile, the conversion using NZ was only 77% and GS had been just 27%. GAC had the highest catalytic activity because it had the largest pore volume, which is 0.478 cm3/g. So GAC was used as catalyst supports. To have a higher conversion in ozone decomposition, GAC was impregnated with metal oxide as the active site of the catalyst. Active site comparison was made using CuOX and ZnO as the active site. Morphology, composition, and crystal phase were analyzed using SEM-EDX, XRF, and XRD methods. Mask filter, which contained catalysts for ozone decomposition, was tested using a fixed bed reactor at room temperature and atmospheric pressure. The result of conversion was analyzed using iodometric method. CuOX/GAC and ZnO/GAC 2%-w showed the highest catalytic activity and conversion reached 100%. From the durability test, CuOX/GAC 2%-w was better than ZnO/GAC 2%-w because the conversion of ozone to oxygen reached 100% with the lowest conversion was 70% for over eight hours.

Moessbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

International Nuclear Information System (INIS)

Millet, J.M.M.; Toyir, J.; Didillon, B.; Candy, J.P.; Nedez, C.; Basset, J.M.

1997-01-01

Moessbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C 4 H 9 ) 3 moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: The influence of zeolite chemical surface characteristics

Energy Technology Data Exchange (ETDEWEB)

Alejandro, Serguei [Laboratorio de Tecnologías Limpias (F. Ingeniería), Universidad Católica de la Santísima Concepción, Alonso de Ribera 2850, Concepción (Chile); Núcleo de Energías Renovables (F. Ingeniería), Universidad Católica de Temuco, Rudecindo Ortega 02950, Temuco (Chile); Valdés, Héctor, E-mail: hvaldes@ucsc.cl [Laboratorio de Tecnologías Limpias (F. Ingeniería), Universidad Católica de la Santísima Concepción, Alonso de Ribera 2850, Concepción (Chile); Manéro, Marie-Hélène [Université de Toulouse (France); INPT, UPS (France); Laboratoire de Génie Chimique, 4, Allée Emile Monso, F–31030 Toulouse (France); CNRS (France); Laboratoire de Génie Chimique, F–31030 Toulouse (France); Zaror, Claudio A. [Departamento de Ingeniería Química (F. Ingeniería), Universidad de Concepción, Concepción, Correo 3, Casilla 160–C (Chile)

2014-06-01

Highlights: • Surface acidity of modified natural zeolite is related to its chemical reactivity. • Brønsted acid sites are associated to toluene adsorption. • Lewis acid sites could decompose ozone generating surface active oxygen species. • Infrared spectra evidence active atomic oxygen and oxidation by-product formation. • 2NH4Z1 sample shows the highest reactivity toward adsorbed toluene. - Abstract: In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823 K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623 K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity.

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: The influence of zeolite chemical surface characteristics

International Nuclear Information System (INIS)

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A.

2014-01-01

Highlights: • Surface acidity of modified natural zeolite is related to its chemical reactivity. • Brønsted acid sites are associated to toluene adsorption. • Lewis acid sites could decompose ozone generating surface active oxygen species. • Infrared spectra evidence active atomic oxygen and oxidation by-product formation. • 2NH4Z1 sample shows the highest reactivity toward adsorbed toluene. - Abstract: In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823 K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623 K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

Science.gov (United States)

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

2014-06-15

In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. Copyright © 2014 Elsevier B.V. All rights reserved.

Isobutane/2-butene alkylation with zeolite Y without BrÆnsted acidity

OpenAIRE

Rosenbach Jr,Nilton; Mota,Claudio J. A.

2005-01-01

Alkylation of isobutane with 2-butene was performed on metal-exchanged Y zeolites, using an alkylchloride as carbocation initiator. The results indicated that, compared with a protonic zeolite, the deactivation was significantly slower and the production of trimethylpentanes was higher on the metal-exchanged zeolites. The metal cations act as Lewis acids, interacting with the chloride initiating the carbocationic reactions. The results also support the view that protonic sites on the catalyst...

Line profile analyses of rhodium metal obtained by decomposition of rhodium carbonyl

International Nuclear Information System (INIS)

Chandra, D.; Mandalia, H.; Garner, M.L.; Blakely, M.K.; Lau, K.H.

1995-01-01

Metal carbonyls are important for chemical vapor deposition (CVD) of metals and alloys and formation of high surface area metallic particles which have potential applications as catalysts. Rhodium carbonyl [Rh 6 (CO) 16 ] produces high surface area metallic particles whose structure has been reported as monoclinic (I2/a) with lattice dimensions, a=17.00(±0.03)Angstrom, b=9.78(±0.02)Angstrom, c=17.53(±0.03)Angstrom and Β=121 degrees 45' ± 30' at room temperature. Generally, metal carbonyl crystals dissociate under vacuum as carbonyl gas and decompose to metallic crystals and carbon monoxide at higher temperatures. However, the behavior of rhodium carbonyl crystals is different; they decompose directly to metallic rhodium without the formation of rhodium carbonyl gas in vacuum. Several residual fine grains of rhodium metal are found after the decomposition in vacuum at relatively low temperatures. The metallic samples of rhodium were obtained from vapor pressure experiments using torsion Knudsen-effusion apparatus. X-ray diffraction analyses performed on these gains showed severely broadened Bragg reflections indicative of small particle size and/or lattice microgram. In this study, a comparison of lattice strains and domain sizes obtained by integral breadth and Fourier methods has been made. In addition a comparison of the lattice strains and domain sizes has been made between the Cauchy, Gaussian, Cauchy-Gaussian and Aqua integral breadth methods

Sub-Micrometer Zeolite Films on Gold-Coated Silicon Wafers with Single-Crystal-Like Dielectric Constant and Elastic Modulus

Energy Technology Data Exchange (ETDEWEB)

Tiriolo, Raffaele [Department of Medical and Surgical Sciences, University Magna Graecia of Catanzaro, Viale Europa 88100 Catanzaro Italy; Rangnekar, Neel [Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave SE Minneapolis MN 55455 USA; Zhang, Han [Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave SE Minneapolis MN 55455 USA; Shete, Meera [Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave SE Minneapolis MN 55455 USA; Bai, Peng [Department of Chemistry and Chemistry Theory Center, University of Minnesota, 207 Pleasant St SE Minneapolis MN 55455 USA; Nelson, John [Characterization Facility, University of Minnesota, 12 Shepherd Labs, 100 Union St. S.E. Minneapolis MN 55455 USA; Karapetrova, Evguenia [Surface Scattering and Microdiffraction, X-ray Science Division, Argonne National Laboratory, 9700 S. Cass Ave, Building 438-D002 Argonne IL 60439 USA; Macosko, Christopher W. [Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave SE Minneapolis MN 55455 USA; Siepmann, Joern Ilja [Department of Chemistry and Chemistry Theory Center, University of Minnesota, 207 Pleasant St SE Minneapolis MN 55455 USA; Lamanna, Ernesto [Department of Health Sciences, University Magna Graecia of Catanzaro, Viale Europa 88100 Catanzaro Italy; Lavano, Angelo [Department of Medical and Surgical Sciences, University Magna Graecia of Catanzaro, Viale Europa 88100 Catanzaro Italy; Tsapatsis, Michael [Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave SE Minneapolis MN 55455 USA

2017-05-08

A low-temperature synthesis coupled with mild activation produces zeolite films exhibiting low dielectric constant (low-k) matching the theoretically predicted and experimentally measured values for single crystals. This synthesis and activation method allows for the fabrication of a device consisting of a b-oriented film of the pure-silica zeolite MFI (silicalite-1) supported on a gold-coated silicon wafer. The zeolite seeds are assembled by a manual assembly process and subjected to optimized secondary growth conditions that do not cause corrosion of the gold underlayer, while strongly promoting in-plane growth. The traditional calcination process is replaced with a non-thermal photochemical activation to ensure preservation of an intact gold layer. The dielectric constant (k), obtained through measurement of electrical capacitance in a metal-insulator-metal configuration, highlights the ultralow k approximate to 1.7 of the synthetized films, which is among the lowest values reported for an MFI film. There is large improvement in elastic modulus of the film (E approximate to 54 GPa) over previous reports, potentially allowing for integration into silicon wafer processing technology.

Investigation into cathode polarization during deposition of rhodium-nickel and rhodium-indium alloys

International Nuclear Information System (INIS)

Evdokimova, N.V.; Byacheslavov, P.M.; Lokshtanova, O.G.

1979-01-01

The results of kinetic regularities experimental investigations during electrodeposition of rhodium-nickel and rhonium-indium alloys are presented. Methods of general and partial polarization curves have been used to show the nature of polarization during the rhonium-nickel and rhodium-indium alloys deposition. It is shown that indium into the rhodium-indium alloy and nickel into the rhodium-nickel alloy deposit with great depolarization ( PHIsub(In)sup(0)=-0.33B, PHIsub(Ni)sup(0)=-0.23B). Indium and nickel in pure form do not deposit from the electrolytes of the given composition (H 2 SO 4 - 50 g/l, HNH 2 SO 3 -10 g/l). The recalculation of partial polarization curve of indium precipitation into the rhodium-indium alloy in the mixed kinetics coordinates gives a straight line with 40 mV inclination angle. This corresponds to the delayed stage of the second electron addition with the imposition of diffusion limitations

Periodic modeling of zeolite Ti-LTA.

Science.gov (United States)

Hernandez-Tamargo, Carlos E; Roldan, Alberto; Ngoepe, Phuti E; de Leeuw, Nora H

2017-08-21

We have proposed a combination of density functional theory calculations and interatomic potential-based simulations to study the structural, electronic, and mechanical properties of pure-silica zeolite Linde Type A (LTA), as well as two titanium-doped compositions. The energetics of the titanium distribution within the zeolite framework suggest that the inclusion of a second titanium atom with configurations Ti-(Si) 0 -Ti, Ti-(Si) 1 -Ti, and Ti-(Si) 2 -Ti is more energetically favorable than the mono-substitution. Infra-red spectra have been simulated for the pure-silica LTA, the single titanium substitution, and the configurations Ti-(Si) 0 -Ti and Ti-(Si) 2 -Ti, comparing against experimental benchmarks where available. The energetics of the direct dissociation of water on these Lewis acid sites indicate that this process is only favored when two titanium atoms form a two-membered ring (2MR) sharing two hydroxy groups, Ti-(OH) 2 -Ti, which suggests that the presence of water may tune the distribution of titanium atoms within the framework of zeolite LTA. The electronic analysis indicates charge transfer from H 2 O to the Lewis acid site and hybridization of their electronic states.

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

Science.gov (United States)

Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

2013-06-25

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

Energetic driving force of H spillover between rhodium and titania surfaces : a DFT view

NARCIS (Netherlands)

Conradie, J.; Gracia, J.; Niemantsverdriet, J.W.

2012-01-01

Hydrogen spillover from a rhodium particle, over the most stable (111) surface, to a TiO2 rutile support occurs at low hydrogen coverage because the adsorption energy of H atoms at low hydrogen coverage on rutile is larger than that on rhodium. H diffuses over the support with an activation barrier

Hydrodeoxygenation of Methyl Laurate over Ni Catalysts Supported on Hierarchical HZSM-5 Zeolite

Directory of Open Access Journals (Sweden)

Nana Li

2017-12-01

Full Text Available The hierarchical HZSM-5 zeolite was prepared successfully by a simple NaOH treatment method. The concentration of NaOH solution was carefully tuned to optimal the zeolite acidity and pore structure. Under NaOH treatment conditions, a large number of mesopores, which interconnected with the retained micropores, were created to facilitate mass transfer performance. There are very good correlations between the decline of the relative zeolite crystallinity and the loss of micropores volume. The Ni nanoclusters were uniformly confined in the mesopores of hierarchical HZSM-5 by the excessive impregnation method. The direct deoxygenation in N2 and hydrodeoxygenation in H2 of the methyl laurate were compared respectively over the Ni/HZSM-5 catalysts. In the N2 atmosphere, the deoxygenation rate of the methyl laurate on the Ni/HZSM-5 catalyst is relatively slow. In the presence of H2, the synergistic effect between the hydrogenation function of the metal and the acid function of the zeolite supports can make the deoxygenation level more obvious. The yield of hydrocarbon products gradually reached the maximum with the appropriate treatment concentration of 1M NaOH, which could be attributed to the improved mass transfer in the hierarchical HZSM-5 supports.

Polypropylene obtained through zeolite supported catalysts

Directory of Open Access Journals (Sweden)

Queli C. Bastos

2004-01-01

Full Text Available Propylene polymerizations were carried out with f2C(Flu(CpZrCl2 and SiMe2(Ind2ZrCl2 catalysts supported on silica, zeolite sodic mordenite (NaM and acid mordenite (HM. The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]. The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f2C(Flu(CpZrCl2, SiO2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereoregularity.

Polypropylene obtained through zeolite supported catalysts

International Nuclear Information System (INIS)

Bastos, Queli C.; Marques, Maria de Fatima V.

2004-01-01

Propylene polymerizations were carried out with φ 2 C(Flu)(Cp)ZrCl 2 and SiMe 2 (Ind)2ZrCl 2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f 2 C(Flu)(Cp)ZrCl 2 , SiO 2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

International Nuclear Information System (INIS)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Ti(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, 13 C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

Energy Technology Data Exchange (ETDEWEB)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

2015-01-15

A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

Inhibiting prolyl isomerase activity by hybrid organic-inorganic molecules containing rhodium(II) fragments.

Science.gov (United States)

Coughlin, Jane M; Kundu, Rituparna; Cooper, Julian C; Ball, Zachary T

2014-11-15

A small molecule containing a rhodium(II) tetracarboxylate fragment is shown to be a potent inhibitor of the prolyl isomerase FKBP12. The use of small molecules conjugates of rhodium(II) is presented as a general strategy for developing new protein inhibitors based on distinct structural and sequence features of the enzyme active site. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rhodium platings – experimental study

OpenAIRE

Rudolf, R.; Budić, B.; Stamenković, D.; Čolić, M.; Ivanič, A.; Kosec, B.

2013-01-01

Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

Synthesis of zeolite NaA membrane from fused fly ash extract.

Science.gov (United States)

Ameh, Alechine E; Musyoka, Nicholas M; Fatoba, Ojo O; Syrtsova, Daria A; Teplyakov, Vladimir V; Petrik, Leslie F

2016-01-01

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.

Rhodium platings – experimental study

Directory of Open Access Journals (Sweden)

R. Rudolf

2013-07-01

Full Text Available Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

Dinuclear ditertiary phosphite derivatives of rhodium

International Nuclear Information System (INIS)

Meintjies, E.

1981-08-01

The overall objective of the research described in this thesis was the design, synthesis, characterization and chemistry of dinuclear complexes of rhodium in which the metal atoms are held in close proximity to each other. Complexes of this nature are of considerable interest owing, in part, to their potential as models for multicentred metal catalysts, as well as to the highly novel and unusual chemistry already discovered for a number of them. A survey of dinuclear complexes of rhodium containing carbonyl and group V donor ligands has been presented as a background introduction to the research reported in this thesis. The coordination behaviour of the diphosphazane ligands, (RO) 2 PN(R')P(OR) 2 (R=Ph or Me, R' = Et; R = Et or Pr/i, R' = Me), and the ditertiary phosphite ligand, (EtO) 2 POP(OEt) 2 , towards certain rhodium precursors has been investigated. A number of highly unusual neutral dinuclear complexes of rhodium, in which these ligands bridge-bond the two rhodium atoms, have been synthesized. Two types of monocarbonyl decarbonylation products are observed for compounds of the type, [Rh 2 Cl 2 (CO) 2 (μ-diphosphazane) 2 ]. 1 H and 31 P[ 1 H] n.m.r. spectral studies have been carried out with the object of establishing the nature of the bridging halogen ligands in the tricarbonyl species. Asymetric zerovalent dinuclear species of the type, [Rh 2 (CO) 3 -[μ-(RO) 2 PN(R')P(OR) 2 ] 2 ] (R = Ph or Me, R' = Et; R = Pr/i, R' = Me), are obtained. A single crystal X-ray analysis has been carried out. Homoleptic cationic species are obtained by reaction of the alkoxydiphosphazane ligands with [Rh(C 8 H 12 )(solvent)(n)] + under the appropriate reaction conditions. The solution and solid-state infrared spectra and the 31 P[ 1 H] n.m.r. spectra of all new compounds synthesized in this study are discussed in terms of possible structures for these compounds. Where appropriate, the n.m.r. spectral data are also discussed in terms of fluxional behaviour

Effects of aeration and natural zeolite on ammonium removal during the treatment of sewage by mesocosm-scale constructed wetlands.

Science.gov (United States)

Araya, F; Vera, I; Sáez, K; Vidal, G

2016-01-01

The objective was to evaluate the effects of intermittent artificial aeration cycles and natural zeolite as a support medium, in addition to the contribution of plants (Schoenoplectus californicus) on NH4(+)-N removal during sewage treatment by Constructed Wetlands (CW). Two lines of Mesocosm Constructed Wetland (MCW) were installed: (a) gravel line (i.e. G-Line) and (b) zeolite line (i.e. Z-Line). Aeration increased the NH4(+)-N removal efficiency by 20-45% in the G-Line. Natural zeolite increased the NH4(+)-N removal efficiency by up to 60% in the Z-Line. Plants contributed 15-30% of the NH4(+)-N removal efficiency and no difference between the G-Line and the Z-Line. Conversely, the NH4(+)-N removal rate was shown to only increase with the use of natural zeolite. However, the MCW with natural zeolite, the NH4(+)-N removal rate showed a direct relationship only with the NH4(+)-N influent concentration. Additionally, relationship between the oxygen, energy and area regarding the NH4(+)-N removal efficiency was established for 2.5-12.5 gO2/(kWh-m(2)) in the G-Line and 0.1-2.6 gO2/(kWh-m(2)) in the Z-Line. Finally, it was established that a combination of natural zeolite as a support medium and the aeration strategy in a single CW could regenerate the zeolite's adsorption sites and maintain a given NH4(+)-N removal efficiency over time.

Industrial tests of rhodium self-powered detectors: the Golfech 2 experimentation

International Nuclear Information System (INIS)

Mourlevat, J.L.; Janvier, D.; Warren, H.D.

2000-01-01

In co-operation with Electricite de France (EDF), FRAMATOME has been testing two in-core strings which are equipped with rhodium self-powered detectors (SPDs) in the Golfech Unit 2 reactor (1300 MW, 4L plant) since August 1997. The rhodium SPDs and the strings which support them were designed and built by the US FRAMATOME subsidiary FRAMATOME-COGEMA-FUEL (FCF). The rhodium signals and some other plant parameters are acquired through the use of a specific device designed by the CEA (Commissariat a l'Energie Atomique) and are processed off-line by FRAMATOME. This demonstration test is planned to last until mid-2000. The following presentation is focused on the results obtained during the first demonstration cycle (from 08/97 to 12/98). The tests that have been conducted consist of checking the rhodium depletion and of comparing the rhodium signals to the movable probes. In order to compensate for the delay in the rhodium signals, a deconvolution algorithm has also been tested. Up to now, the results are very satisfactory and a future large scale industrial application is being discussed with the EDF. The main objective of the next experimentation phase is to test - under industrial conditions - a prototype of an on-line monitoring unit known as the Partial In-Core Monitoring System (PIMS). This system will include 16 rhodium in-core strings and will use an on-line 3-D core model. (authors)

Natural zeolite reactivity towards ozone: the role of compensating cations.

Science.gov (United States)

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Bergem, Haakon

1997-12-31

The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

The role of zeolite in the Fischer–Tropsch synthesis over cobalt–zeolite catalysts

International Nuclear Information System (INIS)

Sineva, L V; Mordkovich, V Z; Asalieva, E Yu

2015-01-01

The review deals with the specifics of the Fischer–Tropsch synthesis for the one-stage syncrude production from CO and H 2 in the presence of cobalt–zeolite catalytic systems. Different types of bifunctional catalysts (hybrid, composite) combining a Fischer–Tropsch catalyst and zeolite are reviewed. Special attention focuses on the mechanisms of transformations of hydrocarbons produced in the Fischer–Tropsch process on zeolite acid sites under the synthesis conditions. The bibliography includes 142 references

Synthesis of zeolite membrane (Y / α-alumina)

International Nuclear Information System (INIS)

Araujo, Ana Paula; Silva, Valmir Jose da; Crispin, Alana Carolyne; Rodrigues, Meiry Glaucia F.; Menezes, Romualdo R.

2009-01-01

The general aim of this study was to develop materials of the type: Y zeolite (hydrothermal synthesis), ceramic support (forming of powder) and zeolite membrane (rubbing). The preparation of the Y zeolite was conducted in accordance with the hydrothermal synthesis method, the time of crystallization was one day. The ceramic support was prepared by means of the forming of powder technique and subsequently subjected to sintering at a temperature of 1400 deg C/1h. The zeolite membrane (Y/α- alumina) was prepared by secondary growth method (rubbing). These materials were characterized by XRD and SEM. Obtaining Y zeolite could be confirmed by X ray diffractograms. From the images obtained by SEM, it was possible to derive from analysis that the Y zeolite is composed of a homogeneous morphology, where the particles are crowded, with uniform size. The results obtained for the ceramic support (α-alumina) showed that it displays characteristics peaks of aluminum oxide. By using micrographs it was possible to observe a heterogeneous microstructure with a compact form, without cracks upon the layers. According to the XRD, for the method of secondary growth (rubbing), it was observed that the Y zeolite which had been synthesized on the ceramic support displayed a crystalline structure. The micrography of the zeolite membrane (Y/α-alumina) showed the formation of a layer of zeolite on the ceramic support. (author)

Hydrodeoxygenation of fatty acid esters catalyzed by Ni on nano-sized MFI type zeolites

Energy Technology Data Exchange (ETDEWEB)

Schreiber, Moritz W.; Rodriguez-Niño, Daniella; Gutiérrez, Oliver Y.; Lercher, Johannes A.

2016-01-01

The impact of support morphology and composition on the intrinsic activity of Ni supported on MFI-type zeolite was explored in the hydrodeoxygenation of methyl stearate, tristearate, and algae oil (mixture of triglycerides). The nano-sized structure of the support (self-pillared nanosheets) is beneficial for the activity of the catalysts. Higher Ni dispersion and concomitant higher reaction rates were obtained on nano-structured supports than on zeolite with conventional morphology. Rates normalized to accessible Ni atoms (TOF), however, varied little with support morphology. Acidity of the support increases the rate of Ni-catalyzed C-O hydrogenolysis per surface metal site.

Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts.

Science.gov (United States)

Hong, Do-Young; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2010-02-21

Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

Distribution of metal and adsorbed guest species in zeolites

Energy Technology Data Exchange (ETDEWEB)

Chmelka, B.F.

1989-12-01

Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

Distribution of metal and adsorbed guest species in zeolites

International Nuclear Information System (INIS)

Chmelka, B.F.

1989-12-01

Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes 129 Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of 129 Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, 129 Xe NMR is insensitive to fine structural details at room temperature

Natural zeolite reactivity towards ozone: The role of compensating cations

International Nuclear Information System (INIS)

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A.

2012-01-01

Highlights: ► Chemical and thermal treatment enhances catalytic activity of natural zeolite. ► Modified natural zeolite exhibits high stability after thermal treatment. ► Reducing the compensating cation content leads to an increase on ozone abatement. ► Surface active atomic oxygen was detected using the DRIFT technique. ► The highest reactivity toward ozone was performed by NH4Z3 zeolite sample. - Abstract: Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L −1 ). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77 K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH 3 -TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

Isobutane/2-butene alkylation with zeolite Y without BrÆnsted acidity

OpenAIRE

Rosenbach Jr, Nilton; Mota, Claudio J. A.

2005-01-01

Alkylation of isobutane with 2-butene was performed on metal-exchanged Y zeolites, using an alkylchloride as carbocation initiator. The results indicated that, compared with a protonic zeolite, the deactivation was significantly slower and the production of trimethylpentanes was higher on the metal-exchanged zeolites. The metal cations act as Lewis acids, interacting with the chloride initiating the carbocationic reactions. The results also support the view that protonic sites on the catalyst...

Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

International Nuclear Information System (INIS)

Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

2003-01-01

Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

International Nuclear Information System (INIS)

Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

2000-01-01

The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

Zeolite function studied by neutron diffraction

International Nuclear Information System (INIS)

Newsam, J.M.

1988-01-01

Some recent figures relating to industrial uses of zeolites are summarized. Recent advances in the application of neutron diffraction to zeolite science are overviewed, with particular emphasis on powder diffraction (PND) results. Single crystal neutron diffraction studies of some 17 hydrated natural and synthetic zeolites have now appeared and they provide a consistent picture of zeolite-water interactions. Complete PND studies of hydrated synthetic ABW- and SOD-framework zeolites have also been reported. Other PND studies have explored the structural consequences of non-framework cation exchange, of framework modification by dealumination, and of framework cation substitution. Relatively simple zeolite-hydrocarbon sorbate complexes that have been studied include benzene in zeolite Y, and benzene and pyridine in zeolite L. Areas that are well poised for further development include further extensions to lower symmetry systems, the use of PND data for zeolite structure solution, studies at elevated temperatures and pressures, and further studies of zeolite sorbate complexes. (author) 68 refs., 7 figs

Natural zeolite reactivity towards ozone: The role of compensating cations

Energy Technology Data Exchange (ETDEWEB)

Valdes, Hector, E-mail: hvaldes@ucsc.cl [Laboratorio de Tecnologias Limpias (F. Ingenieria), Universidad Catolica de la Santisima Concepcion, Alonso de Ribera 2850, Concepcion (Chile); Alejandro, Serguei; Zaror, Claudio A. [Departamento de Ingenieria Quimica (F. Ingenieria), Universidad de Concepcion, Concepcion (Chile)

2012-08-15

Highlights: Black-Right-Pointing-Pointer Chemical and thermal treatment enhances catalytic activity of natural zeolite. Black-Right-Pointing-Pointer Modified natural zeolite exhibits high stability after thermal treatment. Black-Right-Pointing-Pointer Reducing the compensating cation content leads to an increase on ozone abatement. Black-Right-Pointing-Pointer Surface active atomic oxygen was detected using the DRIFT technique. Black-Right-Pointing-Pointer The highest reactivity toward ozone was performed by NH4Z3 zeolite sample. - Abstract: Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L{sup -1}). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77 K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH{sub 3}-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

Energy Technology Data Exchange (ETDEWEB)

Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences (China)

2017-04-18

Supported metal nanocrystals have exhibited remarkable catalytic performance in hydrogen generation reactions, which is influenced and even determined by their supports. Accordingly, it is of fundamental importance to determine the direct relationship between catalytic performance and metal-support interactions. Herein, we provide a quantitative profile for exploring metal-support interactions by considering the highest occupied state in single-atom catalysts. The catalyst studied consisted of isolated Rh atoms dispersed on the surface of VO{sub 2} nanorods. It was observed that the activation energy of ammonia-borane hydrolysis changed when the substrate underwent a phase transition. Mechanistic studies indicate that the catalytic performance depended directly on the highest occupied state of the single Rh atoms, which was determined by the band structure of the substrates. Other metal catalysts, even with non-noble metals, that exhibited significant catalytic activity towards NH{sub 3}BH{sub 3} hydrolysis were rationally designed by adjusting their highest occupied states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Computer simulation of molecular sorption in zeolites

International Nuclear Information System (INIS)

Calmiano, Mark Daniel

2001-01-01

The work presented in this thesis encompasses the computer simulation of molecular sorption. In Chapter 1 we outline the aims and objectives of this work. Chapter 2 follows in which an introduction to sorption in zeolites is presented, with discussion of structure and properties of the main zeolites studied. Chapter 2 concludes with a description of the principles and theories of adsorption. In Chapter 3 we describe the methodology behind the work carried out in this thesis. In Chapter 4 we present our first computational study, that of the sorption of krypton in silicalite. We describe work carried out to investigate low energy sorption sites of krypton in silicalite where we observe krypton to preferentially sorb into straight and sinusoidal channels over channel intersections. We simulate single step type I adsorption isotherms and use molecular dynamics to study the diffusion of krypton and obtain division coefficients and the activation energy. We compare our results to previous experimental and computational studies where we show our work to be in good agreement. In Chapter 5 we present a systematic study of the sorption of oxygen and nitrogen in five lithium substituted zeolites using a transferable interatomic potential that we have developed from ab initio calculations. We show increased loading of nitrogen compared to oxygen in all five zeolites studied as expected and simulate adsorption isotherms, which we compare to experimental and simulated data in the literature. In Chapter 6 we present work on the sorption of ferrocene in the zeolite NaY. We show that a simulated, low energy sorption site for ferrocene is correctly located by comparing to X-ray powder diffraction results for this same system. The thesis concludes with some overall conclusions and discussion of opportunities for future work. (author)

Carbon monoxide hydrogenation over ruthenium zeolites

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P.A.; Nijs, H.H.; Verdonck, J.J.; Uytterhoeven, J.B.

1978-03-01

Ru zeolites are active and stable methanation catalysts. Under Fischer--Tropsch conditions they show a narrow product distribution. Further work is needed to assign this to a possible effect exerted by the zeolite cages. When the size of the Ru particles enclosed in the zeolite cages is increased, a lower methanation activity is found and a higher amount of C/sub 2/ and C/sub 3/ products are formed under Fischer--Tropsch conditions. This effect has not been reported until now on other supports. The less acidic zeolites act as promoters of the CO hydrogenation: under methanation conditions the activity is increased; under Fischer--Tropsch conditions, the selectivity is shifted toward higher hydrocarbons. This is explained by the particular zeolite property that electron deficient metal agglomerates seem to be formed on the acidic zeolites. With respect to kinetic behavior, relative activity of different metals, influence of reaction temperature on product distribution, the zeolite behaves in the same way a conventional alumina support. 4 figs., 4 tables.

Distribution of Rhodium in Mice Submitted to Treatment With the Adduct of Rhodium Propionate and Sodium Isonicotinate

OpenAIRE

de Souza, Aparecido Ribeiro; Najjar, Renato; de Oliveira, Elizabeth; Zyngier, Szulim Ber

1997-01-01

The distribution of rhodium in Balb/c mice following intraperitoneal (ip) administration of a solution of adduct of rhodium propionate and sodium isonicotinate has been investigated. The metal concentration was determined in blood and in the following organ tissues: brain, heart, lung, liver, spleen, kidney, testes, and uterus/ovary, and the rhodium concentration was obtained by Inductively Coupled Argon Atomic Emission Spectroscopy (ICP-AES). The metal was detected in all organ tissues exami...

Synthesis and characterization of the Rhodium (II) citrate complex

International Nuclear Information System (INIS)

Najjar, R.; Santos, F.S. dos; Seidel, W.

1987-01-01

The preparation and characterization of the rhodium (II) citrate is described. Rhodium citrate was prepared by reacting citric acid trihydrated (3,4 g, 16 mmols) with anhydrous rhodium acetate (0,44 g, 1 mmol). Th electronic instruments, thermogravimetric curve and spectrum of rhodium (II) citrate are analysed. (M.J.C.) [pt

Method of producing zeolite encapsulated nanoparticles

DEFF Research Database (Denmark)

2015-01-01

The invention therefore relates to a method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles, the method comprises the steps of: 1) Adding one or more metal precursors to a silica or alumina source; 2) Reducing the one or more metal precursors to form metal...... nanoparticles on the surface of the silica or alumina source; 3) Passing a gaseous hydrocarbon, alkyl alcohol or alkyl ether over the silica or alumina supported metal nanoparticles to form a carbon template coated zeolite, zeolite-like or zeotype precursor composition; 4a) Adding a structure directing agent...... to the carbon template coated zeolite, zeolite-like or zeotype precursor composition thereby creating a zeolite, zeolite-like or zeotype gel composition; 4b) Crystallising the zeolite, zeolite-like or zeotype gel composition by subjecting said composition to a hydrothermal treatment; 5) Removing the carbon...

Method for producing zeolites and zeotypes

DEFF Research Database (Denmark)

2015-01-01

The invention relates to a method for producing zeolite, zeolite-like or zeotype particles comprising the steps of: 1 ) Adding one or more metal precursors to a silica or alumina source; 2) Reducing the one or more metal precursors to form metal nanoparticles on the surface of the silica or alumina...... source; 3) Passing a gaseous hydrocarbon, alkyl alcohol or alkyl ether over the silica or alumina supported metal nanoparticle to form a carbon template coated zeolite, zeolite-like or zeotype precursor composition; 4a) Adding a structure directing agent to the carbon template coated zeolite, zeolite......-like or zeotype precursor composition thereby creating a zeolite, zeolite-like or zeotype gel composition; 4b) Crystallising the zeolite, zeolite-like or zeotype gel composition by subjecting said composition to a hydrothermal treatment; 5) Removing the carbon template and structure directing agent and isolating...

Modifiers in rhodium catalysts for carbon monoxide hydrogenation: Structure-activity relationships

Energy Technology Data Exchange (ETDEWEB)

Bhore, N. A.

1989-05-01

This report is aimed at identifying interesting modified rhodium systems and elucidating structure-activity relationships in these systems with the overall goal of understanding the scientific issues in the catalytic conversion of syngas to oxygenates. Specific additives (sodium and molybdenum) are selected based on the scoping experiments. The effect of the additives on supported rhodium catalysts is then investigated. Throughout the investigation, experiments and analysis were performed on real systems instead of ideal systems. 374 refs., 82 figs., 57 tabs.

Characterization of NaA Zeolite Oxygen Permeable Membrane on TiO2/α-Al2O3 Composite Support

Directory of Open Access Journals (Sweden)

Zhu Mengfu

2016-01-01

Full Text Available The NaA zeolite membrane was synthesized on the surface of TiO2/α-Al2O3 composite support with TiO2 as modifier of α-Al2O3 porous tubular ceramic membrane support by crystallization method. The structure characterization indicated that the TiO2 of the support surface could effectively improve the surface properties of the support. It didn’t affect the crystallization of NaA synthesis liquid and synthesis process of NaA zeolite membrane. There were no obvious defects between the crystal particles with size of approximate 6μm. The perfect and complete membrane with thickness of approximate 15μm combined closely with support to connection together by TiO2 modified. The oxygen permeability of the membrane on TiO2/α-Al2O3 composite support improves of 47% compared with that of α-Al2O3 support. So the process of TiO2 modifying the surface of α-Al2O3 support should increase the oxygen permeability of the NaA zeolite membrane.

EXAFS study of Mo2N and Mo nitrides supported on zeolites

International Nuclear Information System (INIS)

Liu Zhenlin; Meng Ming; Fu Yilu; Jiang Ming; Hu Tiandou; Xie Yaning; Liu Tao

2002-01-01

In the present study, the reaction is applied to prepare molybdenum nitrides with high surface area, and zeolites are used as supports. The EXAFS of the Mo K-absorption edge is measured and the change of coordination environment of Mo atoms before and after the nitridation is revealed

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers

International Nuclear Information System (INIS)

Mattioli, Michele; Giordani, Matteo; Dogan, Meral; Cangiotti, Michela; Avella, Giuseppe; Giorgi, Rodorico; Dogan, A. Umran; Ottaviani, Maria Francesca

2016-01-01

Highlights: • Differently carcinogenic zeolite fibers were investigated combining physico-chemical methods. • For the first time, zeolite fibers were studied by means of the EPR technique using different spin probes. • The structural properties and the adsorption capability are function of different types and distributions of adsorption sites. • The interacting ability of erionite is higher than that of other fibrous zeolites. • The surface interacting properties may be related with the carcinogenicity of the zeolite fibers. - Abstract: Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si–O–Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity.

Theoretical determination of proton affinity differences in zeolites

NARCIS (Netherlands)

Kramer, G.J.; Santen, van R.A.

1993-01-01

An important factor in zeolite catalysis is the proton affinity, i.e., the energy required to remove a proton from the zeolite lattice. Differences in proton affinity are expected to influence the catalytic activity of acid sites, making the catalytically active sites inhomogeneous (within one

Transient-response study of CO insertion into CHx surface intermediates on a vanadium-promoted rhodium catalyst

NARCIS (Netherlands)

Koerts, T.; Santen, van R.A.

1992-01-01

The rate of CO insertion into surface CHx species was investigated on silica-supported rhodium and rhodium-vanadium catalysts. Isotopically labelled 13CO was used in a transient kinetic experiment under steady-state conditions. A main conclusion is that vanadium promotion does not affect the rate of

Positron spectroscopy studies of zeolites

Science.gov (United States)

Hung, Ku-Jung

The lineshapes of two-dimensional angular correlation of electron-positron annihilation radiation (2D-ACAR) in alumina and several zeolites were measured as a function of internal surface areas. In all cases, the lineshape parameter S from 2D-ACAR spectra were found to vary proportionally with internal surface area. In order to investigate the Bronsted acidity in NaHY zeolite, the lineshape parameter evaluation from 2D-ACAR measurements for varied acidity in NaHY zeolites by ion-exchange and thermal desorption were presented. The result from this investigation has demonstrated that the Bronsted acidity in NaHY zeolite was found to vary linearly with the lineshape parameter of the angular correlation spectrum of the sample. The lineshapes of 2D-ACAR spectra were determined for different base adsorbed HY-zeolite samples under a temperature controlled heating system in order to investigate, in-situ, the acid strength and number of Bronsted acid sites in the sample. Results have shown that the lineshape parameter of the angular correlation spectrum of the sample increases with the strength of adsorbed base and decreases with the number of Bronsted acid sites in the sample. This indicated that the lineshape parameter is sensitive to all of the strengths and concentrations of Bronsted acid sites in the HY-zeolite samples. The result from this study has also demonstrated that the large size base, pyridine, would reduce the possibility of positronium formation in the sample by filling the cage to eliminate the internal surface areas where the positroniums are likely to form. However, the small size base, ammonia, did not show any effect on the internal surface areas. Owing to the fact that this technique monitors only the Bronsted acid sites that situate on the surface which relates to the catalytic activity, there is little ambiguity about the location of the source of information obtained. The findings presented in this dissertation point out the fact that such lineshape

Chemical reactivity of cation-exchanged zeolites

OpenAIRE

Pidko, E.A.

2008-01-01

Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

Science.gov (United States)

Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

TNU-9 Zeolite: Aluminum Distribution and Extra-Framework Sites of Divalent Cations

Czech Academy of Sciences Publication Activity Database

Karcz, R.; Dědeček, Jiří; Supronowicz, B.; Thomas, Haunani M.; Klein, Petr; Tabor, Edyta; Sazama, Petr; Pashková, Veronika; Sklenák, Štěpán

2017-01-01

Roč. 23, JUL 2017 (2017), s. 8857-8870 ISSN 1521-3765 R&D Projects: GA ČR(CZ) GA15-14007S; GA MŠk(CZ) LM2015073 Grant - others:Ga MŠk(CZ) LM2015070 Institutional support: RVO:61388955 Keywords : Aluminum * Cobalt * Density functional calculations * Structure elucidation * Zeolites Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Correction of rhodium detector signals for comparison to design calculations

International Nuclear Information System (INIS)

Judd, J.L.; Chang, R.Y.; Gabel, C.W.

1989-01-01

Rhodium detectors are used in many commercial pressurized water reactors PWRs [pressurized water reactor] as in-core neutron detectors. The signals from the detectors are the result of neutron absorption in 103 Rh and the subsequent beta decay of 104 Rh to 104 Pd. The rhodium depletes ∼1% per full-power month, so corrections are necessary to the detector signal to account for the effects of the rhodium depletion. These corrections result from the change in detector self-shielding with rhodium burnup and the change in rhodium concentration itself. Correction for the change in rhodium concentration is done by multiplication of the factor N(t)/N 0 , where N(t) is the rhodium concentration at time t and N 0 is the initial rhodium concentration. The calculation of the self-shielding factor is more complicated and is presented. A self-shielding factor based on the fraction of rhodium remaining was calculated with the CASMO-3 code. The results obtained from our comparisons of predicted and measured in-core detector signals show that the CASMO-3/SIMULATE-3 code package is an effective tool for estimating pin peaking and power distributions

ADSORPTION MALACHITE GREEN ON NATURAL ZEOLITE

OpenAIRE

Eko Ariyanto

2012-01-01

A natural zeolite was employed as adsorbent for reducing of malachite green from aqueous solution. A batch system was applied to study the adsorption of malachite green in single system on natural zeolite. The adsorption studies indicate that malachite green in single component system follows the second-order kinetics and the adsorption is diffusion process with two stages for malachite green. Malachite green adsorption isotherm follows the Langmuir model.

Metal supported on natural zeolite as catalysts for conversion of ethanol to gasoline

Directory of Open Access Journals (Sweden)

Kristiani Anis

2017-01-01

Full Text Available A various of metal supported into natural zeolite was prepared via wet impregnation method. The transition metals impregnated are nickel, cobalt, copper and zinc. The catalytic properties both of physical and chemical properties were characterized by X-ray Diffraction (XRD, Thermo Gravimetri Analysis (TGA-Differential Scanning Calorimetry (DSC, Surface Area Analyzer-Porositymeter and also gravimetry method for acidity measurement following by the adsorption of organic bases. The results showed that different metals impregnated into natural zeolite affected physical and chemical properties, i.e. crystalinity, surface area, pore size, pore volume and acidity. Their catalytic activity was tested for conversion ethanol to gasoline and showed high conversion up to 80-90% with the aromatics as major product.

Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

International Nuclear Information System (INIS)

Peri, J.B.

1975-01-01

The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

Preparation of rhodium target for cyclone-30 accelerator

International Nuclear Information System (INIS)

Deng Xuesong; Li Dakang; Xie Xiangqian; Li Chao

2002-01-01

The rhodium target for Cyclone-30 accelerator is prepared by pulse electroplating method. The effects of pulse parameters, rhodium concentration, acidity and temperature on the properties of the target layer are studied, and the optimal process is determined. The rhodium target, mass thickness is more than 150 mg/cm 2 , adapts to producing 103 Pd on Cyclone-30 accelerator

Molecular recognition in protein modification with rhodium metallopeptides

Science.gov (United States)

Ball, Zachary T.

2015-01-01

Chemical manipulation of natural, unengineered proteins is a daunting challenge which tests the limits of reaction design. By combining transition-metal or other catalysts with molecular recognition ideas, it is possible to achieve site-selective protein reactivity without the need for engineered recognition sequences or reactive sites. Some recent examples in this area have used ruthenium photocatalysis, pyridine organocatalysis, and rhodium(II) metallocarbene catalysis, indicating that the fundamental ideas provide opportunities for using diverse reactivity on complex protein substrates and in complex cell-like environments. PMID:25588960

Carbon monoxide adsorption on low-silica zeolites-from single to dual and to multiple cation sites

Czech Academy of Sciences Publication Activity Database

Otero Areán, C.; Rodríguez Delgado, M.; López Bauca, C.; Vrbka, Luboš; Nachtigall, Petr

2007-01-01

Roč. 9, č. 33 (2007), s. 4657-4661 ISSN 1463-9076 R&D Projects: GA MŠk LC512; GA ČR GA203/06/0324 Grant - others:UIB(ES) MAT2005-05350 Institutional research plan: CEZ:AV0Z40550506 Keywords : zeolite * adsorption * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.343, year: 2007

Bioenvironmental aspects of europium and rhodium: a selected bibliography

International Nuclear Information System (INIS)

Fore, C.S.; Carrier, R.F.; Talmage, S.S.; Fielden, J.M.; Daniel, E.W.

1983-09-01

This bibliography of 428 abstracted references represents a summary of the domestic and foreign literature relevant to the biological and environmental aspects of europium and rhodium. The collected data are organized by current NAEG interests - research highlighting inventory and distribution of the radionulcides, ecological studies covering terrestrial and aquatic systems, and biological studies in both man and animals. Studies that focus directly on research conducted at specific sites (e.g., the Nevada Test Site) are emphasized throughout the bibliography

for zeolite coating

Directory of Open Access Journals (Sweden)

Carlos Renato Rambo

2006-01-01

Full Text Available Biotemplating is the processing of microcellular ceramics by reproduction of natural morphologies, where the microstructural features of the biotemplate are maintained in the biomorphic ceramic. Different biotemplates with distinct pore anatomies were used to produce biomorphic supports for the zeolite coating: wood, cardboard, sea-sponge and sisal. The biomorphic ceramics were produced by distinguished processing routes: Al-gas infiltration-reaction, liquid-metal infiltration, dip-coating and sol-gel synthesis, in order to produce nitrides, carbides and oxides, depending on the processing conditions. The zeolite coating was performed by hydrothermal growth of MFI-type (Silicalite-1 and ZSM-5 zeolite crystals onto the internal pore walls of the biomorphic templates. The final biomorphic ceramic-zeolite composites were physically characterized, evaluated in terms of their gas adsorption capabilities and correlated to their microstructure and specific pore anatomy. The combination of the properties of the biomorphic ceramics with the adsorption properties of zeolites results in materials with distinct properties as potential candidates for adsorption and catalytic applications due to their characteristic porosity, molecular sieving capabilities and high thermo-mechanical strength.

Intergrown new zeolite beta polymorphs with interconnected 12-ring channels solved by combining electron crystallography and single-crystal X-ray diffraction

KAUST Repository

Yu, Zhengbao

2012-10-09

Two new polymorphs of zeolite beta, denoted as SU-78A and SU-78B, were synthesized by employing dicyclohexylammonium hydroxides as organic structure-directing agents. The structure was solved by combining transmission electron microscopy and single-crystal X-ray diffraction. SU-78 is an intergrowth of SU-78A and SU-78B and contains interconnected 12-ring channels in three directions. The two polymorphs are built from the same building layer, similar to that for the zeolite beta family. The layer stacking in SU-78, however, is different from those in zeolite beta polymorph A, B, and C, showing new zeolite framework topologies. SU-78 is thermally stable up to 600 °C. © 2012 American Chemical Society.

Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

Energy Technology Data Exchange (ETDEWEB)

Leyrit, P

1999-06-28

Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

ADSORPTION MALACHITE GREEN ON NATURAL ZEOLITE

Directory of Open Access Journals (Sweden)

Eko Ariyanto

2012-02-01

Full Text Available A natural zeolite was employed as adsorbent for reducing of malachite green from aqueous solution. A batch system was applied to study the adsorption of malachite green in single system on natural zeolite. The adsorption studies indicate that malachite green in single component system follows the second-order kinetics and the adsorption is diffusion process with two stages for malachite green. Malachite green adsorption isotherm follows the Langmuir model.

Szilard-Chalmers cation recoil studies in zeolites X and Y

International Nuclear Information System (INIS)

Lai, P.P.; Rees, L.V.C.

1976-01-01

The Szilard-Chalmers recoil of the cations Rb + , Cs + , Ba 2+ , La 3+ , Co 2+ , Zn 2+ , Cu 2+ and Na + from the sodalite cage and hexagonal prism sites into the supercage sites of zeolites X and Y has been studied. This study is complementary to that described in Lai et al, JCS Faraday I; 72:181 (1976). It has been found that these cations recoil from the sodalite cage sites into the supercage sites with a probability of approximately 90% whereas the corresponding probability for these cations in the hexagonal prism sites (site I) is between 40 and 50% depending on the cation. It is thus possible to determine the preferences shown by these cations for these 'locked-in' sites as a function of temperature of calcination, Tsub(c), concentration and type of other cations contained in these sites. In these studies the cations present in the supercage sites before irradiation were usually NH 4 + but Ba 2+ , Ca 2+ and Na + have also been used. When Tsub(c) > 400 0 C, Rb + and Cs + began to populate site I. These ions populated this site in zeolite X at lower calcination temperatures than required for zeolite Y. When Tsub(c) was increased from 110 to 220 0 C the occupancy of site I by Ba 2+ was greatly enhanced and when Tsub(c) > 440 0 C Ba 2+ ions now occupied this site in preference to all other 'locked-in' sites. Barium exhibited a higher affinity for site I in zeolite X than in zeolite Y when Tsub(c) = 110 0 C. If dehydrated La-Y was assumed to have 5 La 3+ ions per u.c. in site I, the hydration of this material did not change the concentration of La 3+ in site I. Co 2+ , Zn 2+ and Cu 2+ ions all exhibited similar affinities for the 'locked-in' sites of zeolites X and Y. (author)

Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

International Nuclear Information System (INIS)

Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

2014-01-01

Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

Obtaining of supports macro and micro nutrients with base in zeolites mexicans

International Nuclear Information System (INIS)

Cordova H, A.; Islas M, M.; Bascunan S, C.; Martines G, M.; Nikolaev N, S.

2001-01-01

Study the effect of application of the zeolites modified by the ionico interchange with fertilizers (NPK), N-p in the production of tomatos. The cultive of tomatos was made in lands of the Benemerita Autonoma Universidad de Puebla, Mexico, taking equal quadrants with the following ground treatments: 1) zeolite interchanged with fertilizers, 2) zeolite interchanged with a solution that contained only N-p, 3) natural zeolite without ionica modification and a quadrant witness represented by the ground without treatment. The collected data show an increase in the harvest of tomatos, as well as the retention of the decomposition of the harvested tomatos. In addition, it determinated that the optimal concentrations in the case of the zeolite dealt with 3% of fertilizer NPK are: 0,91% of potassium and 0.61% of nitrogen. These results allow to suggest the use of zeolites modified by ionico interchange in agriculture to elevate the level of the harvests of the tomato [es

Evaluation of photocatalytic activities of supported catalysts on NaX zeolite or activated charcoal

Energy Technology Data Exchange (ETDEWEB)

Brites-Nóbrega, Fernanda F. de [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil); Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Polo, Aldino N.B.; Benedetti, Angélica M. [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Leão, Mônica M.D. [Sanitary and Environmental Engineering Department, Universidade Federal de Minas Gerais (UFMG), Av. Antônio Carlos, 6627, Campus Pampulha, Belo Horizonte, MG (Brazil); Slusarski-Santana, Veronice, E-mail: veronice.santana@unioeste.br [Chemical Engineering Department, Universidade Estadual do Oeste do Paraná (UNIOESTE), Rua da Faculdade, 645, CEP 85903-000 Toledo, PR (Brazil); Fernandes-Machado, Nádia R.C. [Chemical Engineering Department, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, CEP 87020-900 Maringá, PR (Brazil)

2013-12-15

Highlights: • The synergic effect between ZnO and NaX was positive, which increased its activity. • The best results were obtained at pH 3 and 9 with ZnO/NaX and at pH 3 with Nb{sub 2}O{sub 5}/AC. • High degradation and considerable mineralization were attained with 10% ZnO/NaX. • ZnO and Nb{sub 2}O{sub 5} supported on NaX and AC are promising alternatives as photocatalysts. -- Abstract: This study aimed to evaluate the photocatalytic activity of ZnO and Nb{sub 2}O{sub 5} catalysts, both supported on NaX zeolite and activated charcoal (AC). The synergistic effect between oxide and support and the influence of solution pH (3, 7 and 9) on photocatalytic degradation of reactive blue 5G (C.I. 222) were analyzed. The catalysts Nb{sub 2}O{sub 5}/NaX, Nb{sub 2}O{sub 5}/AC and ZnO/NaX, ZnO/AC with 5 and 10% (wt%) were prepared by wet impregnation. The results showed that the catalysts exhibit quite different structural and textural properties. The synergic effect between ZnO and NaX support was higher than that with the activated charcoal, showing that these catalysts were more efficient. The most photoactive catalyst was 10% ZnO/NaX which showed 100% discoloration of the dye solution at pH 3, 7 and 9 after 0.5, 5 and 2 h of irradiation, respectively. The hydrolytic nature of zeolite favored the formation of surface hydroxyl radicals, which increased the activity of the photocatalyst. Thus, catalysts supported on NaX zeolite are promising for use in photocatalysis.

The influence of rhodium burn-up on the sensitivity of rhodium self-powered neutron detectors

International Nuclear Information System (INIS)

Erben, O.

1980-01-01

Depression and self-shielding coefficients are presented for thermal and epithermal neutron flux densities. Functions are shown describing the distribution of beta particle sources on the emitter cross section for 0 to 50% rhodium burnup. The values are calculated of detector sensitivity to thermal and epithermal neutron flux densities for the said burnup for main types of rhodium SPN detectors made by SODERN. (J.B.)

A Concise Synthesis of the Erythrina Alkaloid 3–Demethoxyerythratidinone via Combined Rhodium Catalysis

Science.gov (United States)

Joo, Jung Min; David, Ramoncito A.; Yuan, Yu; Lee, Chulbom

2010-01-01

The total synthesis of the erythrina alkaloid 3–demethoxyerythratidinone has been achieved via a strategy based on combined rhodium catalysis. The catalytic tandem cyclization effected by the interplay of alkynyl and vinylidene rhodium species allows for efficient access to the A and B rings of the tetracyclic erythrinane skeleton in a single step. The synthesis also features rapid preparation of the requisite precursor for the double ring closure and thus has been completed in only 7 total steps in 41% overall yield. PMID:21090648

Antitumor effect and toxicity of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles in mice bearing breast cancer.

Science.gov (United States)

Carneiro, Marcella Lemos Brettas; Peixoto, Raphael C A; Joanitti, Graziela A; Oliveira, Ricardo G S; Telles, Luis A M; Miranda-Vilela, Ana L; Bocca, Anamélia L; Vianna, Leonora M S; da Silva, Izabel C R; de Souza, Aparecido R; Lacava, Zulmira G M; Báo, Sônia N

2013-02-16

Magnetic fluids containing superparamagnetic iron oxide nanoparticles represent an attractive platform as nanocarriers in chemotherapy. Recently, we developed a formulation of maghemite nanoparticles coated with rhodium (II) citrate, which resulted in in vitro cytotoxicity enhanced up to 4.6 times when compared to free rhodium (II) citrate formulation on breast carcinoma cells. In this work, we evaluate the antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Mice were evaluated with regard to the treatments' toxicity through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine; DNA fragmentation and cell cycle of bone marrow cells; and liver, kidney and lung histology. In addition, the antitumor activity of rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate was verified by tumor volume reduction, histology and immunohistochemistry. Regarding the treatments' toxicity, no experimental groups had alterations in levels of serum ALT or creatinine, and this suggestion was corroborated by the histopathologic examination of liver and kidney of mice. Moreover, DNA fragmentation frequency of bone marrow cells was lower than 15% in all experimental groups. On the other hand, the complexes rhodium (II) citrate-functionalized maghemite and free rhodium (II) citrate led to a marked growth inhibition of tumor and decrease in CD31 and Ki-67 staining. In summary, we demonstrated that both rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate formulations exhibited antitumor effects against 4T1 metastatic breast cancer cell line following intratumoral administration. This antitumor effect was followed by inhibition of both cell proliferation and microvascularization and by tumor tissue injury characterized as necrosis and fibrosis. Remarkably, this is the first published report demonstrating the therapeutic efficacy of maghemite

Biotemplating of Luffa cylindrica sponges to self-supporting hierarchical zeolite macrostructures for bio-inspired structured catalytic reactors

International Nuclear Information System (INIS)

Zampieri, Alessandro; Mabande, Godwin T.P.; Selvam, Thangaraj; Schwieger, Wilhelm; Rudolph, Alexander; Hermann, Ralph; Sieber, Heino; Greil, Peter

2006-01-01

Biomorphic self-supporting MFI-type zeolite frameworks with hierarchical porosity and complex architecture were prepared using a 2-step (in-situ seeding and secondary crystal growth) hydrothermal synthesis in the presence of a biological template (Luffa sponge), employed as a macroscale sacrificial structure builder. The bio-inspired zeolitic replica inherited the complex spongy morphology and the intricate open-porous architecture of the biotemplate. Moreover, it exhibited reasonable mechanical stability in order to study the applicability of the biomorphic catalyst in a technical catalytic process. A bio-inspired catalytic reactor utilising the self-supporting ZSM-5 scaffold in monolithic configuration was developed in order to test the catalytic performance of the material

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

International Nuclear Information System (INIS)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15 -500 ) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15 -500 supported zirconium complexes were characterized by in situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands

Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

Energy Technology Data Exchange (ETDEWEB)

Leyrit, P.

1999-06-28

Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

Measurement of the hyperfine magnetic field on rhodium in chromium

International Nuclear Information System (INIS)

Peretto, P.; Teisseron, G.; Berthier, J.

1978-01-01

Hyperfine magnetic field of rhodium in a chromium matrix is studied. Anisotropy of rhodium 100 is + 0.17. Time dependence of angular correlation is given with a sample containing 145 ppm of rhodium despite the short life [fr

Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

Science.gov (United States)

Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

2009-01-01

One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

Nanodispersed Suspensions of Zeolite Catalysts for Converting Dimethyl Ether into Olefins

Science.gov (United States)

Kolesnichenko, N. V.; Yashina, O. V.; Ezhova, N. N.; Bondarenko, G. N.; Khadzhiev, S. N.

2018-01-01

Nanodispersed suspensions that are effective in DME conversion and stable in the reaction zone in a three-phase system (slurry reactor) are obtained from MFI zeolite commercial samples (TsVM, IK-17-1, and CBV) in liquid media via ultrasonic treatment (UST). It is found that the dispersion medium, in which ultrasound affects zeolite commercial sample, has a large influence on particle size in the suspension. UST in the aqueous medium produces zeolite nanoparticles smaller than 50 nm, while larger particles of MFI zeolite samples form in silicone or hydrocarbon oils. Spectral and adsorption data show that when zeolites undergo UST in an aqueous medium, the acid sites are redistributed on the zeolite surface and the specific surface area of the mesopores increases. Preliminary UST in aqueous media of zeolite commercial samples (TsVM, IK-17-1, and CBV) affects the catalytic properties of MFI zeolite nanodispersed suspensions. The selectivity of samples when paraffins and olefins form is largely due to superacid sites consisting of OH groups of hydroxonium ion H3O+.

Rhodium complexes as therapeutic agents.

Science.gov (United States)

Ma, Dik-Lung; Wang, Modi; Mao, Zhifeng; Yang, Chao; Ng, Chan-Tat; Leung, Chung-Hang

2016-02-21

The landscape of inorganic medicinal chemistry has been dominated by the investigation of platinum, and to a lesser extent ruthenium, complexes over the past few decades. Recently, complexes based on other metal centers such as rhodium have attracted attention due to their tunable chemical and biological properties as well as distinct mechanisms of action. This perspective highlights recent examples of rhodium complexes that show diverse biological activities against various targets, including enzymes and protein-protein interactions.

Synthesis of mesoporous zeolite catalysts by in situ formation of carbon template over nickel nanoparticles

DEFF Research Database (Denmark)

Abildstrøm, Jacob Oskar; Kegnæs, Marina; Hytoft, Glen

2016-01-01

A novel synthesis procedure for the preparation of the hierarchical zeolite materials with MFI structure based on the carbon templating method with in situ generated carbon template is presented in this study. Through chemical vapour deposition of coke on nickel nanoparticles supported on silica...... oxide, a carbon-silica composite is obtained and exploited as a combined carbon template/silica source for zeolite synthesis. This approach has several advantages in comparison with conventional carbon templating methods, where relatively complicated preparative strategies involving multistep...... impregnation procedures and rather expensive chemicals are used. Removal of the carbon template by combustion results in zeolite single crystals with intracrystalline pore volumes between 0.28 and 0.48 cm3/g. The prepared zeolites are characterized by XRD, SEM, TEM and physisorption analysis. The isomerization...

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

Energy Technology Data Exchange (ETDEWEB)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

2015-01-15

Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15{sub -500}) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15{sub -500} supported zirconium complexes were characterized by in situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

On multi-site damage identification using single-site training data

Science.gov (United States)

Barthorpe, R. J.; Manson, G.; Worden, K.

2017-11-01

This paper proposes a methodology for developing multi-site damage location systems for engineering structures that can be trained using single-site damaged state data only. The methodology involves training a sequence of binary classifiers based upon single-site damage data and combining the developed classifiers into a robust multi-class damage locator. In this way, the multi-site damage identification problem may be decomposed into a sequence of binary decisions. In this paper Support Vector Classifiers are adopted as the means of making these binary decisions. The proposed methodology represents an advancement on the state of the art in the field of multi-site damage identification which require either: (1) full damaged state data from single- and multi-site damage cases or (2) the development of a physics-based model to make multi-site model predictions. The potential benefit of the proposed methodology is that a significantly reduced number of recorded damage states may be required in order to train a multi-site damage locator without recourse to physics-based model predictions. In this paper it is first demonstrated that Support Vector Classification represents an appropriate approach to the multi-site damage location problem, with methods for combining binary classifiers discussed. Next, the proposed methodology is demonstrated and evaluated through application to a real engineering structure - a Piper Tomahawk trainer aircraft wing - with its performance compared to classifiers trained using the full damaged-state dataset.

Rhodium(II) Proximity-Labeling Identifies a Novel Target Site on STAT3 for Inhibitors with Potent Anti-Leukemia Activity.

Science.gov (United States)

Minus, Matthew B; Liu, Wei; Vohidov, Farrukh; Kasembeli, Moses M; Long, Xin; Krueger, Michael J; Stevens, Alexandra; Kolosov, Mikhail I; Tweardy, David J; Sison, Edward Allan R; Redell, Michele S; Ball, Zachary T

2015-10-26

Nearly 40 % of children with acute myeloid leukemia (AML) suffer relapse arising from chemoresistance, often involving upregulation of the oncoprotein STAT3 (signal transducer and activator of transcription 3). Herein, rhodium(II)-catalyzed, proximity-driven modification identifies the STAT3 coiled-coil domain (CCD) as a novel ligand-binding site, and we describe a new naphthalene sulfonamide inhibitor that targets the CCD, blocks STAT3 function, and halts its disease-promoting effects in vitro, in tumor growth models, and in a leukemia mouse model, validating this new therapeutic target for resistant AML. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zeolite ZSM5 catalysts for abatement of nitrogen oxide

Energy Technology Data Exchange (ETDEWEB)

Ganemi, Bager

1999-07-01

Airborne pollutants from the combustion of fossil fuels are a global problem. Emission of nitrogen oxides (NO{sub x}) is increasing with the worldwide increase in the use of energy. Atmospheric and photochemical reactions link nitrogen oxides to hydrocarbons and tropospheric ozone. The emission of NO{sub x} has to be tackled urgently in order to limit the harmful effects of anthropogenic activity on the environment. The subject of this thesis is catalytic nitrogen oxide abatement through direct decomposition and reduction by methane over ion-exchanged zeolite ZSM5. The work covers catalytic conversion and surface intermediates, including correlations with the level of exchanged Cu{sup 2+} cations and Ni{sup 2+} or Pd{sup 2+} co-cations. Special attention is given to the aluminium content of the support and changes in structural parameters. It was found that NO{sub x} conversion over cation-exchanged ZSM5 is strongly influenced by the ion-exchange procedure and by the above material parameters. Characterization of Cu-ZSM5 reveals that approximately two molecules of water per Cu{sup 2+} ion desorb at temperatures between 150 and 350 Deg C, in addition to the conventional dehydration at lower temperatures. The desorbed water comes from the decomposition of Cu(OH){sub 2}. Decomposition of hydroxylated copper ions results in the formation Of Cu{sup 2+}-O-Cu{sup 2+} dimers, which are suggested to be the active sites for catalytic decomposition of NO. Acid sites are important for the dispersion of copper ions on the catalyst surface. Acid sites are also important for the interaction between copper species and the zeolite. Increased acidity leads to a stronger interaction between the exchanged cation and the framework, i.e. the exchanged cations become more resistant to mobility. The stronger bond between the exchanged cations and lattice oxygen also prevents dealumination of the catalyst and decreases the thermal expansion at higher temperatures. The temperature of

Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

Directory of Open Access Journals (Sweden)

Zeeshan Nawaz

2009-12-01

Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

Co-remediation of the lead-polluted garden soil by exogenous natural zeolite and humic acids.

Science.gov (United States)

Shi, Wei-yu; Shao, Hong-bo; Li, Hua; Shao, Ming-an; Du, Sheng

2009-08-15

The current study reported the co-remediation effect on the lead-polluted garden soil by zeolite and humic acids (HA), which was from comparing with the remediation of single zeolite in term of the lead fraction of sequential extraction in the soil and the distribution of lead in different parts of rape. Mixed treatment (zeolite and HA) and single treatment (zeolite) were, respectively, applied to the artificially polluted garden soil to examine the difference of their remediation effects in pot experiment. Results indicated that the co-remediation led to significantly greater (plead concentration in plants than by singly adding to zeolite. The co-application of zeolite and HA reduced the available fraction of lead compounds, but slightly increased (plead compounds in the garden soil, compared with the application of single zeolite, especially in the severe lead-polluted soil (> or =1000 mg kg(-1)). This method might be an efficient way to remediate the lead-polluted soils on a large scale, although zeolite is a kind of hazardous material.

Effect of Ge/Si substitutions on the local geometry of Si framework sites in zeolites: A combined high resolutionsup29/supSi MAS NMR and DFT/MM study on zeolite Beta polymorph C (BEC)

Czech Academy of Sciences Publication Activity Database

Whittleton, Sarah R.; Vicente, A.; Fernandez, C.; Rastegar, Somayeh F.; Fishchuk, Anna V.; Sklenák, Štěpán

2018-01-01

Roč. 267, SEP 2018 (2018), s. 124-133 ISSN 1387-1811 R&D Projects: GA ČR(CZ) GA15-14007S Grant - others:Ga MŠk(CZ) LM2015070 Institutional support: RVO:61388955 Keywords : 29 Si MAS NMR * bec * Ge-zeolites * Germanoaluminosilicates * Zeolite Beta polymorph C Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.615, year: 2016

Application of Zeolitic Additives in the Fluid Catalytic Cracking (FCC

Directory of Open Access Journals (Sweden)

A. Nemati Kharat

2013-06-01

Full Text Available Current article describes application of zeolites in fluid catalytic cracking (FCC. The use of several zeolitic additives for the production light olefins and reduction of pollutants is described. Application of zeolites as fluid catalytic cracking (FCC catalysts and additives due to the presence of active acid sites in the zeolite framework  increase the formation of desired cracking products (i.e., olefin and branched products  in the FCC unit.

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers.

Science.gov (United States)

Mattioli, Michele; Giordani, Matteo; Dogan, Meral; Cangiotti, Michela; Avella, Giuseppe; Giorgi, Rodorico; Dogan, A Umran; Ottaviani, Maria Francesca

2016-04-05

Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si-O-Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity. Copyright © 2015 Elsevier B.V. All rights reserved.

Sorption of Fe3+ , Co2+ , Ce3+ , Cs+ and Ba2+ in zeolite X

International Nuclear Information System (INIS)

Martinez M, V.

1994-01-01

The sorption behavior of Fe 3+ , Co 2+ , Ce 3+ , Cs + , and Ba 2+ in aqueous solutions, was studied in presence of zeolite X. Solutions of Fe(NO 3 ) 3 . 9 H 2 O, Co(NO 3 ) 2 . 6 H 2 O, Ce(NO 3 ) 3 . 6 H 2 O, Cs NO 3 and Ba(NO 3 ) 2 were labelled with the respectively radioactive isotopes Fe 59 , Co 60 , Cs 134 , Ba 139 and Ce 141 . 20 ml. of each solution was left in contact with 200 mg. of zeolite for different periods. Later the zeolites were separated by centrifugation from the aqueous solutions and the radioactivity of the aqueous phases was measured with a NaI(Tl) solid-state well detector coupled to a single-channel Picker analyzer or with a Gel hyper pure solid-state detector coupled to a 2048 channel pulse height analyzer. When Cs + in the aqueous solutions was left in contact with zeolite X it was found that it does not occupy all cationic sites in the zeolite due to the ionic radium effect. A similar behavior was found for the divalent ions. In all cases, when the pH was not controlled, the zeolite lost part of its crystallinity and when the divalent ions were exchanged again by Na + , the zeolite recovered completely its crystallinity. During the sorption, the ionic radius, and the charge are important parameters as well as the pH. When the pH of the solution was adjusted between 6.5 - 7.0 the crystallinity was maintained in some cases. For Fe 3+ the crystallinity after the ion exchange was 94 % and when the pH was not adjusted the crystallinity was completely lost. It was found as well that the zeolite X induces the formation of H 3 O + which competes with the cations for the sites in the zeolite. (Author)

Zeolite Chemistry Studied at the Level of Single Particles, Molecules and Atoms

NARCIS (Netherlands)

Ristanovic, Z.

2016-01-01

Zeolites are microporous aluminosilicates that find a wide-spread application as catalysts in the oil refining and petrochemical industries. Zeolite acidity and related chemistry play a major role in numerous catalytic processes and it is of significant practical interest to understand their

Cyclopentadiene-mediated hydride transfer from rhodium complexes.

Science.gov (United States)

Pitman, C L; Finster, O N L; Miller, A J M

2016-07-12

Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

Kinetic method of determination of rhodium trace amounts

International Nuclear Information System (INIS)

Kalinina, V.E.; Lyakushina, V.M.; Rybina, A.E.

1978-01-01

A catalytic action of rhodium compounds has been detected and studied in the reaction of copper (2) tellurate oxidation with hypobromite to ditelluratocuprate (3) in an alkaline medium. The relationships between the reaction rate and concentrations of copper, tellurate, and hypobromite have been established. The optimum concentrations of the used compounds have been found: Csub(Cu(2))=4x10 -5 g-ion/l; Csub(OHsup(-))=3.0 g-ion/l; Csub(Te)=1.4x10 -2 g-ion/l; Csub(NaBrO)=2.17x10 -3 M. It has been established for chloride, sulphate, and perchlorate solutions of rhodium (3) and (4) that the reaction sensitivity increases by 2-3-fold with a temperature rise from 25-60 deg C. The technique of determining rhodium traces has been developed based on its catalytic action. The low limit of determined rhodium amounts is about 10 -3 mkg/ml

Rhodium enalcarbenoids: direct synthesis of indoles by rhodium(II)-catalyzed [4+2] benzannulation of pyrroles.

Science.gov (United States)

Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Kalepu, Jagadeesh; Chennamsetti, Haribabu; Lad, Bapurao Sudam; Katukojvala, Sreenivas

2014-04-14

Disclosed herein is the design of an unprecedented electrophilic rhodium enalcarbenoid which results from rhodium(II)-catalyzed decomposition of a new class of enaldiazo compounds. The synthetic utility of these enalcarbenoids has been successfully demonstrated in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles, thus leading to substituted indoles. The new benzannulation has been applied to the efficient synthesis of the natural product leiocarpone as well as a potent adipocyte fatty-acid binding protein inhibitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A bioscaffolding strategy for hierarchical zeolites with a nanotube-trimodal network.

Science.gov (United States)

Li, Guannan; Huang, Haibo; Yu, Bowen; Wang, Yun; Tao, Jiawei; Wei, Yingxu; Li, Shougui; Liu, Zhongmin; Xu, Yan; Xu, Ruren

2016-02-01

Hierarchical zeolite monoliths with multimodal porosity are of paramount importance as they open up new horizons for advanced applications. So far, hierarchical zeolites based on nanotube scaffolds have never been reported. Inspired by the organization of biominerals, we have developed a novel precursor scaffolding-solid phase crystallization strategy for hierarchical zeolites with a unique nanotube scaffolding architecture and nanotube-trimodal network, where biomolecular self-assembly (BSA) provides a scaffolding blueprint. By vapor-treating Sil-1 seeded precursor scaffolds, zeolite MFI nanotube scaffolds are self-generated, during which evolution phenomena such as segmented voids and solid bridges are observed, in agreement with the Kirkendall effect in a solid-phase crystallization system. The nanotube walls are made of intergrown single crystals rendering good mechanical stability. The inner diameter of the nanotube is tunable between 30 and 90 nm by varying the thickness of the precursor layers. Macropores enclosed by cross-linked nanotubes can be modulated by the choice of BSA. Narrow mesopores are formed by intergrown nanocrystals. Hierarchical ZSM-5 monoliths with nanotube (90 nm), micropore (0.55 nm), mesopore (2 nm) and macropore (700 nm) exhibit superior catalytic performance in the methanol-to-hydrocarbon (MTH) conversion compared to conventional ZSM-5. BSA remains intact after crystallization, allowing a higher level of organization and functionalization of the zeolite nanotube scaffolds. The current work may afford a versatile strategy for hierarchical zeolite monoliths with nanotube scaffolding architectures and a nanotube-multimodal network leading to self-supporting and active zeolite catalysts, and for applications beyond.

The effects of primary beam filters on the analysis of rhodium and cadmium using a rhodium target x-ray tube

International Nuclear Information System (INIS)

Anzelmo, J.A.; Boyer, B.W.

1986-01-01

Since its introduction in 1964, the thin end-window rhodium target x-ray tube has been considered to be an excellent general purpose source of excitation. Heavy elements are efficiently excited by high Bremsstrahlung and the K lines of rhodium while the light elements are excited by the L lines of rhodium. The ability to efficiently excite both heavy and light elements is essential to special applications such as auto catalysts, which are composed of precious metals in a clay-like matrix. Close control of the light elements, including sodium, phosphorous, aluminum and silicon, and the heavy element precious metals, such as rhodium, are necessary to keep operating characteristics and manufacturing expense at desired levels. A quick survey of typical x-ray tube targets shows that some targets are more efficient for light elements while others are more efficient for heavy elements. The few general purpose x-ray tubes that are available have characteristic lines which overlap on elements to be determined. The rhodium target, which is a good excitation source for most of the elements mentioned, contains line overlaps on cadmium (RHKB) and rhodium (RHKA). When using a sequential wavelength dispersive XRF spectrometer, the characteristic lines of the tube scattered from the sample can be removed by a programmable primary beam filter having an absorption edge just higher in wavelength than the wavelengths to be removed. The thickness and composition of the filter, as well as the choice of KV and MA, will determine the operating parameter necessary to achieve the optimum precision and lowest limits of detection. For this study, synthetic samples are made up using Kaolin as the matrix

Processing of radioactive waste solution with zeolites. I. Thermal transformation of Na, Cs and Sr type zeolites

Energy Technology Data Exchange (ETDEWEB)

Kanno, T; Mimura, H; Kitamura, T [Tohoku Univ., Sendai (Japan). Research Inst. of Mineral Dressing and Metallurgy

1976-08-01

Thermal transformation of Na, Cs and Sr type zeolites were studied by means of differential thermal analysis (DTA), thermogravimetric analysis (TGA) and X-ray powder diffraction. Synthetic zeolites A, X and Y, synthetic mordenite (Zeolon) and natural mordenite were used in this study. Na type zeolites of A and X recrystallized to Nepheline (NaAlSiO/sub 4/) above 1,000/sup 0/C, but the structures of zeolite Y and mordenite collapsed above about 900/sup 0/C and did not recrystallize until 1,200/sup 0/C. Cs type zeolites of A and X recrystallized to pollucite (CsAlSi/sub 2/O/sub 6/) above 1,000/sup 0/C and Cs type of zeolite Y recrystallized to it above 1,100/sup 0/C, but the structure of mordenite collapsed above 1,000/sup 0/C and did not recrystallize until 1,200/sup 0/C. On Sr type zeolites, zeolite A and X recrystallized to strontium aluminosilicate (SrAl/sub 2/Si/sub 2/O/sub 8/) above 1,100/sup 0/C and zeolite Y recrystallized to it above 1,200/sup 0/C, but the structure of mordenite collapsed above 1,000/sup 0/C. The results described above were supported by microscopic observation and the measurement of density. If this solidifications by calcination of zeolites are further studied, new informations concerning the fixation of Cs and Sr will be obtained.

Electronic and magnetic properties of ultrathin rhodium nanowires

CERN Document Server

Wang Bao Lin; Ren-Yun; Sun Hou Qian; Chen Xiao Shuang; Zhao Ji Jun

2003-01-01

The structures of ultrathin rhodium nanowires are studied using empirical molecular dynamics simulations with a genetic algorithm. Helical multishell cylindrical and pentagonal packing structures are found. The electronic and magnetic properties of the rhodium nanowires are calculated using an spd tight-binding Hamiltonian in the unrestricted Hartree-Fock approximation. The average magnetic moment and electronic density of states are obtained. Our results indicate that the electronic and magnetic properties of the rhodium nanowires depend not only on the size of the wire but also on the atomic structure. In particular, centred pentagonal and hexagonal structures can be unusually ferromagnetic.

Rhodium Catalyzed Decarbonylation

DEFF Research Database (Denmark)

Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

2017-01-01

Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

Zeolitic materials with hierarchical porous structures.

Science.gov (United States)

Lopez-Orozco, Sofia; Inayat, Amer; Schwab, Andreas; Selvam, Thangaraj; Schwieger, Wilhelm

2011-06-17

During the past several years, different kinds of hierarchical structured zeolitic materials have been synthesized due to their highly attractive properties, such as superior mass/heat transfer characteristics, lower restriction of the diffusion of reactants in the mesopores, and low pressure drop. Our contribution provides general information regarding types and preparation methods of hierarchical zeolitic materials and their relative advantages and disadvantages. Thereafter, recent advances in the preparation and characterization of hierarchical zeolitic structures within the crystallites by post-synthetic treatment methods, such as dealumination or desilication; and structured devices by in situ and ex situ zeolite coatings on open-cellular ceramic foams as (non-reactive as well as reactive) supports are highlighted. Specific advantages of using hierarchical zeolitic catalysts/structures in selected catalytic reactions, such as benzene to phenol (BTOP) and methanol to olefins (MTO) are presented. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroformylation of methyl oleate catalyzed by rhodium complexes

International Nuclear Information System (INIS)

Mendes, Ana Nery Furlan; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro

2012-01-01

In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H 2 ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

Quantification of Rhodium in a Series of Inorganic and ...

African Journals Online (AJOL)

NICO

... such as rhodium hydridocarbonyl tristriphenylphosphine, [HRh(CO)(PPh3)3], .... The selection of the most suitable wavelengths for rhodium, yttrium and cobalt ... chloride ions were removed from the CRM samples as chlorine gas with the ...

INTERKALASI XILENOL ORANGE PADA ZEOLIT ALAM LAMPUNG SEBAGAI ELEKTRODA ZEOLIT TERMODIFIKASI

Directory of Open Access Journals (Sweden)

Fitriyah Fitriyah

2016-07-01

Full Text Available Zeolit terbagi menjadi zeolit alam dan zeolit sintesis, kapasitas adsorpsi zeolit alam umumnya lebih rendah daripada zeolit sintesis, sehingga untuk meningkatkan kapasitas adsorpsinya, karakter permukaan zeolit alam perlu diubah dengan melakukan proses modifikasi permukaan melalui berbagai metode, salah satunya dengan metode interkalasi. Tujuan penelitian ini yaitu menginterkalasi zat warna xilenol orange ke dalam zeolit alam Lampung dan mengaplikasikannya sebagai elektroda zeolit termodifikasi. Melalui proses interkalasi diharapkan dapat meningkatkan kegunaan dan nilai tambah dari zeolit. Data hasil penelitian menunjukkan bahwa xilenol orange (XO dapat diinterkalasikan ke dalam zeolit, hal ini dapat dilihat dari pita spektrum FTIR yang memiliki serapan pada bilangan gelombang 1383 cm-1, yaitu menunjukkan serapan dari S=O simetris dan asimetris pada gugus –SO3H,hal ini diduga karena XO memiliki gugus SO3 sehingga menyebabkan adanya serangan pada proton zeolit. Berdasarkan penelitian dapat disarikan bahwa xilanol orange dapat terinterkalasi pada zeolit alam Lampung dan dapat dimanfaatkan sebagai elektroda pendeteksi logam.

An Extended X-ray Absorption Fine Structure Study of Rhodium-Oxygen Bonds in a Highly Dispersed Rhodium/Aluminum Oxide Catalyst

NARCIS (Netherlands)

Koningsberger, D.C.; Zon, J.B.A.D. van; Blik, H.F.J. van 't; Visser, G.J.; Prins, R.; Mansour, A.N.; Sayers, D.E.; Short, D.R.

1985-01-01

Analysis of in situ EXAFS measurements on a 2.4 wt % Rh/A120, catalyst, reduced at 473 K after calcination at 623 K, shows the presence of two different rhodium-oxygen bonds (viz. 2.05 and 2.68 A). The oxygen neighbors of rhodium at a distance of 2.05 A disappear after reduction at 673 K. The

Identification and Quantification of Copper Sites in Zeolites by Electron Paramagnetic Resonance Spectroscopy

DEFF Research Database (Denmark)

Godiksen, Anita; Vennestrøm, Peter N. R.; Rasmussen, Søren Birk

2017-01-01

Recent quantitative electron paramagnetic resonance spectroscopy (EPR) data on different copper species present in copper exchanged CHA zeolites are presented and put into context with the literature on other copper zeolites. Results presented herein were obtained using ex situ and in situ EPR...

Three Mile Island zeolite vitirification demonstration program

International Nuclear Information System (INIS)

Siemens, D.H.; Knowlton, D.E.; Shupe, M.W.

1981-06-01

The cleanup of the high-activity-level water at Three Mile Island (TMI) provides an opportunity to further develop waste management technology. Approximately 790,000 gallons of high-activity-level water at TMI's Unit-2 Nuclear Power Station will be decontaminated at the site using the submerged demineralizer system (SDS). In the SDS process, the cesium and strontium in the water are sorbed onto zeolite that is contained within metal liners. The Department of Energy has asked the Pacific Northwest Laboratory (PNL) to take a portion of the zeolite from the SDS process and demonstrate, on a production scale, that this zeolite can be vitrified using the in-can melting process. This paper is a brief overview of the TMI zeolite vitrification program. The first section discusses the formulation of a glass suitable for immobilizing SDS zeolite. The following section describes a feed system that was developed to feed zeolite to the in-can melter. It also describes the in-can melting process and the government owned facilities in which the demonstrations will take place. Finally, the schedule for completing the program activities is outlined

Multicomponent liquid ion exchange with chabazite zeolites

International Nuclear Information System (INIS)

Robinson, S.M.; Arnold, W.D. Jr.; Byers, C.W.

1993-10-01

In spite of the increasing commercial use of zeolites for binary and multicomponent sorption, the understanding of the basic mass-transfer processes associated with multicomponent zeolite ion-exchange systems is quite limited. This study was undertaken to evaluate Na-Ca-Mg-Cs-Sr ion exchange from an aqueous solution using a chabazite zeolite. Mass-transfer coefficients and equilibrium equations were determined from experimental batch-reactor data for single and multicomponent systems. The Langmuir isotherm was used to represent the equilibrium relationship for binary systems, and a modified Dubinin-Polyani model was used for the multicomponent systems. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. Macropore diffusion also significantly contributes to the mass-transfer resistance. Various mass-transfer models were compared to the experimental data to determine mass-transfer coefficients. Effective diffusivities were obtained which accurately predicted experimental data using a variety of models. Only the model which accounts for micropore and macropore diffusion occurring in series accurately predicted multicomponent data using single-component diffusivities. Liquid and surface diffusion both contribute to macropore diffusion. Surface and micropore diffusivities were determined to be concentration dependent

Zeolite studies. Aluminium phosphate zeolites

Energy Technology Data Exchange (ETDEWEB)

Haegh, G.S.; Blindheim, U.

1983-12-01

Alpo-zeolites (ALPO4-zeolites) have been synthesized by hydrothermal synthesis in an autoclave from alumina, tetralkylammonium hydroxide and phosphorus acid. Catalysis tests with hydrocarbons indicate that the compounds have good olefinisomerization activity and selectivity.

Nonlinear upconversion based infrared spectroscopy on ZSM-5 zeolite

DEFF Research Database (Denmark)

Kehlet, Louis Martinus; Beato, Pablo; Tidemand-Lichtenberg, Peter

2017-01-01

We present a spectroscopic measurement of zeolite ZSM-5 in the mid-IR following the methanol attachment to active sites at 200 °C. The spectra are measured using nonlinear frequency upconversion to the near-IR spectral region.......We present a spectroscopic measurement of zeolite ZSM-5 in the mid-IR following the methanol attachment to active sites at 200 °C. The spectra are measured using nonlinear frequency upconversion to the near-IR spectral region....

TPR investigations on the reducibility of Cu supported on Al2O3, zeolite Y and SAPO-5

International Nuclear Information System (INIS)

Hoang, Dang Lanh; Dang, Thi Thuy Hanh; Engeldinger, Jana; Schneider, Matthias; Radnik, Joerg; Richter, Manfred; Martin, Andreas

2011-01-01

Reducibility of Cu supported on Al 2 O 3 , zeolite Y and silicoaluminophosphate SAPO-5 has been investigated in dependence on the Cu content using a method combining conventional temperature programmed reduction (TPR) by hydrogen with reoxidation in N 2 O followed by a second the so-called surface-TPR (s-TPR). The method enables discrimination and a quantitative estimation of the Cu oxidation states +2, +1 and 0. The quantitative results show that the initial oxidation state of Cu after calcination in air at 400 deg. C, independent on the nature of the support, is predominantly +2. Cu 2+ supported on Al 2 O 3 is quantitatively reduced by hydrogen to metallic Cu 0 . Comparing the TPR of the samples calcined in air and that of samples additionally pre-treated in argon reveals that in zeolite Y and SAPO-5 Cu 2+ cations are stabilized as weakly and strongly forms. In both systems, strongly stabilized Cu 2+ ions are not auto-reduced by pre-treatment in argon at 650 deg. C, but are reduced in hydrogen to form Cu + . The weakly stabilized Cu 2+ ions, in contrast, may be auto-reduced by pre-treatment in argon at 650 deg. C forming Cu + but are reduced in hydrogen to metallic Cu 0 . - Graphical Abstract: TPR, TPR-(act), s-TPR and s-TPR-(act) profiles of (1.36)Cu/SAPO-5 (A), (4.55)Cu/SAPO-5 (B) and (9.19)Cu/SAPO-5 (C) samples. The intensities of TCD signals in (A) and (B) are multiplied by 4.5 and 2, respectively. Highlights: → Cu supported on SAPO-5, alumina and zeolite Y was investigated by TPR and s-TPR. → Cu oxidation states can be discriminated and quantitatively determined. → In zeolite Y and SAPO-5 Cu 2+ cations are stabilized at weak and strong forms. → Strongly stabilized Cu 2+ cannot be auto-reduced in argon at 650 deg. C.

Mesoporous MEL, BEA, and FAU zeolite crystals obtained by in situ formation of carbon template over metal nanoparticles

DEFF Research Database (Denmark)

Abildstrøm, Jacob Oskar; Ali, Zahra Nasrudin; Mentzel, Uffe Vie

2016-01-01

Here, we report the synthesis and characterization of hierarchical zeolite materials with MEL, BEA and FAU structures. The synthesis is based on the carbon templating method with an in situ-generated carbon template. Through the decomposition of methane and deposition of coke over nickel nanopart......Here, we report the synthesis and characterization of hierarchical zeolite materials with MEL, BEA and FAU structures. The synthesis is based on the carbon templating method with an in situ-generated carbon template. Through the decomposition of methane and deposition of coke over nickel...... nanoparticles supported on silica, a carbon–silica composite is obtained and exploited as a combined carbon template/silica source for the zeolite synthesis. The mesoporous zeolite materials were all prepared by hydrothermal crystallization in alkaline media followed by removal of the carbon template...... by combustion, which results in zeolite single crystals with intracrystalline pore volumes of up to 0.44 cm3 g−1. The prepared zeolite structures are characterized by XRD, SEM, TEM and N2 physisorption measurements....

Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

Science.gov (United States)

Martin, S C; Minus, M B; Ball, Z T

2016-01-01

Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

Kalman filtering for rhodium self-powered neutron detectors

International Nuclear Information System (INIS)

Kantrowitz, M.L.

1988-01-01

Rhodium self-powered neutron detectors are utilized in many pressurized water reactors to determine the neutronic behavior within the core. In order to compensate for the inherent time delay associated with the response of these detectors, a dynamic compensation algorithm is currently used in Combustion Engineering plants to reconstruct the dynamic flux signal which is being sensed by the rhodium detectors. This paper describes a new dynamic compensation algorithm, based on Kalman filtering, which improves on the noise gain and response time characteristics of the algorithm currently used, and offers the possibility of utilizing the proven rhodium detector based fixed in-core detector system as an integral part of advanced core control and/or protection systems

Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites.

Science.gov (United States)

Sökmen, Ilkay; Sevin, Fatma

2003-08-01

The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.

Bifunctional Rhodium Intercalator Conjugates as Mismatch-Directing DNA Alkylating Agents

OpenAIRE

Schatzschneider, Ulrich; Barton, Jacqueline K.

2004-01-01

A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covale...

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

Energy Technology Data Exchange (ETDEWEB)

Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.; Miller, Jeffrey T.; Delferro, Massimiliano; Stair, Peter C.; Marks, Tobin J.

2016-08-23

A single-site molybdenum dioxo catalyst, (O_c)₂Mo(=O)₂@C, was prepared via direct grafting of MoO₂Cl₂(dme) (dme = 1,2-dimethoxyethane) on high-surface- area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N₂ physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H₂ (TPR-H₂), and temperature-programmed NH₃ desorption (TPD-NH₃). The single-site nature of the Mo species is corroborated by XPS and TPR-H₂ data, and it exhibits the lowest reported MoO_x Tmax of reduction reported to date, suggesting a highly reactive MoVI center. (O_c)₂Mo(=O)₂@C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60-90 °C) and with negligible deactivation. (O_c)₂Mo(=O)₂@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol^-1 and ΔS = -32(2) eu. The low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and lowcost catalyst with significant potential for transesterification processes.

Robotic-assisted single-port donor nephrectomy using the da Vinci single-site platform.

Science.gov (United States)

LaMattina, John C; Alvarez-Casas, Josue; Lu, Irene; Powell, Jessica M; Sultan, Samuel; Phelan, Michael W; Barth, Rolf N

2018-02-01

Although single-port donor nephrectomy offers improved cosmetic outcomes, technical challenges have limited its application to selected centers. Our center has performed over 400 single-port donor nephrectomies. The da Vinci single-site robotic platform was utilized in an effort to overcome the steric, visualization, ergonomic, and other technical limitations associated with the single-port approach. Food and Drug Administration device exemption was obtained. Selection criteria for kidney donation included body mass index da Vinci single-site platform. Our experience supported the safety of this approach but found that the technology added cost and complexity without tangible benefit. Development of articulating instruments, energy, and stapling devices will be necessary for increased application of robotic single-site surgery for donor nephrectomy. Copyright © 2017 Elsevier Inc. All rights reserved.

Preparation and Characterization of Zeolite Membrane for Bioethanol Purification

Directory of Open Access Journals (Sweden)

Aprilina Purbasari

2013-06-01

Full Text Available The use of bioethanol as an alternative fuel with a purity of more than 99.5% wt has prompted research on bioethanol purification. One of the promising methods used for bioethanol purification is pervaporation membrane. This research is aimed to prepare and characterize zeolite membranes for pervaporation membrane. The membrane preparation consisted of two stages, namely support preparation and zeolite deposition on the support. In support preparation, α- alumina and kaolin with specific composition (50:30; 40:40; 50:30 was mixed with additives and water. After pugging and aging process, the mixture became paste and extruded into tubular shape. The tube was then calcined at temperature of 1250 °C for 3 hours. After that, zeolite 4A was deposited on the tubes using clear solution made of 10 %wt zeolite and 90 %wt water and heated at temperature of 80 °C for 3 hours. Furthermore, the resulting zeolite membranes was washed with deionized water for 5 minutes and dried in oven at temperature of 100 °C for 24 hours. Characterization of zeolite membranes included mechanical strength test, XRD, and SEM. In the mechanical strength test, the membrane sample with α- alumina:kaolin = 50:30 (membrane A has the highest mechanical strength of 46.65 N/mm2. Result of XRD analysis for the membrane A indicated that mullite and corundum phases were formed, which mullite phase was more dominant. Meanwhile the result of SEM analysis shows that zeolite crystals have been formed and covered the pores support, but the deposition of zeolite has not been optimal yet. The performance examination for bioethanol purification showed that the membrane could increase the purity of bioethanol from 95% to 98.5% wt. © 2013 BCREC UNDIP. All rights reservedReceived: 23rd October 2012; Revised: 15th February 2013; Accepted: 16th February 2013[How to Cite: Purbasari, A., Istirokhatun, T., Devi, A.M., Mahsunnah, L. , Susanto, H. (2013. Preparation and Characterization of Zeolite

Low gravity containerless processing of immiscible gold rhodium alloys

Science.gov (United States)

Andrews, J. Barry

1986-01-01

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

Science.gov (United States)

2011-01-01

Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development. PMID:21443799

Optimization of sodium loading on zeolite support for catalyzed transesterification of triolein with methanol.

Science.gov (United States)

Wang, Yu-Yuan; Chou, Hsin-Yu; Chen, Bing-Hung; Lee, Duu-Jong

2013-10-01

Optimization of sodium loading on zeolite HY for catalyzed transesterification of triolein in excess methanol to biodiesel was studied. Zeolite HY catalyst was activated by loading sodium ions to their surface via an ion-exchange method. The effects of ion-exchange process parameters, including the temperature, the process time, the pH value, as well as concentrations and sources of Na(+) cations (NaOH, NaCl and Na2SO4), on the conversion yield of triolein to biodiesel were investigated. Most of these Na(+)-activated zeolite HY catalysts could really facilitate the catalyzed transesterification reaction of triolein to biodiesel at a lower temperature near 65°C. Consequently, a high conversion yield of triglycerides to biodiesel at 97.3% was obtained at 65°C. Moreover, the durability of zeolite catalysts was examined as well. Catalytic performance tests of these zeolite catalysts in transesterification did not show a significant decrease in catalysis at least for three batch cycles. Copyright © 2013 Elsevier Ltd. All rights reserved.

Local Electric Field Effects on Rhodium-Porphyrin and NHC-Gold Catalysts

Science.gov (United States)

2015-01-05

AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium -Porphyrin and NHC-Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...Stanford University Grant/Contract Title The full title of the funded effort. (NII)-Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold

Cell-Selective Biological Activity of Rhodium Metalloinsertors Correlates with Subcellular Localization

Science.gov (United States)

Komor, Alexis C.; Schneider, Curtis J.; Weidmann, Alyson G.; Barton, Jacqueline K.

2013-01-01

Deficiencies in the mismatch repair (MMR) pathway are associated with several types of cancers, as well as resistance to commonly used chemotherapeutics. Rhodium metalloinsertors have been found to bind DNA mismatches with high affinity and specificity in vitro, and also exhibit cell-selective cytotoxicity, targeting MMR-deficient cells over MMR-proficient cells. Ten distinct metalloinsertors with varying lipophilicities have been synthesized and their mismatch binding affinities and biological activities determined. Although DNA photocleavage experiments demonstrate that their binding affinities are quite similar, their cell-selective antiproliferative and cytotoxic activities vary significantly. Inductively coupled plasma mass spectrometry (ICP-MS) experiments have uncovered a relationship between the subcellular distribution of these metalloinsertors and their biological activities. Specifically, we find that all of our metalloinsertors localize in the nucleus at sufficient concentrations for binding to DNA mismatches. However, the metalloinsertors with high rhodium localization in the mitochondria show toxicity that is not selective for MMR-deficient cells, whereas metalloinsertors with less mitochondrial rhodium show activity that is highly selective for MMR-deficient versus proficient cells. This work supports the notion that specific targeting of the metalloinsertors to nuclear DNA gives rise to their cell-selective cytotoxic and antiproliferative activities. The selectivity in cellular targeting depends upon binding to mismatches in genomic DNA. PMID:23137296

Intergrown new zeolite beta polymorphs with interconnected 12-ring channels solved by combining electron crystallography and single-crystal X-ray diffraction

KAUST Repository

Yu, Zhengbao; Han, Yu; Zhao, Lan; Huang, Shiliang; Zheng, Qiyu; Lin, Shuangzheng; Cõ rdova, Armando C.; Zou, Xiaodong; Sun, Junliang

2012-01-01

Two new polymorphs of zeolite beta, denoted as SU-78A and SU-78B, were synthesized by employing dicyclohexylammonium hydroxides as organic structure-directing agents. The structure was solved by combining transmission electron microscopy and single

Catalytic hydrodeoxygenation of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolites

International Nuclear Information System (INIS)

Lee, Hyung Won; Jun, Bo Ram; Kim, Hannah; Kim, Do Heui; Jeon, Jong-Ki; Park, Sung Hoon; Ko, Chang Hyun; Kim, Tae-Wan; Park, Young-Kwon

2015-01-01

The hydrodeoxygenation of 2-methoxy phenol and dibenzofuran, which are representative model compounds of bio-oil, was performed using two different Pt/mesoporous zeolite catalysts, Pt/mesoporous Y and Pt/mesoporous MFI. The reforming of 2-methoxy phenol and dibenzofuran via catalytic hydrodeoxygenation was investigated using a batch reactor at 40 bar and 250 °C. The characteristics of the catalysts were analyzed by N 2 adsorption-desorption, X-ray diffraction, and NH 3 temperature programmed desorption. Pt/mesoporous zeolite catalysts containing both strong acid sites and mesopores showed the higher conversion of 2-methoxy phenol than Pt/SiO 2 and Pt/Si-MCM-48 with no acid sites, Pt/γ-Al 2 O 3 , and a mixture of mesoporous Y and Pt/SiO 2 , indicating the importance of both Pt and strong acid sites for high catalytic activity. Among the two Pt/mesoporous zeolite catalysts tested, the conversion of 2-methoxy phenol to cyclohexane over Pt/mesoporous Y was much higher than that over the Pt/mesoporous MFI. This was attributed to the better textural properties, such as surface area, pore volume and micropore size, compared to those of Pt/mesoporous MFI. The catalytic conversions of dibenzofuran obtained using two Pt/mesoporous zeolite catalysts were similar and the main products were 1,1′-bicyclohexyl, cyclopentylmethyl-cyclohexane and cyclohexane. In addition, the reaction mechanisms of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolite were suggested. - Highlights: • HDO of 2-methoxy phenol and dibenzofuran was performed over Pt/mesoporous zeolites. • Pt/mesoporous zeolites have mesopores and strong acid sites. • Main product of HDO of 2-methoxy phenol was cyclohexane. • Main products of HDO of dibenzofuran were bicyclohexyl (BCH), i-BCH, and cyclohexane

Transition phases of zeolite Faujasite type to Sodalite by thermal treatment

Directory of Open Access Journals (Sweden)

Katia K. Kaminishikawahara

2015-10-01

Full Text Available The zeolites can have several functions as catalysts (biofuel production and molecular sieves (treatment of contaminated areas. This study aims to characterize the zeolites obtained in the transition of a Faujasite like zeolite into a Sodalite, when submitted to different thermal treatment times. The synthesized zeolites were characterized by X-ray diffraction where the crystalline phases were identified: Faujasite, Sodalite, SiO2 and amorphous material. The 4 hours heat treatment produces zeolite crystal structure similar to Faujasite, having basic sites, surface area of 552.7 m2 g-1 , and pore volume of 0.3391 cm3 g-1. With increasing time of heat treatment was observed the transition to the Sodalite phase witch containing 0.277 mmol g-1 of basic active sites with surface area of 11.38 m2 g-1 and pore volume of 0.0651 cm3 g-1. By the Rietveld method was identified and quantified the presence of Sodalite and Hidrossodalite in samples with 24 and 30 hours of reaction times.

Electronic and magnetic properties of small rhodium clusters

Energy Technology Data Exchange (ETDEWEB)

Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework. The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.

The UV Plasmonic Behavior of Distorted Rhodium Nanocubes

Directory of Open Access Journals (Sweden)

Yael Gutiérrez

2017-12-01

Full Text Available For applications of surface-enhanced spectroscopy and photocatalysis, the ultraviolet (UV plasmonic behavior and charge distribution within rhodium nanocubes is explored by a detailed numerical analysis. The strongest plasmonic hot-spots and charge concentrations are located at the corners and edges of the nanocubes, exactly where they are the most spectroscopically and catalytically active. Because intense catalytic activity at corners and edges will reshape these nanoparticles, distortions of the cubical shape, including surface concavity, surface convexity, and rounded corners and edges, are also explored to quantify how significantly these distortions deteriorate their plasmonic and photocatalytic properties. The fact that the highest fields and highest carrier concentrations occur in the corners and edges of Rh nanocubes (NCs confirms their tremendous potential for plasmon-enhanced spectroscopy and catalysis. It is shown that this opportunity is fortuitously enhanced by the fact that even higher field and charge concentrations reside at the interface between the metal nanoparticle and a dielectric or semiconductor support, precisely where the most chemically active sites are located.

Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms.

Science.gov (United States)

Demirci, Selami; Ustaoğlu, Zeynep; Yılmazer, Gonca Altın; Sahin, Fikrettin; Baç, Nurcan

2014-02-01

Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag(+) ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.

Retention of Cs on zeolite, bentonite and their mixtures

International Nuclear Information System (INIS)

Atun, G.

2002-01-01

The sorption behavior of cesium on zeolite and bentonite minerals and their mixtures was studied by means of a batch method and a tracer technique. All experiments were carried out in the presence of CsCl spiked with 137 Cs and NaCl as a supporting electrolyte in varying concentrations. The distribution coefficients (K D ) did not show significant differences at low Cs + loadings while they decreased in the high loading region. Freundlich and D-R isotherms were applied to the adsorption data of zeolite and bentonite. Adsorption capacities and mean energies calculated from D-R isotherm parameters decreased by increasing ionic strength on both minerals. The identification of the specific uptake sites was attempted on the basis of the Freundlich isotherm. Experimentally observed distribution coefficients of Cs on two mineral mixtures were smaller than theoretically calculated values, except at the highest NaCl concentration. (author)

Electrochemical behavior of rhodium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in

2008-02-15

Electrochemical behavior of rhodium(III) chloride in 1-butyl-3-methylimidazolium chloride was investigated by various electrochemical transient techniques at glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram of rhodium(III) in bmimCl consisted of a surge in reduction current occurring at a potential of -0.48 V (vs. Pd) is due to the reduction of Rh(III) to metallic rhodium and a very small oxidation wave occurring at -0.1 V. Increase of scan rate increases the peak current and remarkably shifts the cathodic peak potential (E{sub p}{sup c1}) in negative direction indicating the irreversibility of electroreduction of rhodium(III). The diffusion coefficient of rhodium(III) in bmimCl ({approx}10{sup -9} cm{sup 2}/s) was determined and the energy of activation ({approx}25 kJ/mol) was deduced from cyclic voltammograms at various temperatures. The cathodic ({tau}{sub r}) and anodic ({tau}{sub o}) transition times were measured from chronopotential transients and the ratio {tau}{sub o}/{tau}{sub r} was found to be 1:7. Electrowinning of rhodium from bmimCl medium results in a deposition of metallic rhodium with lower (20-25%) Faradaic efficiency. A separation factor of rhodium from co-existing noble metal fission product palladium in bmimCl was determined during electrodeposition.

Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

DEFF Research Database (Denmark)

Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren

2013-01-01

on the four different zeolite supports H-beta, H-Y, H-mordenite, and H-ZSM-5 with 1–10 wt% vanadia loading were prepared and characterized by nitrogen physisorption, X-ray powder diffraction, scanning electron  microscopy, ammonia temperature-programmed desorption, Raman spectroscopy and UV...

Zeolite from fly ash: synthesis and characterization

Indian Academy of Sciences (India)

Unknown

to attempt making zeolite from fly ash (Höller and Wir- sching 1985; Henmi ... thermal treatment method to synthesize low silica NaX- type zeolite from .... catalytic applications. Mixture of ... amount of Fe2O3 and the oxides of Mg, Ca, P, Ti etc. The chemical ..... This work is partly supported by the Ministry of Human. Resource ...

Hydrothermal conversion of FAU zeolite into RUT zeolite in TMAOH system

OpenAIRE

Jon, Hery; Takahashi, Shoutarou; Sasaki, Hitoshi; Oumi, Yasunori; Sano, Tsuneji

2008-01-01

The highly crystalline and pure RUT (RUB-10) zeolite could be obtained from the hydrothermal conversion of FAU zeolite used as a crystalline Si/Al source in tetramethylammonium hydroxide (TMAOH) media. As compared to amorphous silica/Al(OH)3 and amorphous silica/γ-Al2O3 sources, the crystallization rate for the formation of RUT zeolite was clearly faster when FAU zeolite was employed as the Si/Al source. Moreover, it was found that the hydrothermal conversion of FAU zeolite into RUT zeolite d...

Substitution clustering in a non-stoichiometric celsian synthesized by the thermal transformation of barium exchanged zeolite X

International Nuclear Information System (INIS)

Clayden, Nigel J.; Esposito, Serena; Ferone, Claudio; Pansini, Michele

2006-01-01

The thermal transformation of Ba exchanged zeolite X to celsian has been studied by 27 Al and 29 Si MAS NMR spectroscopy. Evidence for the degradation of the zeolite framework is present in the 29 Si NMR spectra after thermal treatment at 850 deg. C. Confirmation is provided by the 29 Si NMR data that synthesis of celsian via the decomposition of Ba exchanged zeolite leads to a single defect phase. Clustering of the isomorphous replacement of aluminium by silicon must occur to explain the observed 29 Si chemical shifts. The 27 Al NMR data show distorted aluminium co-ordination sites upon the thermal transformation of Ba exchanged zeolite X. The distortions present in the amorphous matrix are greater than those present in the monoclinic and hexagonal crystalline phases of celsian. - Graphical abstract: Monte Carlo simulation of the Q 4 (mAl) silicon connectivity in the α-hexagonal celsian lattice, for a Si/Al ratio of 1:1. Si atoms are shown in yellow and the Al atoms in black

Bendable Zeolite Membranes: Synthesis and Improved Gas Separation Performance.

Science.gov (United States)

Wang, Bo; Ho, W S Winston; Figueroa, Jose D; Dutta, Prabir K

2015-06-23

Separation and sequestration of CO2 emitted from fossil energy fueled electric generating units and industrial facilities will help in reducing anthropogenic CO2, thereby mitigating its adverse climate change effects. Membrane-based gas separation has the potential to meet the technical challenges of CO2 separation if high selectivity and permeance with low costs for large-scale manufacture are realized. Inorganic zeolite membranes in principle can have selectivity and permeance considerably higher than polymers. This paper presents a strategy for zeolite growth within the pores of a polymer support, with crystallization time of an hour. With a thin coating of 200-300 nm polydimethylsiloxane (PDMS) on the zeolite-polymer composite, transport data for CO2/N2 separation indicate separation factors of 35-45, with CO2 permeance between 1600 and 2200 GPU (1 GPU = 3.35 × 10(-10) mol/(m(2) s Pa)) using dry synthetic mixtures of CO2 and N2 at 25 °C. The synthesis process results in membranes that are highly reproducible toward transport measurements and exhibit long-term stability (3 days). Most importantly, these membranes because of the zeolite growth within the polymer support, as contrasted to conventional zeolite growth on top of a support, are mechanically flexible.

Solvent extraction of no-carrier-added 103Pd from irradiated rhodium target with α-furyldioxime

International Nuclear Information System (INIS)

Mahdi Sadeghi; Behrouz Shirazi; Nami Shadanpour

2006-01-01

Solvent extraction of no-carrier-added 103 Pd was investigated from irradiated rhodium target with a-furyldioxime in chloroform from diluted hydrochloric acid. Extraction yield was 85.3% for a single extraction from 0.37M HCl and 103 Pd purity was better than 99%. (author)

Hydrogen storage in Chabazite zeolite frameworks.

Science.gov (United States)

Regli, Laura; Zecchina, Adriano; Vitillo, Jenny G; Cocina, Donato; Spoto, Giuseppe; Lamberti, Carlo; Lillerud, Karl P; Olsbye, Unni; Bordiga, Silvia

2005-09-07

We have recently highlighted that H-SSZ-13, a highly siliceous zeolite (Si/Al = 11.6) with a chabazitic framework, is the most efficient zeolitic material for hydrogen storage [A. Zecchina, S. Bordiga, J. G. Vitillo, G. Ricchiardi, C. Lamberti, G. Spoto, M. Bjørgen and K. P. Lillerud, J. Am. Chem. Soc., 2005, 127, 6361]. The aim of this new study is thus to clarify both the role played by the acidic strength and by the density of the polarizing centers hosted in the same framework topology in the increase of the adsorptive capabilities of the chabazitic materials towards H2. To achieve this goal, the volumetric experiments of H2 uptake (performed at 77 K) and the transmission IR experiment of H2 adsorption at 15 K have been performed on H-SSZ-13, H-SAPO-34 (the isostructural silico-aluminophosphate material with the same Brønsted site density) and H-CHA (the standard chabazite zeolite: Si/Al = 2.1) materials. We have found that a H2 uptake improvement has been obtained by increasing the acidic strength of the Brønsted sites (moving from H-SAPO-34 to H-SSZ-13). Conversely, the important increase of the Brønsted sites density (moving from H-SSZ-13 to H-CHA) has played a negative role. This unexpected behavior has been explained as follows. The additional Brønsted sites are in mutual interaction via H-bonds inside the small cages of the chabazitic framework and for most of them the energetic cost needed to displace the adjacent OH ligand is higher than the adsorption enthalpy of the OH...H2 adduct. From our work it can be concluded that proton exchanged chabazitic frameworks represent, among zeolites, the most efficient materials for hydrogen storage. We have shown that a proper balance between available space (volume accessible to hydrogen), high contact surface, and specific interaction with strong and isolated polarizing centers are the necessary characteristics requested to design better materials for molecular H2 storage.

Synthesis, single-crystal structure refinement and Fe/T site preference in the ternary borides Fe {sub x}T{sub 7-x}B{sub 3} (T = Ru, Rh; 0 < x {<=} 1.5)

Energy Technology Data Exchange (ETDEWEB)

Fokwa, Boniface P.T. [Institut fuer Anorganische Chemie, Rheinisch-Westfaelische Technische Hochschule Aachen, D-52056 Aachen (Germany); Dronskowski, Richard [Institut fuer Anorganische Chemie, Rheinisch-Westfaelische Technische Hochschule Aachen, D-52056 Aachen (Germany)]. E-mail: drons@HAL9000.ac.rwth-aachen.de

2007-01-31

Single crystals of the borides Fe {sub x}Rh{sub 7-x}B{sub 3} (1 < x < 1.5) and Fe {sub x}Ru{sub 7-x}B{sub 3} (0 < x < 1) have been synthesized by arc-melting the elements in a water-cooled copper crucible under argon atmosphere. The silver-like products, structurally characterized by single-crystal X-ray analysis, adopt the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3} mc, no. 186) with Z = 2. Their structures consist of layers of boron-centered trigonal prisms of rhodium or ruthenium (Rh;Ru) and iron on the one side, and one-dimensional channels of face-sharing octahedral (Rh;Ru){sub 6} clusters on the other. Unlike in FeRh{sub 6}B{sub 3}, the iron substitution takes place at two (6c and 2b) of the three available rhodium/ruthenium positions, with a preference for the 6c site in the case of the Fe {sub x}Rh{sub 7-x}B{sub 3} compounds but not for Fe {sub x}Ru{sub 7-x}B{sub 3}.

Adsorption of aqueous Zn(II) species on synthetic zeolites

International Nuclear Information System (INIS)

Badillo-Almaraz, Veronica; Trocellier, Patrick; Davila-Rangel, Ignacio

2003-01-01

To supply a good quality drinkable water tends to become a strategic task in both developed and under development countries in the world due to the number of potential contamination sources. One of the major problems is derived from the presence of heavy toxic metals like zinc or lead resulting from industrial activities. Zeolites are known as very efficient mineral substrates for fixing aqueous ionic species through their wide range of channels present in the crystalline structure and due to their strong surface reactivity. MicroPIXE coupled with microRBS (3.05 MeV 4 He + ions) have been used to quantify the incorporation of zinc within two commercial zeolites containing alkali elements (zeolite X and clinoptilolite) in the concentration range of: 0.0002-0.05 M at neutral pH. At the beginning of the interaction between zeolite and Zn(II) solution, the adsorption process exhibits a direct proportionality between the content of zinc fixed on the mineral substrate and the aqueous concentration up to 0.01 M. Beyond this point a saturation effect seems to occur, indicating the strong decrease of available adsorption sites. Sodium or potassium ions are probably exchanged with Zn(II) ions during this process. The compared behaviour of the two zeolites is then discussed in terms of kinetic effects based on ionic radius values. A co-adsorption test carried on with a 50-50% Zn(II) 0.001 M-Pb(II) 0.001 M solution shows that lead does not occupy the same sites as zinc because the content of zinc fixed on the zeolite sample exactly corresponds to the result obtained with a pure 0.001 M Zn(II) solution. All these data clearly showed that zeolite surface reactivity is greatly influenced by the mineral cage-like structure and particularly the presence of pockets, spaces and channels

About the extraction recovery of fission rhodium from radioactive wastes

International Nuclear Information System (INIS)

Khaperskaya, A.V.; Renard, E.V.; Koltunov, V.S.

2000-01-01

The report will cover a radically new approach to the problem of rhodium recovery from HLLW after the transformation of kinetically inert poly-aqua cation of trivalent rhodium (which is not recoverable by the majority known extractants) to Rh (IV) form by chemical methods. Presented are the research results of Rh (IV) extraction from nitric acid solutions by several extractants that are of considerable current use in noble metals and radiochemical industries (tri-n-butyl phosphate, di-octyl-sulphide, tri-n-octylamine, quaternary ammonium bases). High level of rhodium extraction has been found for the above extractants: for several systems, for example, tri-n-octylamine - diethyl-benzene, rhodium distribution coefficient achieves high values (10-plus), as well as the sufficient extraction kinetics. Rhodium extraction increases with a decrease of the acidity, a rise in phase mixing time and in the following series: tri-n-butyl phosphate → di-octyl-sulphide → quaternary ammonium bases → tri-n-octylamine. Rh (IV) can be easily reduced to non-extractable Rh (III) by such reductants as Fe (II), HCOOH, C 6 H 8 O 6 , NH 2 OH, N 2 H 4 et al, that may be applied for the re-extraction process. (authors)

Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

Science.gov (United States)

Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

2015-04-08

Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.

Study of iron exchanged zeolites by Moessbauer effect and electron spin resonance spectroscopy

International Nuclear Information System (INIS)

Aguirre Campuzano, C.E.

1993-01-01

Crystalline iron exchanged NaY zeolites, prepared from aqueous solutions and calcined at atmospheric conditions, have been studied and characterized by XRD, Moessbauer and EPR spectroscopies and TGA analysis. Three iron sites are clearly distinguished from Moessbauer and EPR measurements. Firstly, characteristic Moessbauer and EPR spectra may arise from framework sites, suggesting that Fe has substituted Al. It is also found that their spectroscopic signals are not intensity affected by thermal treatments. Secondly, a Moessbauer doublet which may arise from octahedral sites in the large cavity of the zeolite, shows however, that this doublet and its EPR signal are intensity temperature affected. An additional line broadening is observed on the low velocity line of this doublet, Thirdly, characteristic Moessbauer and EPR signals, which are also intensity temperature dependent have been associated to accluded material, where the Moessbauer doublet presents the line broadening effect before mentioned. Such line broadening effect may be due to perturbing signals from iron ions in tetrahedral sites. Finally, it has been observed that during calcination of the FeY zeolites, the three characteristic EPR signals for the three iron sites, do not increase at the expenses of the other. A result that may suggest a strong bonding between Fe-site of the Y zeolite, irrespective of the iron source. (Author)

Suspending Zeolite Particles In Tanks

International Nuclear Information System (INIS)

Poirier, M.R.

1999-01-01

The Savannah River Site (SRS) is in the process of removing waste (sludge and salt cake) from million gallon waste tanks. The current practice for removing waste from the tanks is adding water, agitating the tanks with long shaft vertical centrifugal pumps, and pumping the sludge/salt solution from the tank to downstream treatment processes. This practice has left sludge heels (tilde 30,000 gallons) in the bottom of the tanks. SRS is evaluating shrouded axial impeller mixers for removing the sludge heels in the waste tanks. The authors conducted a test program to determine mixer requirements for suspending sludge heels using the shrouded axial impeller mixers. The tests were performed with zeolite in scaled tanks which have diameters of 1.5, 6.0, and 18.75 feet. The mixer speeds required to suspend zeolite particles were measured at each scale. The data were analyzed with various scaling methods to compare their ability to describe the suspension of insoluble solids with the mixers and to apply the data to a full-scale waste tank. The impact of changes in particle properties and operating parameters was also evaluated. The conclusions of the work are: Scaling of the suspension of fast settling zeolite particles was best described by the constant power per unit volume method. Increasing the zeolite particle concentration increased the required mixer power needed to suspend the particles. Decreasing the zeolite particle size from 0.7 mm 0.3 mm decreased the required mixer power needed to suspend the particles. Increasing the number of mixers in the tank decreased the required mixer power needed to suspend the particles. A velocity of 1.6 ft/sec two inches above the tank bottom is needed to suspend zeolite particles

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations.

Science.gov (United States)

Cmoch, Piotr; Głaszczka, Rafał; Jaźwiński, Jarosław; Kamieński, Bohdan; Senkara, Elżbieta

2014-03-01

Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters. Copyright © 2013 John Wiley & Sons, Ltd.

Biological effects of simple changes in functionality on rhodium metalloinsertors

Science.gov (United States)

Weidmann, Alyson G.; Komor, Alexis C.; Barton, Jacqueline K.

2013-01-01

DNA mismatch repair (MMR) is crucial to ensuring the fidelity of the genome. The inability to correct single base mismatches leads to elevated mutation rates and carcinogenesis. Using metalloinsertors–bulky metal complexes that bind with high specificity to mismatched sites in the DNA duplex–our laboratory has adopted a new chemotherapeutic strategy through the selective targeting of MMR-deficient cells, that is, those that have a propensity for cancerous transformation. Rhodium metalloinsertors display inhibitory effects selectively in cells that are deficient in the MMR machinery, consistent with this strategy. However, a highly sensitive structure–function relationship is emerging with the development of new complexes that highlights the importance of subcellular localization. We have found that small structural modifications, for example a hydroxyl versus a methyl functional group, can yield profound differences in biological function. Despite similar binding affinities and selectivities for DNA mismatches, only one metalloinsertor shows selective inhibition of cellular proliferation in MMR-deficient versus -proficient cells. Studies of whole-cell, nuclear and mitochondrial uptake reveal that this selectivity depends upon targeting DNA mismatches in the cell nucleus. PMID:23776288

Transformation of Indonesian Natural Zeolite into Analcime Phase under Hydrothermal Condition

Science.gov (United States)

Lestari, W. W.; Hasanah, D. N.; Putra, R.; Mukti, R. R.; Nugrahaningtyas, K. D.

2018-04-01

Natural zeolite is abundantly available in Indonesia and well distributed especially in the volcano area like Java, Sumatera, and Sulawesi. So far, natural zeolite from Klaten, Central Java is one of the most interesting zeolites has been widely studied. This research aims to know the effect of seed-assisted synthesis under a hydrothermal condition at 120 °C for 24 hours of Klaten’s zeolite toward the structural change and phase transformation of the original structure. According to XRD and XRF analysis, seed-assisted synthesis through the addition of aluminosilicate mother solution has transformed Klaten’s zeolite which contains (mordenite and clinoptilolite) into analcime type with decreasing Si/Al ratio from 4.51 into 1.38. Morphological analysis using SEM showed the shape changes from irregular into spherical looks like takraw ball in the range of 0.3 to 0.7 micrometer. Based on FTIR data, structure of TO4 site (T = Si or Al) was observed in the range of 300-1300 cm-1 and the occupancy of Brønsted acid site as OH stretching band from silanol groups was detected at 3440-3650 cm-1. Nitrogen adsorption-desorption analysis confirmed that transformation Klaten’s zeolite into analcime type has decreased the surface area from 55.41 to 22.89 m2/g and showed inhomogeneous pore distribution which can be classified as micro-mesoporous aluminosilicate materials.

Synthesis of Diphenylamine Catalyzed by Zeolites

Czech Academy of Sciences Publication Activity Database

Hronec, M.; Cvengrošová, Z.; Čejka, Jiří

2003-01-01

Roč. 255, - (2003), s. 197-202 ISSN 0926-860X Institutional research plan: CEZ:AV0Z4040901 Keywords : zeolites beta * bentonite * Bronsted site Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.825, year: 2003

Determination of water content in natural zeolites by reflection method

International Nuclear Information System (INIS)

Sarria, Lopez P.; Desdin Garcia, V.; Freixas Lemus, V.; Dominguez Ley, O.; Csikai, G.

1989-01-01

Water content in natural zeolites collected from different site places in Cuba has been determined by neutron reflection method. Results show that it is possible to separate the minerals abundant in zeolite from the surrounding barren rocks. Water content of about 10% can be determined with 2-3% relative accuracy for different matrices, using 10 m measuring time

Effect of alkali-treatment on the characteristics of natural zeolites with different compositions.

Science.gov (United States)

Ates, Ayten

2018-08-01

A series of natural zeolites with different compositions were modified by post-synthesis modification with sodium hydroxide (NaOH) solution. Natural and modified zeolites were characterized by XRD, SEM, nitrogen adsorption, FTIR, zeta potential and temperature programmed desorption of ammonia (NH 3 -TPD). The adsorption capacities of these samples were evaluated by the adsorption of manganese from aqueous solution. The treatment with NaOH led to a decrease in the surface area and microporosity of all natural zeolites as well as partly damage of the zeolite structure depending on zeolite composition. In addition, the amount of weak, medium and strong acid sites in the zeolites was changed significantly by NaOH treatment depending on zeolite composition. The NaOH treatment resulted in a four-fold improvement in adsorption capacity of natural zeolite originated from Bigadic and a twofold decrease in that of the natural zeolite originated from Manisa-Gordes. Although the improved adsorption capacity might be mainly due to modification of porosity in the zeolites and formation of hydroxysodalite, the reduced adsorption capacity of the zeolite might be mainly due to a significant deformation of the zeolite structure. The pseudo-second-order kinetic model for the adsorption of manganese on all natural and modified zeolites fits well. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalytic reactions of synthesis gas. Part 2. Methanol carbonylation and homologation

Energy Technology Data Exchange (ETDEWEB)

Niemelae, M.

1993-01-01

The aim of the review is to evaluate the applicability of methanol hydrocarbonylation as a second test reaction to study the nondissociative activation of CO by heterogeneous rhodium and cobalt catalysts. The main emphasis in methanol (hydro)carbonylation chemistry has been on homogeneous reactions. These systems have been seen advantageous in selectivity, activity and ease of modification. The heterogenization attempts have been carried out to obtain easier separation of the catalyst and the product. The activity of cobalt, rhodium and other metals supported on different materials have been studied in heterogeneous methanol (hydro)carbonylation. The observed activities have been considerably influenced by the support. The most effective catalyst support has been activated carbon. Good carbonylation activities and selectivities have also been observed in conjunction with zeolite supports. The literature study indicates that the typical experimental conditions of methanol (hydro)carbonylation do not exceed the constructional and operational limits of the available reactor system, i.e. 500 C and 50 bar. The reaction is suitable for testing Co and Rh precursors, since both cobalt and rhodium compounds have shown carbonylation activity.

"On-water" rhodium-catalysed hydroformylation for the production of linear alcohols

NARCIS (Netherlands)

Diebolt, O.H.; Müller, Christian; Vogt, D.

2012-01-01

Optimisation of the reaction conditions for the rhodium-catalysed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcohols. One-pot hydroformylation–hydrogenation using rhodium as the only transition

Redox behavior of transition metal ions in zeolites--7. Characterization of a nickel metal phase in zeolite NaY

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P.A. (Katholieke Univ. Leuven); Derouane, E.G.; Nijs, H.; Verdonck, J.; Gilson, J.P.; Simoens, A.J.

1979-01-01

NiY zeolite was calcined under steaming and nonsteaming conditions, at 823/sup 0/ and 1200/sup 0/K, respectively, then reduced in hydrogen at 673/sup 0/ to 873/sup 0/K for two hours. Characterization of the Ni(0) metal phase by temperature programed reduction and oxidation techniques and by ferromagnetic resonance spectroscopy indicated a bidisperse metal particle size distribution. Inside the zeolite, small Ni(0) particles were found, the sizes of which were limited by the dimensions of the supercage or of the structural defects occurring with high reduction temperatures; the particles interacted strongly with the support or were Vertical Bar3; 100Vertical Bar3< reduced. On the zeolite surface, large Ni(0) particles were formed which were ellipsoidal and completely reduced and did not interact with the support. Calcining under steaming conditions did not affect the reducibility of the nickel but did promote sintering during reduction.

Adsorption of CO2 in FAU zeolites: Effect of zeolite composition

Czech Academy of Sciences Publication Activity Database

Thang, H. V.; Grajciar, L.; Nachtigall, P.; Bludský, Ota; Areán, C. O.; Frýdová, E.; Bulánek, R.

2014-01-01

Roč. 227, May 15 (2014), s. 50-56 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388963 Keywords : DFT/CC * CO2 * carbon capture and storage * zeolite * adsorption calorimetry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.893, year: 2014

Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

Science.gov (United States)

Schatzschneider, Ulrich; Barton, Jacqueline K

2004-07-21

A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

Methanation of CO2 over Zeolite-Encapsulated Nickel Nanoparticles

DEFF Research Database (Denmark)

Goodarzi, Farnoosh; Kang, Liqun; Wang, Feng Ryan

2018-01-01

in an increased metal dispersion and, consequently, a high catalytic activity for CO2 methanation. With a gas hourly space velocity of 60000 ml/g catalyst h-1 and H2/CO2=4, the zeolite-encapsulated Ni nanoparticles result in 60% conversion at 450°C, which corresponds to a site-time yield of around 304 mol CH4/mol......Efficient methanation of CO2 relies on the development of more selective and stable heterogeneous catalysts. Here we present a simple and effective method to encapsulate Ni nanoparticles in zeolite silicalite-1. In this method, the zeolite is modified by selective desilication, which creates intra...

Antagonizing STAT3 dimerization with a rhodium(III) complex.

Science.gov (United States)

Ma, Dik-Lung; Liu, Li-Juan; Leung, Ka-Ho; Chen, Yen-Ting; Zhong, Hai-Jing; Chan, Daniel Shiu-Hin; Wang, Hui-Min David; Leung, Chung-Hang

2014-08-25

Kinetically inert metal complexes have arisen as promising alternatives to existing platinum and ruthenium chemotherapeutics. Reported herein, to our knowledge, is the first example of a substitutionally inert, Group 9 organometallic compound as a direct inhibitor of signal transducer and activator of transcription 3 (STAT3) dimerization. From a series of cyclometalated rhodium(III) and iridium(III) complexes, a rhodium(III) complex emerged as a potent inhibitor of STAT3 that targeted the SH2 domain and inhibited STAT3 phosphorylation and dimerization. Significantly, the complex exhibited potent anti-tumor activities in an in vivo mouse xenograft model of melanoma. This study demonstrates that rhodium complexes may be developed as effective STAT3 inhibitors with potent anti-tumor activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-step synthesis of mesoporous pentasil zeolite with single-unit-cell lamellar structural features

Science.gov (United States)

Tsapstsis, Michael; Zhang, Xueyi

2015-11-17

A method for making a pentasil zeolite material includes forming an aqueous solution that includes a structure directing agent and a silica precursor; and heating the solution at a sufficient temperature and for sufficient time to form a pentasil zeolite material from the silica precursor, wherein the structure directing agent includes a quaternary phosphonium ion.

Synthesis and structural study of the transition metal doped rhodium perovskites

International Nuclear Information System (INIS)

Ting, J.; Kennedy, B.; Zhang, Z.

2009-01-01

Full text: One of the most common structures encountered in solid state chemistry is the perovskite structure. With a general formula of AB0 3, the A-type cations are 12-coordinate within a cubo-octahedral environment, while the B-type cations are 6-coordinate, forming an interconnecting three-dimensional octahedral network with neighbouring oxygen anions. While the ideal perovskite structure is cubic in Pm 3 m, many perovskites exhibit symmetry lowering tilting of the corner-sharing B0 6o ctahedral units as a result of A- and B-type cation size disparity. This is also evident in substituted perovskites, where two cations occupy the smaller octahedral site, AB 1- xB' x0 3' Electronic effects can also lower the symmetry. The two most commonly observed effects are the polarisation of the B-cation with a d 0 electronic configuration and Jahn-Teller distortion where the B-cation has a d 4 or d 9 electronic configuration, such as Mn 3+ or Cu 2+ respectively. Manganese containing perovskites have been shown in some compounds to exhibit long-range orbital ordering, giving rise to interesting properties. Heavier transition metals such as ruthenium and iridium have been previously incorporated into these perovskites as an avenue to regulate the properties of these materials. Two orthorhombic rhodium perovskite structures are presented, LaMn 0 . 5 Rh 0 . 5 O 3 and LaCu 05 Rh 0 . 5 O 3 ' A combination of synchrotron x-ray and neutron powder diffraction has been used to elucidate their structures, and have shown both B- and B'-type cations to be disordered across the same crystallographic site for both compounds. x-ray absorption spectroscopy measurements have been used to provide an insight into the valence states of the cations, which show a valency of +3.5 for rhodium due to an extensive charge delocalisation between copper and rhodium.

Structure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of Alcohols

OpenAIRE

Briggs, Daniel Neal

2010-01-01

AbstractStructure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of AlcoholsbyDaniel Neal BriggsDoctor of Philosophy in Chemical EngineeringUniversity of California, BerkeleyProfessor Alexis T. Bell, Chair The oxidative carbonylation of alcohols to produce dialkyl carbonates is a process that takes place commercially in a slurry of cuprous chloride in the appropriate alcohol. While this process is chemically efficient, it incurs costs in terms of ene...

Synthesis of Zeolite NaA from Low Grade (High Impurities) Indonesian Natural Zeolite

OpenAIRE

Mustain, Asalil; Wibawa, Gede; Nais, Mukhammad Furoiddun; Falah, Miftakhul

2014-01-01

The zeolite NaA has been successfully synthesized from the low grade natural zeolite with high impurities. The synthesis method was started by mixing natural zeolite powder with NH4Cl aqueous solution in the reactor as pretreatment. The use of pretreatment was to reduce the impurities contents in the zeolite. The process was followed by alkaline fusion hydrothermal treatment to modify the framework structure of natural zeolite and reduce the SiO2/Al2O3 ratio. Finally, the synthesized zeolite ...

Rhodium and Hafnium Influence on the Microstructure, Phase Composition, and Oxidation Resistance of Aluminide Coatings

OpenAIRE

Maryana Zagula-Yavorska; Małgorzata Wierzbińska; Jan Sieniawski

2017-01-01

A 0.5 μm thick layer of rhodium was deposited on the CMSX 4 superalloy by the electroplating method. The rhodium-coated superalloy was hafnized and aluminized or only aluminized using the Chemical vapour deposition method. A comparison was made of the microstructure, phase composition, and oxidation resistance of three aluminide coatings: nonmodified (a), rhodium-modified (b), and rhodium- and hafnium-modified (c). All three coatings consisted of two layers: the additive layer and the interdi...

Formation of Broensted acids sites in the reaction of cyclohexanol on NaCeY zeolites

International Nuclear Information System (INIS)

Vogt, O.; Nattich, M.; Datka, J.; Gil, B.

2002-01-01

This study was undertaken to elucidate why the catalytic activity of NaCeY in cyclohexanol reactions carried out in a pulse reactor increases with the pulse number. We studied therefore the effect of cyclohexanol and also of ethanol and water on catalytic activity NaCeY (of exchange degrees 36 and 72%) in cyclohexanol reactions: isomerization and disproportionation. We also studied the reaction of cyclohexanol and water with NaCeY zeolite by IR spectroscopy. Our results evidenced that new Broensted acid sites were formed by the reaction of cyclohexanol and water. This was shown by IR spectroscopy: the increase of Si-O 1 H-Al band 3638 cm -1 and in increase of ammonium ions band (upon ammonia adsorption). The new sites were formed by hydrolysis of Ce 3+ ions with water introduced in a pulse, or produced by dehydration of cyclohexanol catalyzed by acid sites. Formation of new Broensted acid sites resulted in an increase of catalytic activity of NaCeY in cyclohexane reaction as observed in this study and also in cyclohexanol reactions. (author)

The effect of positioning cations on acidity and stability of the framework structure of Y zeolite

Science.gov (United States)

Deng, Changshun; Zhang, Junji; Dong, Lihui; Huang, Meina; Bin Li; Jin, Guangzhou; Gao, Junbin; Zhang, Feiyue; Fan, Minguang; Zhang, Luoming; Gong, Yanjun

2016-01-01

The investigation on the modification of NaY zeolite on LaHY and AEHY (AE refers Ca and Sr and the molar ratio of Ca and Sr is 1:1) zeolites was proformed by XRD, N2-physisorption (BET), XRF, XPS, NH3-TPD, Py-IR, hydrothermal stability, and catalytic cracking test. These results indicate that HY zeolite with ultra low content Na can be obtained from NaY zeolite through four exchange four calcination method. The positioning capability of La3+ in sodalite cage is much better than that of AE2+ and about 12 La3+ can be well coordinated in sodalite cages of one unit cell of Y zeolite. Appropriate acid amount and strength favor the formation of propylene and La3+ is more suitable for the catalytic cracking of cyclohexane than that of AE2+. Our results not only elaborate the variation of the strong and weak acid sites as well as the Brönsted and Lewis acid sites with the change of exchanged ion content but also explore the influence of hydrothermal aging of LaHY and AEHY zeolites and find the optimum ion exchange content for the most reserved acid sites. At last, the coordination state and stabilization of ion exchanged Y zeolites were discussed in detail. PMID:26987306

Antitumor effect of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles on mice bearing breast cancer: a systemic toxicity assay.

Science.gov (United States)

Peixoto, Raphael Cândido Apolinário; Miranda-Vilela, Ana Luisa; de Souza Filho, José; Carneiro, Marcella Lemos' Brettas; Oliveira, Ricardo G S; da Silva, Matheus Oliveira; de Souza, Aparecido R; Báo, Sônia Nair

2015-05-01

Breast cancer is one of the most prevalent cancer types among women. The use of magnetic fluids for specific delivery of drugs represents an attractive platform for chemotherapy. In our previous studies, it was demonstrated that maghemite nanoparticles coated with rhodium (II) citrate (Magh-Rh2Cit) induced in vitro cytotoxicity and in vivo antitumor activity, followed by intratumoral administration in breast carcinoma cells. In this study, our aim was to follow intravenous treatment to evaluate the systemic antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Female Balb/c mice were evaluated with regard to toxicity of intravenous treatments through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine and liver, kidney, and lung histology. The antitumor activity of rhodium (II) citrate (Rh2Cit), Magh-Rh2Cit, and maghemite nanoparticles coated with citrate (Magh-Cit), used as control, was evaluated by tumor volume reduction, histology, and morphometric analysis. Magh-Rh2Cit and Magh-Cit promoted a significant decrease in tumor area, and no experimental groups presented hematotoxic effects or increased levels of serum ALT and creatinine. This observation was corroborated by the histopathological examination of the liver and kidney of mice. Furthermore, the presence of nanoparticles was verified in lung tissue with no morphological changes, supporting the idea that our nanoformulations did not induce toxicity effects. No studies about the systemic action of rhodium (II) citrate-loaded maghemite nanoparticles have been carried out, making this report a suitable starting point for exploring the therapeutic potential of these compounds in treating breast cancer.

Acid-catalyzed Synthesis of Mono and Diakyl Benzenes over Zeolites. Active Sites, Zeolite Topology, and Reaction Mechanisms

Czech Academy of Sciences Publication Activity Database

Čejka, Jiří; Wichterlová, Blanka

2002-01-01

Roč. 44, - (2002), s. 375-422 ISSN 0161-4940 R&D Projects: GA AV ČR IAA4040001; GA AV ČR IAA4040707 Institutional research plan: CEZ:AV0Z4040901 Keywords : alkyl aromatic * zeolites * molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.455, year: 2002

Electron irradiation of zeolites

International Nuclear Information System (INIS)

Wang, S.X.; Wang, L.M.; Ewing, R.C.

1999-01-01

Three different zeolites (analcime, natrolite, and zeolite-Y) were irradiated with 200 keV and 400 keV electrons. All zeolites amorphized under a relatively low electron fluence. The transformation from the crystalline-to-amorphous state was continuous and homogeneous. The electron fluences for amorphization of the three zeolites at room temperature were: 7.0 x 10 19 e - /cm 2 (analcime), 1.8 x 10 20 e - /cm 2 (natrolite), and 3.4 x 10 20 e - /cm 2 (zeolite-Y). The different susceptibilities to amorphization are attributed to the different channel sizes in the structures which are the pathways for the release of water molecules and Na + . Natrolite formed bubbles under electron irradiation, even before complete amorphization. Analcime formed bubbles after amorphization. Zeolite-Y did not form bubbles under irradiation. The differences in bubble formation are attributed to the different channel sizes of the three zeolites. The amorphization dose was also measured at different temperatures. An inverse temperature dependence of amorphization dose was observed for all three zeolites: electron dose for amorphization decreased with increasing temperature. This unique temperature effect is attributed to the fact that zeolites are thermally unstable. A semi-empirical model was derived to describe the temperature effect of amorphization in these zeolites

Applications of natural zeolites on agriculture and food production.

Science.gov (United States)

Eroglu, Nazife; Emekci, Mevlut; Athanassiou, Christos G

2017-08-01

Zeolites are crystalline hydrated aluminosilicates with remarkable physical and chemical properties, which include losing and receiving water in a reverse way, adsorbing molecules that act as molecular sieves, and replacing their constituent cations without structural change. The commercial production of natural zeolites has accelerated during the last 50 years. The Structure Commission of the International Zeolite Association recorded more than 200 zeolites, which currently include more than 40 naturally occurring zeolites. Recent findings have supported their role in stored-pest management as inert dust applications, pesticide and fertilizer carriers, soil amendments, animal feed additives, mycotoxin binders and food packaging materials. There are many advantages of inert dust application, including low cost, non-neurotoxic action, low mammalian toxicity and safety for human consumption. The latest consumer trends and government protocols have shifted toward organic origin materials to replace synthetic chemical products. In the present review, we summarize most of the main uses of zeolites in food and agruculture, along with the with specific paradigms that illustrate their important role. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Selective alkane activation with single-site atoms on amorphous support

Science.gov (United States)

Hock, Adam S.; Schweitzer, Neil M.; Miller, Jeffrey T.; Hu, Bo

2015-11-24

The present invention relates generally to catalysts and methods for use in olefin production. More particularly, the present invention relates to novel amorphously supported single-center, Lewis acid metal ions and use of the same as catalysts.

Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

Science.gov (United States)

Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

2018-05-01

A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

Rhodium-Catalyzed Linear Codimerization and Cycloaddition of Ketenes with Alkynes

Directory of Open Access Journals (Sweden)

Teruyuki Kondo

2010-06-01

Full Text Available A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh33, and are highly dependent on the structure and reactivity of the starting ketenes.

Effects of Zeolite and Vermicompost on Changes of Zn Chemical Fractionation in a Polluted Soil

Directory of Open Access Journals (Sweden)

Mohsen Hamidpour

2017-02-01

decreased significantly with co-application of vermicompost and zeolite. This may be due to redistribution of Zn from this form to less available forms (e.g. organic and residual fractions. The addition of vermicompost had not significant effect on the carbonated fraction of Zn, whereas co-application of zeolite and vermicompost significantly decreased concentration of Zn bound in carbonates. Singly zeolite and co-application of amendments decreased the concentration of Zn in Fe and Mn oxides bound. Although singly compost and zeolite amendments increased concentration of Zn bound to organics, this form decreased furthest with co-application of them. Zeolite and vermicompost alone had not significant effect on mobility factor (MF of Zn over the un-amended soil. Co-application of vermicompost and zeolite to polluted soil resulted in a significant decrease in MF values of Zn compared to control. Conclusion: Co-application of vermicompost and zeolite to polluted soil resulted in redistribution of Zn from available forms (exchangeable +water soluble to less available form (e.g. organic, thus may be useful for the immobilization of Zn from polluted sites.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential and challenges of zeolite chemistry in the catalytic conversion of biomass.

Science.gov (United States)

Ennaert, Thijs; Van Aelst, Joost; Dijkmans, Jan; De Clercq, Rik; Schutyser, Wouter; Dusselier, Michiel; Verboekend, Danny; Sels, Bert F

2016-02-07

Increasing demand for sustainable chemicals and fuels has pushed academia and industry to search for alternative feedstocks replacing crude oil in traditional refineries. As a result, an immense academic attention has focused on the valorisation of biomass (components) and derived intermediates to generate valuable platform chemicals and fuels. Zeolite catalysis plays a distinct role in many of these biomass conversion routes. This contribution emphasizes the progress and potential in zeolite catalysed biomass conversions and relates these to concepts established in existing petrochemical processes. The application of zeolites, equipped with a variety of active sites, in Brønsted acid, Lewis acid, or multifunctional catalysed reactions is discussed and generalised to provide a comprehensive overview. In addition, the feedstock shift from crude oil to biomass involves new challenges in developing fields, like mesoporosity and pore interconnectivity of zeolites and stability of zeolites in liquid phase. Finally, the future challenges and perspectives of zeolites in the processing of biomass conversion are discussed.

The fabrication of porous 4A-zeolite-supported Ag nanoparticles catalysts and its catalytic activity for styrene epoxidation

Directory of Open Access Journals (Sweden)

Youkui Wu

Full Text Available Binderless hierarchically porous 4A-zeolite has been successful produced through hydrothermal crystallization, in which silicon-aluminum sol binded to the carbon nanofibers (CNFs, that is to say, where the CNFs powder was coated during the crystallization 4A-zeolite. The mixing of silica-alumina sol and CNFs was only a simple physical mixing process. The samples of micropores-macroporous hierarchical 4A-zeolite (P-4A-zeolite was analyzed by a series of characterization techniques, such as field emission scanning electron microscope (FESEM, transmission electron microscopy (TEM, simultaneous thermal analysis (STA and CO2 adsorption-desorption (BET and BJH, and so on. In addition, the adsorption test of silver nanoparticles was carried out. The characterization results indicated the presence of micropores and the formation of macroporous. At the same time, silver adsorption test proved that the prepared P-4A-zeolite had good adsorption performance and the catalytic performance of Ag/P-4A-zeolite was further investigated through the epoxidation of styrene. Keywords: Carbon nanofibers, Porous 4A-zeolite, Silver nanoparticles, Styrene epoxidation

Molecular simulation of water removal from simple gases with zeolite NaA.

Science.gov (United States)

Csányi, Eva; Ható, Zoltán; Kristóf, Tamás

2012-06-01

Water vapor removal from some simple gases using zeolite NaA was studied by molecular simulation. The equilibrium adsorption properties of H(2)O, CO, H(2), CH(4) and their mixtures in dehydrated zeolite NaA were computed by grand canonical Monte Carlo simulations. The simulations employed Lennard-Jones + Coulomb type effective pair potential models, which are suitable for the reproduction of thermodynamic properties of pure substances. Based on the comparison of the simulation results with experimental data for single-component adsorption at different temperatures and pressures, a modified interaction potential model for the zeolite is proposed. In the adsorption simulations with mixtures presented here, zeolite exhibits extremely high selectivity of water to the investigated weakly polar/non-polar gases demonstrating the excellent dehydration ability of zeolite NaA in engineering applications.

In vitro permeation of platinum and rhodium through Caucasian skin.

Science.gov (United States)

Franken, A; Eloff, F C; Du Plessis, J; Badenhorst, C J; Jordaan, A; Du Plessis, J L

2014-12-01

During platinum group metals (PGMs) refining the possibility exists for dermal exposure to PGM salts. The dermal route has been questioned as an alternative route of exposure that could contribute to employee sensitisation, even though literature has been focused on respiratory exposure. This study aimed to investigate the in vitro permeation of platinum and rhodium through intact Caucasian skin. A donor solution of 0.3mg/ml of metal, K2PtCl4 and RhCl3 respectively, was applied to the vertical Franz diffusion cells with full thickness abdominal skin. The receptor solution was removed at various intervals during the 24h experiment, and analysed with high resolution ICP-MS. Skin was digested and analysed by ICP-OES. Results indicated cumulative permeation with prolonged exposure, with a significantly higher mass of platinum permeating after 24h when compared to rhodium. The mass of platinum retained inside the skin and the flux of platinum across the skin was significantly higher than that of rhodium. Permeated and skin retained platinum and rhodium may therefore contribute to sensitisation and indicates a health risk associated with dermal exposure in the workplace. Copyright © 2014 Elsevier Ltd. All rights reserved.

Positron annihilation in modified zeolites LTA and 13X

Energy Technology Data Exchange (ETDEWEB)

Cabral-Prieto, A.; Garcia-Sosa, I.; Jimenez-Becerril, J. [Departamento de Quimica, Instituto Nacional de Investigaciones Nucleares, Apartado Postal 18-1027, Col. Escandon, Del. M. Hidalgo, Mexico D. F., c. p. 11801 (Mexico); Lopez-Castanares, R.; Olea-Cardoso, O. [Facultad de Quimica, Universidad Autonoma del Estado de Mexico, Paseo Tollocan esquina paseo Tollocan, esquina paseo Colon, Toluca, c. p. 50120, Estado de Mexico (Mexico)

2007-07-01

The pick-off annihilation lifetimes of o -Ps, {tau}{sub po}, in dehydrated Co{sup 2+} and Mn{sup 2+} exchanged zeolites LTA, in dehydrated Co{sup 2+} exchanged zeolite 13X, and in dehydrated Na{sup +} zeolites LTA and 13X, are estimated. Although {tau}{sub po} can be estimated from the lifetime spectra of the cation exchanged zeolites LTA and 13X, this lifetime can not be estimated from those spectra of Na{sup +} zeolite LTA unambiguously. The estimated pick-off lifetimes due to the annihilation of o-Ps in the internal walls of the zeolites are systematically lower than the average lifetime of p-Ps and o-Ps in vacuum {tau}{sub a}=0.5 ns. Since the pick-off process of o-Ps occurs particularly on the internal cavity walls of dehydrated zeolites, the replacement of {tau}{sub a} by {tau}{sub po} within the classical model of Tao-Eldrup to calculate cavity radius should provide more realistic cavity radii of these porous materials than when using {l_brace}{tau}{sub a}{r_brace}. This suggestion is supported by previous and present results. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Hydrogenation of Anthracene in Supercritical Carbon Dioxide Solvent Using Ni Supported on Hβ-Zeolite Catalyst

Directory of Open Access Journals (Sweden)

Ashraf Aly Hassan

2012-01-01

Full Text Available Catalytic hydrogenation of anthracene was studied over Ni supported on Hβ-zeolite catalyst under supercritical carbon dioxide (sc-CO2 solvent. Hydrogenation of anthracene in sc-CO2 yielded 100% conversion at 100 °C, which is attributed to the reduced mass transfer limitations, and increased solubility of H2 and substrate in the reaction medium. The total pressure of 7 MPa was found to be optimum for high selectivity of octahydroanthracene (OHA. The conversion and selectivity for OHA increased with an increase in H2 partial pressure, which is attributed to higher concentration of hydrogen atoms at higher H2 pressures. The selectivity reduced the pressure below 7 MPa because of enhanced desorption of the tetrahydro-molecules and intermediates from Ni active sites, due to higher solubility of the surface species in sc-CO2. The selectivity of OHA increased with the increase in catalyst weight and reaction time. The rate of hydrogenation of anthracene was compared with that found for napthalene and phenanthrene. The use of acetonitrile as co-solvent or expanded liquid with CO2 decreased the catalytic activity.

IR and TPD studies of the interaction of alkenes with Cu + sites in CuNaY and CuNaX zeolites of various Cu content. The heterogeneity of Cu + sites

Science.gov (United States)

Datka, J.; Kukulska-Zajaç, E.; Kozyra, P.

2006-08-01

Cu + ions in zeolites activate organic molecules containing π electrons by π back donation, which results in a distinct weakening of multiple bonds. In this study, we followed the activation of alkenes (ethene and propene) by Cu + ions in CuY and CuX zeolites of various Cu content. We also studied the strength of bonding of alkenes to Cu + ions. IR studies have shown that there are two kinds of Cu + sites of various electron donor properties. We suppose that they could be attributed to the presence of Cu + ions of various number of oxygen atoms surrounding the cation. IR studies have shown that Cu ions introduced into Y and X zeolites in the first-order (at low Cu content) form Cu + ions of stronger electron donor properties (i.e. activate alkenes to larger extend) than Cu ions introduced in the next order (at higher Cu content). IR and TPD studies of alkenes desorption evidenced that Cu + ions of stronger electron donor properties bond alkenes stronger than less electron donor ones. It suggests that π back donation has more important contribution to the strength of bonding alkenes to cation than π donation.

Rhodium-Catalyzed Decarbonylation of Aldoses

DEFF Research Database (Denmark)

Monrad, Rune; Madsen, Robert

2007-01-01

A catalytic procedure is described for decarbonylation of unprotected aldoses to afford alditols with one less carbon atom. The reaction is performed with the rhodium complex Rh(dppp)2Cl in a refluxing diglyme - DMA solution. A slightly improved catalyst turnover is observed when a catalytic amount...

Hierarchical zeolites from class F coal fly ash

Science.gov (United States)

Chitta, Pallavi

Fly ash, a coal combustion byproduct is classified as types class C and class F. Class C fly ash is traditionally recycled for concrete applications and Class F fly ash often disposed in landfills. Class F poses an environmental hazard due to disposal and leaching of heavy metals into ground water and is important to be recycled in order to mitigate the environmental challenges. A major recycling option is to reuse the fly ash as a low-cost raw material for the production of crystalline zeolites, which serve as catalysts, detergents and adsorbents in the chemical industry. Most of the prior literature of fly ash conversion to zeolites does not focus on creating high zeolite surface area zeolites specifically with hierarchical pore structure, which are very important properties in developing a heterogeneous catalyst for catalysis applications. This research work aids in the development of an economical process for the synthesis of high surface area hierarchical zeolites from class F coal fly ash. In this work, synthesis of zeolites from fly ash using classic hydrothermal treatment approach and fusion pretreatment approach were examined. The fusion pretreatment method led to higher extent of dissolution of silica from quartz and mullite phases, which in turn led to higher surface area and pore size of the zeolite. A qualitative kinetic model developed here attributes the difference in silica content to Si/Al ratio of the beginning fraction of fly ash. At near ambient crystallization temperatures and longer crystallization times, the zeolite formed is a hierarchical faujasite with high surface area of at least 360 m2/g. This work enables the large scale recycling of class F coal fly ash to produce zeolites and mitigate environmental concerns. Design of experiments was used to predict surface area and pore sizes of zeolites - thus obviating the need for intense experimentation. The hierarchical zeolite catalyst supports tested for CO2 conversion, yielded hydrocarbons

Adsorption site of ammonia on copper-exchanged Y-type zeolite under coexisting water vapor. Temperature-programed desorption and infrared adsorption spectra

Energy Technology Data Exchange (ETDEWEB)

Kasaoka, S.; Sasaoka, E.; Shiraga, T.; Ono, Y.

1978-03-01

Sodium Y zeolites were copper-exchanged with cupric nitrate in water, in aqueous ammonia, and in aqueous ammonia/ammonium chloride, and calcined at 500/sup 0/C. Temperature-programed desorption and IR spectroscopy showed three types of adsorption sites for 0.1-1.0% ammonia gas from nitrogen containing 0-12% water vapor: physisorption, adsorption as tetraamminocopper(II) on copper(II) sites (type 2 site), and adsorption as ammonium ion on hydroxyl sites (type 3 site). Adsorption on type 2 sites occurred only at high ammonia concentration; desorption occurred around 175/sup 0/C. Type 3 sites consisted of Cu(OH)/sup +/ and Al(OH)/sup +/, adsorbed ammonia from low concentrations, and at temperatures above 200/sup 0/C, were probably the active sites for the reduction of nitric oxide by ammonia.

Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

Science.gov (United States)

Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

2015-03-21

Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of Enhanced Accessibility of Acid Sites in Micromesoporous Mordenite Zeolites on Hydroisomerization of n-Hexane

Czech Academy of Sciences Publication Activity Database

Pastvová, Jana; Kaucký, Dalibor; Morávková, Jaroslava; Rathouský, Jiří; Sklenák, Štěpán; Vorokhta, Maryna; Brabec, Libor; Pilař, Radim; Jakubec, Ivo; Tabor, Edyta; Klein, Petr; Sazama, Petr

2017-01-01

Roč. 7, č. 9 (2017), s. 5781-5795 ISSN 2155-5435 R&D Projects: GA ČR GA15-12113S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388955 ; RVO:61388980 ; RVO:67985891 Keywords : micromesoporous mordenite (MOR) zeolites * isomerization * n-hexane Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T); CA - Inorganic Chemistry (USMH-B) OBOR OECD: Physical chemistry; Inorganic and nuclear chemistry (UACH-T); Inorganic and nuclear chemistry (USMH-B) Impact factor: 10.614, year: 2016

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

A rhodium(III) complex for high-affinity DNA base-pair mismatch recognition

Science.gov (United States)

Junicke, Henrik; Hart, Jonathan R.; Kisko, Jennifer; Glebov, Oleg; Kirsch, Ilan R.; Barton, Jacqueline K.

2003-01-01

A rhodium(III) complex, rac-[Rh(bpy)2phzi]3+ (bpy, 2,2′-bipyridine; phzi, benzo[a]phenazine-5,6-quinone diimine) has been designed as a sterically demanding intercalator targeted to destabilized mismatched sites in double-helical DNA. The complex is readily synthesized by condensation of the phenazine quinone with the corresponding diammine complex. Upon photoactivation, the complex promotes direct strand scission at single-base mismatch sites within the DNA duplex. As with the parent mismatch-specific reagent, [Rh(bpy)2(chrysi)]3+ [chrysene-5,6-quinone diimine (chrysi)], mismatch selectivity depends on the helix destabilization associated with mispairing. Unlike the parent chrysi complex, the phzi analogue binds and cleaves with high affinity and efficiency. The specific binding constants for CA, CC, and CT mismatches within a 31-mer oligonucleotide duplex are 0.3, 1, and 6 × 107 M−1, respectively; site-specific photocleavage is evident at nanomolar concentrations. Moreover, the specificity, defined as the ratio in binding affinities for mispaired vs. well paired sites, is maintained. The increase in affinity is attributed to greater stability in the mismatched site associated with stacking by the heterocyclic aromatic ligand. The high-affinity complex is also applied in the differential cleavage of DNA obtained from cell lines deficient in mismatch repair vs. those proficient in mismatch repair. Agreement is found between photocleavage by the mismatch-specific probes and deficiency in mismatch repair. This mismatch-specific targeting, therefore, offers a potential strategy for new chemotherapeutic design. PMID:12610209

Relationship between electronic structure and electric conductivity of double rhodium oxides from X-ray spectral data

International Nuclear Information System (INIS)

Firsov, M.N.; Nefedov, V.I.; Shaplygin, I.S.

1983-01-01

Quantum yield spectra of X-ray photoemission of O K - and Rh M 3 -bands of double rhodium oxides with Be, Mg, Ca, Sr, Ba, Cd, V, Nb, Ta, Mo, W are obtained. Quantum yield spectra are analogous to absorption spectra and reflect vacant states in a crystal, in particular, the quantum yield spectrum of O K-band is associated with oxygen vacant states of p-symmetry while Rh M 3 -band spectrum with rhomium vacant states of d-symmetry. In all rhodium compounds investigated the first vacant band is formed by the rhodium 4d-states. The forbidden zone between the last occupied and first free states of rhodiUm has a small width (eV fractions), which explains the semiconductor character of electric conductivity of the investigated compounds. Electric resistance variation in investigated series of rhodium compounds is in agreement with peculiarities of their electronic structure and entirely depends on variation in the electron density on rhodium atoms

Synthesis of zeolite NaA membrane from fused fly ash extract

CSIR Research Space (South Africa)

Ameh, AE

2016-01-01

Full Text Available Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer...

XAFS Study on TiO2 Photocatalyst Loaded on Zeolite Synthesized from Steel Slag

International Nuclear Information System (INIS)

Kuwahara, Yasutaka; Ohmichi, Tetsutaro; Mori, Kosuke; Katayama, Iwao; Yamashita, Hiromi

2007-01-01

The convenient route for the synthesis of Y-zeolites by utilizing steel slag as a material source was developed. Through hydrothermal treatment, well-crystallized Y-zeolite was obtained. We also synthesized TiO2-loaded Y-zeolites by an impregnation method. The structure of titanium oxide species highly dispersed on the zeolite, which couldn't be detected by XRD patterns, was investigated by XAFS analysis. Photocatalytic activity for decomposition of 2-propanol in liquid phase was found to be enhanced by the hydrophobic surface property of zeolite. It has been demonstrated that the zeolite synthesized from steel slag would be applicable as a promising support of TiO2 photocatalyst

Use of Natural Zeolite to Upgrade Activated Sludge Process

Directory of Open Access Journals (Sweden)

Hanife Büyükgüngör

2003-01-01

Full Text Available The objective of this study was to achieve better efficiency of phosphorus removal in an enhanced biological phosphorus removal process by upgrading the system with different amounts of natural zeolite addition. The system performance for synthetic wastewater containing different carbon sources applied at different initial concentrations of phosphorus, as well as for municipal wastewater, was investigated. Natural zeolite addition in the aerobic phase of the anaerobic/aerobic bioaugmented activated sludge system contributed to a significant improvement of phosphorus removal in systems with synthetic wastewater and fresh municipal wastewater. Improvement of phosphorus removal with regard to the control reactors was higher with the addition of 15 than with 5 g/L of natural zeolite. In reactors with natural zeolite addition with regard to the control reactors significantly decreased chemical oxygen demand, ammonium and nitrate, while higher increment and better-activated sludge settling were achieved, without changes in the pH-values of the medium. It was shown that the natural zeolite particles are suitable support material for the phosphate-accumulating bacteria Acinetobacter calcoaceticus (DSM 1532, which were adsorbed on the particle surface, resulting in increased biological activity of the system. The process of phosphorus removal in a system with bioaugmented activated sludge and natural zeolite addition consisted of: metabolic activity of activated sludge, phosphorus uptake by phosphate-accumulating bacteria adsorbed on the natural zeolite particles and suspended in solution, and phosphorus adsorption on the natural zeolite particles.

Superconductivity in zirconium-rhodium alloys

Science.gov (United States)

Zegler, S. T.

1969-01-01

Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

Low-Temperature Pd/Zeolite Passive NO _x Adsorbers: Structure, Performance, and Adsorption Chemistry

Energy Technology Data Exchange (ETDEWEB)

Zheng, Yang [Institute for Integrated; Kovarik, Libor [Institute for Integrated; Engelhard, Mark H. [Institute for Integrated; Wang, Yilin [Institute for Integrated; Wang, Yong [Institute for Integrated; Gao, Feng [Institute for Integrated; Szanyi, János [Institute for Integrated

2017-07-14

Pd/zeolite passive NOx adsorber (PNA) materials were prepared with solution ion-exchange between NH4/zeolites (Beta, ZSM-5 and SSZ-13) and PdCl2 solutions. The nature of Pd (dispersion, distribution and oxidation states) in these materials was characterized with Na+ ion-exchange, TEM imaging, CO titration with FTIR and in situ XPS. The NOx trapping and release properties were tested using feeds with different compositions. It is concluded that multiple Pd species coexist in these materials: atomically dispersed Pd in the cationic sites of zeolites, and PdO2 and PdO particles on the external surfaces. While Pd is largely atomically dispersed in ZSM-5, the small pore opening for SSZ-13 inhibits Pd diffusion such that the majority of Pd stays as external surface PdO2 clusters. NOx trapping and release are not simple chemisorption and desorption events, but involve rather complex chemical reactions. In the absence of CO in the feed, cationic Pd(II) sites with oxygen ligands and PdO2 clusters are reduced by NO to Pd(I) and PdO clusters. These reduced sites are the primary NO adsorption sites. In the presence of H2O, the as-formed NO2 desorb immediately. In the presence of CO in the feed, metallic Pd, “naked” Pd2+, and Pd+ sites are responsible for NO adsorption. For Pd adsorption sites with the same oxidation states but in different zeolite frameworks, NO binding energies are not expected to vary greatly. However, NO release temperatures do vary substantially with different zeolite structures. This indicates that NO transport within these materials play an important role in determining release temperatures. Finally, some rational design principles on efficient PNA materials are suggested. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a

Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

Science.gov (United States)

Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

2015-03-15

Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Catalysis on singly dispersed bimetallic sites

Science.gov (United States)

Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia; Shan, Junjun; Liu, Jingyue; Frenkel, Anatoly I.; Patlolla, Anitha; Huang, Weixin; Li, Jun; Tao, Franklin

2015-08-01

A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh1Co3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh1Co3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.

Thermal change and ion exchange properties of zeolite L with cesium and strontium

International Nuclear Information System (INIS)

Mimura, Hitoshi; Akiba, Kenichi

1986-01-01

Thermal change and ion exchange properties of Cs and Sr have been studied for zeolite L. The zeolite structure is stable below 900 deg C and converts to the amorphous phase above 1000 deg C. The cesium form of zeolite L recrystallized to pollucite (CsAlSi 2 O 6 ) by calcination at 1400 deg C for 1 h or under hydrothermal condition (300 deg C, 290 atm, 24 h). Hydrogen-form zeolites were prepared by the acid treatment in 10 -2 ∼ 10 -1 M HNO 3 solutions or thermal decomposition of NH 4 form zeolites at 460 ∼ 500 deg C. The distribution of Cs and Sr was dependent on equilibrium pH and the distribution coefficient (K d ) was about 10 4 (ml/g) at pH 5 ∼ 7. The exchange capacity of Cs and Sr was 0.89 (meq./g zeolite) and exchanging ratio was 68 % at D sites in main channel. These cations in zeolite were completely eluted with 10 -1 M HNO 3 solution. (author)

Synthesis of zeolite-zeolite (mfi-fau) composite catalysts for the isomerization of n-hexane

International Nuclear Information System (INIS)

Ghouri, A.S; Usman, M.R.

2017-01-01

In this research work, the aim is to produce a relatively novel zeolite-zeolite (MFI-FAU) composite catalyst having better potential of catalyzing isomerization of lighter hydrocarbons such as light naphtha, n-pentane, n-hexane, n-heptane and mixture thereof. A series of zeolite-zeolite (MFI-FAU) composite catalysts have been synthesized by incorporating previous practices and techniques. The catalytic performance of as-synthesized zeolite-zeolite (MFI-FAU) composite catalysts have been investigated by isomerizing 95% pure n-hexane in conventional fixed bed flow micro-reactor at temperature 200-240 ºC under atmospheric pressure. In order to explore chemical and physical features of zeolite-zeolite (MFI-FAU) composite catalysts, they are examined and characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectrometry (EDX), N2 adsorption-desorption measurements (BET, BJH, t-plot measurements) and Fourier transform infrared (FTIR) spectroscopy equipped with attenuated total reflectance (ATR) arrangements. (author)

Nanosized zeolites as a perspective material for conductometric biosensors creation

Science.gov (United States)

Kucherenko, Ivan; Soldatkin, Oleksandr; Kasap, Berna Ozansoy; Kirdeciler, Salih Kaan; Kurc, Burcu Akata; Jaffrezic-Renault, Nicole; Soldatkin, Alexei; Lagarde, Florence; Dzyadevych, Sergei

2015-05-01

In this work, the method of enzyme adsorption on different zeolites and mesoporous silica spheres (MSS) was investigated for the creation of conductometric biosensors. The conductometric transducers consisted of gold interdigitated electrodes were placed on the ceramic support. The transducers were modified with zeolites and MSS, and then the enzymes were adsorbed on the transducer surface. Different methods of zeolite attachment to the transducer surface were used; drop coating with heating to 200°C turned out to be the best one. Nanozeolites beta and L, zeolite L, MSS, and silicalite-1 (80 to 450 nm) were tested as the adsorbents for enzyme urease. The biosensors with all tested particles except zeolite L had good analytical characteristics. Silicalite-1 (450 nm) was also used for adsorption of glucose oxidase, acetylcholinesterase, and butyrylcholinesterase. The glucose and acetylcholine biosensors were successfully created, whereas butyrylcholinesterase was not adsorbed on silicalite-1. The enzyme adsorption on zeolites and MSS is simple, quick, well reproducible, does not require use of toxic compounds, and therefore can be recommended for the development of biosensors when these advantages are especially important.

Highly Oriented Growth of Catalytically Active Zeolite ZSM-5 Films with a Broad Range of Si/Al Ratios

NARCIS (Netherlands)

Fu, Donglong|info:eu-repo/dai/nl/412516918; Schmidt, Joel E.|info:eu-repo/dai/nl/413333736; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Chowdhury, Abhishek Dutta|info:eu-repo/dai/nl/412438003; Meirer, Florian; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2017-01-01

Highly b-oriented zeolite ZSM-5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films.

A study on the sensitivity depletion laws for rhodium self-powered neutron detectors

International Nuclear Information System (INIS)

Kim, Gil Gon

1999-02-01

The rhodium self-powered neutron detectors (SPND) in a reactor core provide the operator with the on-line 3-dimensional nuclear power distribution. The signal produced by rhodium SPND is interpreted into the local neutron flux by using a sensitivity depletion law and the local neutron flux is interpreted into the local power by using a power conversion factor. This work on the sensitivity depletion laws for rhodium self-powered neutron detectors (SPND) is performed to improve the uncertainty of the sensitivity depletion law used in ABB-CE reactors employing a rhodium SPND and to develop a calculational tool for providing the sensitivity depletion laws to interpret the signal of the newly designed rhodium SPND into the local neutron flux. The calculational tools for a time dependent neutron flux distribution in the rhodium emitter during depletion and for a time dependent beta escape probability that a beta generated in the emitter is escaped into the collector were developed. Due to the cost, the exposure to the radiation, and the longer fuel cycle, there is a strong incentive that the loading density of an in-core instrumentation is reduced and the lifetime of the detector is lengthened. These objectives can be achieved by reducing the uncertainty which is amplified as it depletes. The calculational tools above provide the sensitivity depletion law and show the reduction of the uncertainty to about 1 % in interpreting the signal into the local neutron flux compared to the method employed by ABB-CE. The reduction in the uncertainty of 1 % in interpreting the signal into the local neutron flux is equivalent to the reduction in the uncertainty of 1 % or more in interpreting the signal into the local power and to the extension of the lifetime of rhodium SPND to about 10 % as reported by ABB-CE

Remarkable catalytic properties of hierarchical zeolite-Beta in epoxide rearrangement reactions

Czech Academy of Sciences Publication Activity Database

García-Munoz, J.L.; Serrano, D. P.; Vicente, G.; Linares, M.; Vitvarová, Dana; Čejka, Jiří

2015-01-01

Roč. 243, APR 2015 (2015), s. 141-152 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : hierarchical zeolites * zeolite beta * hybridzeolitic - mesostructured materials Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

Rhodium Phosphine-π-Arene Intermediates in the Hydroamination of Alkenes

Science.gov (United States)

Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

2011-01-01

A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine are reported. The active catalyst is shown to contain the phosphine ligand bound in a κ1, η6 form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C=C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes. PMID:21309512

A Novel Seeding Method of Interfacial Polymerization-Assisted Dip Coating for the Preparation of Zeolite NaA Membranes on Ceramic Hollow Fiber Supports.

Science.gov (United States)

Cao, Yue; Wang, Ming; Xu, Zhen-Liang; Ma, Xiao-Hua; Xue, Shuang-Mei

2016-09-28

A novel seeding method combining interfacial polymerization (IP) technique with dip-coating operation was designed for directly coating nanosized NaA seed crystals (150 nm) onto the micrometer-sized α-Al2O3 hollow fiber support, in which the polyamide (PA) produced by IP acted as an effective medium to freeze and fix seed crystals at the proper position so that the controlled seed layer could be accomplished. While a coating suspension with only 0.5 wt % seed content was used, a very thin seed layer with high quality and good adhesion was achieved through dip coating twice without drying between, and the whole seeding process was operated at ambient conditions. The resulting zeolite NaA membranes not only exhibited high pervaporation (PV) performance with an average separation factor above 10000 and flux nearly 9.0 kg/m(2)·h in dehydration of 90 wt % ethanol aqueous solution at 348 K but also demonstrated great reproducibility by testing more than eight batches of zeolite membranes. In addition, this seeding strategy could be readily extended to the preparation of other supported zeolite membranes for a wide range of separation applications.

Characterization of gallium-containing zeolites for catalytic applications

Energy Technology Data Exchange (ETDEWEB)

Garcia Sanchez, M.

2003-12-08

The present study considers the synthesis, characterization, and catalytic evaluation of extra-framework gallium-containing zeolites. We focus on modification of zeolites by chemical vapor deposition of trimethylgallium on HZSM-5 and Mordenite zeolites. Chapter 2 is dedicated to the chemisorption and stability of TMG on HZSM-5 and HMOR zeolites. The effect of silylation is also addressed. Some theoretical calculations are also shown in this study to support part of the experimental results. In Chapter 3, the effect of oxidation and reduction treatments on these catalysts is investigated by FTIR, ICP and multinuclei NMR. In Chapter 4, the oxidation state and Ga coordination obtained during and after thermal treatment with H2 and O2 is analysed by X-ray adsorption spectroscopy (XANES and EXAFS) and IR analysis of CO adsorption. These results allow a better understanding of the catalytic behaviour of Ga-containing zeolites catalyst. Chapter 5 consists of two parts: one discusses the H2 activation over Ga/HZSM5 and Ga/MOR catalysts by H2/D2 isotopic exchange reaction, and the second part deals with the aromatization of n-heptane over the same catalysts.

Synthesis of ceramic hollow fiber supported zeolitic imidazolate framework-8 (ZIF-8) membranes with high hydrogen permeability

KAUST Repository

Pan, Yichang; Wang, Bo; Lai, Zhiping

2012-01-01

Purification and recovery of hydrogen from hydrocarbons in refinery streams in the petrochemical industry is an emerging research field in the study of membrane gas separation. Hollow fiber membrane modules can be easily implemented into separation processes at the industrial scale. In this report, hollow yttria-stabilized zirconia (YSZ) fiber-supported zeolitic imidazole framework-8 (ZIF-8) membranes were successfully prepared using a mild and environmentally friendly seeded growth method. Our single-component permeation studies demonstrated that the membrane had a very high hydrogen permeance (~15×10 -7mol/m 2sPa) and an ideal selectivity of H 2/C 3H 8 of more than 1000 at room temperature. This high membrane permeability and selectivity caused serious concentration polarization in the separation of H 2/C 3H 8 mixtures, which led to almost 50% drop in both the H 2 permeance and the separation factor. Enhanced mixing on the feed side could reduce the effect of the concentration polarization. Our experimental data also indicated that the membranes had excellent reproducibility and long-term stability, indicating that the hollow fiber-supported ZIF-8 membranes developed in this study have great potential in industry-scale separation of hydrogen. © 2012 Elsevier B.V.

Synthesis of ceramic hollow fiber supported zeolitic imidazolate framework-8 (ZIF-8) membranes with high hydrogen permeability

KAUST Repository

Pan, Yichang

2012-12-01

Purification and recovery of hydrogen from hydrocarbons in refinery streams in the petrochemical industry is an emerging research field in the study of membrane gas separation. Hollow fiber membrane modules can be easily implemented into separation processes at the industrial scale. In this report, hollow yttria-stabilized zirconia (YSZ) fiber-supported zeolitic imidazole framework-8 (ZIF-8) membranes were successfully prepared using a mild and environmentally friendly seeded growth method. Our single-component permeation studies demonstrated that the membrane had a very high hydrogen permeance (~15×10 -7mol/m 2sPa) and an ideal selectivity of H 2/C 3H 8 of more than 1000 at room temperature. This high membrane permeability and selectivity caused serious concentration polarization in the separation of H 2/C 3H 8 mixtures, which led to almost 50% drop in both the H 2 permeance and the separation factor. Enhanced mixing on the feed side could reduce the effect of the concentration polarization. Our experimental data also indicated that the membranes had excellent reproducibility and long-term stability, indicating that the hollow fiber-supported ZIF-8 membranes developed in this study have great potential in industry-scale separation of hydrogen. © 2012 Elsevier B.V.

Mechanistic insights into aqueous phase propanol dehydration in H-ZSM-5 zeolite

Energy Technology Data Exchange (ETDEWEB)

Mei, Donghai [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate & Institute for Integrated Catalysis, Richland WA 99352; Lercher, Johannes A. [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate & Institute for Integrated Catalysis, Richland WA 99352; Dept. of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 Garching 85748 Germany

2016-10-06

Aqueous phase dehydration of 1-propanol over H-ZSM-5 zeolite was investigated using density functional theory (DFT) calculations. The water molecules in the zeolite pores prefer to aggregate via the hydrogen bonding network and be protonated at the Brønsted acidic sites (BAS). Two typical configurations, i.e., dispersed and clustered, of water molecules were identified by ab initio molecular dynamics simulation of the mimicking aqueous phase H-ZSM-5 zeolite unit cell with 20 water molecules per unit cell. DFT calculated Gibbs free energies suggest that the dimeric propanol-propanol, the propanol-water complex, and the trimeric propanol-propanol-water are formed at high propanol concentrations, which provide a kinetically feasible dehydration reaction channel of 1-propanol to propene. However, calculation results also indicate that the propanol dehydration via the unimolecular mechanism becomes kinetically discouraged due to the enhanced stability of the protonated dimeric propanol and the protonated water cluster acting as the BAS site for alcohol dehydration reaction. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide

Directory of Open Access Journals (Sweden)

M.S. Fal Desai

2015-03-01

Full Text Available The catalytic activity of PdO/MnO2 and Rh2O3/MnO2 is investigated for NO-CO redox reaction. Supported catalysts are prepared by wet impregnation method. Among the tested catalysts, PdO/MnO2 shows higher activity for this reaction. Active metal dispersion on MnO2 enhances the selectivity for N2 over N2O in this reaction. The XRD substantiate the formation of MnO2 monophasic phase. SEM images show the formation of elongated particles. TEM images indicate nano-size rod-like morphologies. An increase in the catalytic activity is observed on supported Pd and Rh oxides on MnO2. Temperature programed desorption studies with NO and CO are undertaken to investigate the catalytic surface studies. © 2015 BCREC UNDIP. All rights reservedReceived: 22nd November 2014; Revised: 31st December 2014; Accepted: 2nd January 2015How to Cite: Fal Desai, M.S., Kunkalekar, R.K., Salker, A.V. (2015. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 98-103. (doi:10.9767/bcrec.10.1.7802.98-103Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7802.98-103 

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

Science.gov (United States)

Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

2017-10-17

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of Rhodium in an Ultradispersed Rhodium/Alumina Catalyst as Studied by EXAFS and Other Technique

NARCIS (Netherlands)

Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Huizinga, T.; Vis, J.C.; Prins, R.

1985-01-01

The structure of rhodium in an ultradispersed 0.57 wt % Rh/y-Al,O, catalyst before and after CO adsorption was studied with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), temperature programmed reduction (TPR), CO infrared

Removal of Na+ from Ionic Liquids by Zeolite for High Quality Electrolyte Manufacture

International Nuclear Information System (INIS)

Cho, Wonje; Seo, Yongseong; Jung, Soon Jae; Lee, Won Gil; Kim, Byung Chul; Yu, Kookhyun

2013-01-01

This study develops a novel method to remove the free cations created during the synthesis of ionic liquid. The cations are removed from the ionic liquid by size-selective adsorption onto chemically surface-modified Zeolite. The porous crystal nano-structure of Zeolite has several electron-rich Al sites to attract cations. While large cations of an ionic liquid cannot access the Zeolite nano-structure, small cations like Na + have ready access and are adsorbed. This study confirms that: Na + can be removed from ionic liquid effectively using Zeolite; and, in contrast to the conventional and extensively applied ion exchange resin method or solvent extraction methods, this can be done without changing the nature of the ionic liquid

Evidence for F-/SiO- anion exchange in the framework of As-synthesized all-silica zeolites

KAUST Repository

Liu, Xiaolong; Ravon, Ugo; Tuel, Alain

2011-01-01

Not everything changes: Charge-compensating anions can be exchanged in as-synthesized zeolite frameworks with changes in both the density of defect sites and of the hydrophobic character of the zeolite. The reversible transformation occurs without

Investigation of mircroorganisms colonising activated zeolites during anaerobic biogas production from grass silage.

Science.gov (United States)

Weiss, S; Zankel, A; Lebuhn, M; Petrak, S; Somitsch, W; Guebitz, G M

2011-03-01

The colonisation of activated zeolites (i.e. clinoptilolites) as carriers for microorganisms involved in the biogas process was investigated. Zeolite particle sizes of 1.0-2.5mm were introduced to anaerobic laboratory batch-cultures and to continuously operated bioreactors during biogas production from grass silage. Incubation over 5-84 days led to the colonisation of zeolite surfaces in small batch-cultures (500 ml) and even in larger scaled and flow-through disturbed bioreactors (28 l). Morphological insights were obtained by using scanning electron microscopy (SEM). Single strand conformation polymorphism (SSCP) analysis based on amplification of bacterial and archaeal 16S rRNA fragments demonstrated structurally distinct populations preferring zeolite as operational environment. via sequence analysis conspicuous bands from SSCP patterns were identified. Populations immobilised on zeolite (e.g. Ruminofilibacter xylanolyticum) showed pronounced hydrolytic enzyme activity (xylanase) shortly after re-incubation in sterilised sludge on model substrate. In addition, the presence of methanogenic archaea on zeolite particles was demonstrated. Copyright © 2010 Elsevier Ltd. All rights reserved.

Some unusual properties of activated and reduced AgNaA zeolites

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P.A. (Katholieke Univ. Leuven); Uytterhoeven, J.B.; Beyer, H.K.

1979-01-01

In a study of chemisorption on dehydrated silver-exchanged A zeolite by volumetric sorption and temperature-programed desorption techniques, an autoreductive process which created intense color centers, occurred on degassing the zeolite because of the formation of silver covalent bonds. The chemisorption of hydrogen was proportional to the amount of autoreduction, indicating that the process occurred on the color centers. Both oxygen and hydrogen chemisorbed dissociatively, as shown by tracing with labeled oxygen and by the ability of one water molecule to replace two hydrogen atoms. Carbon monoxide, however, was chemisorbed on the available silver ions in the zeolite supercages, whether or not they were a part of the cluster formation. Linear silver ion/silver/silver ion clusters are apparently formed in the zeolite cubo-octahedra upon activation; the ends form chemisorption sites for hydrogen and oxygen.

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template

KAUST Repository

Zhu, Jie; Zhu, Yihan; Zhu, Liangkui; Rigutto, Marcello S.; Van Der Made, Alexander W.; Yang, Chengguang; Pan, Shuxiang; Wang, Liang; Zhu, Longfeng; Jin, Yinying; Sun, Qi; Wu, Qinming; Meng, Xiangju; Zhang, Daliang; Han, Yu; Li, Jixue; Chu, Yueying; Zheng, Anmin; Qiu, Shilun; Zheng, Xiaoming; Xiao, Fengshou

2014-01-01

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a

Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

Science.gov (United States)

Lyu, Cong; Yang, Xuejiao; Zhang, Shengyu; Zhang, Qihui; Su, Xiaosi

2017-12-29

A promising and easily prepared catalytic filler media, manganese-oxide-coated zeolite (MOCZ), for the removal of Mn (II) contamination in groundwater was studied. The optimal condition for MOCZ preparation was given as follows: acid activation of zeolite with 5% HCl mass percent for 12 h, then soaking of acid-activated zeolite with 7% KMnO 4 mass percent for 8 h, and finally calcination at 300°C for 5 h. Acid activation significantly enlarged the specific surface area of the zeolite (>79 m 2  g -1 ), subsequently enhancing the coating of manganese oxides onto the surface of the zeolite. This was further supported by the manganese-to-zeolite ratio (γ Mn ) and Energy dispersive analysis-mapping. The γ Mn was over 12.26 mg Mn g -1 zeolite, representing more active sites for the adsorption and catalytic-oxidation of Mn (II). As such, great performance of Mn (II) removal by MOCZ was obtained in the filter experiment. An estimated 98-100% removal efficiency of Mn (II) was achieved in a greatly short startup time (only 2 h). During the filtration process, newborn flocculent manganese oxides with a mixed-valence of manganese (Mn (II) and Mn (IV)) were generated on the MOCZ surface, further facilitating the adsorption and catalytic-oxidation of Mn (II). The filter with MOCZ as adsorbent had a great performance on the Mn (II) removal in a wide range of hydraulic retention time (HRT) (4-40 min), particularly in a short HRT. Besides, the filter prolonged the filtration period (60 days), which would significantly reduce the frequency of backwash. Thus, it could be concluded that MOCZ prepared in this study showed a good performance in terms of Mn (II) removal in waterworks, especially small waterworks in the villages/towns.

Design and characterization of chitosan/zeolite composite films — Effect of zeolite type and zeolite dose on the film properties

International Nuclear Information System (INIS)

Barbosa, Gustavo P.; Debone, Henrique S.; Severino, Patrícia; Souto, Eliana B.; Silva, Classius F. da

2016-01-01

Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance. - Highlights: • Zeolite/chitosan composite films were prepared by casting technique. • Micrographs showed slight difference according to the content and A-type zeolite. • The barrier properties of the films were suitable to the dressing application. • Film characterization suggested that zeolites interacted with the chitosan chain.

Design and characterization of chitosan/zeolite composite films — Effect of zeolite type and zeolite dose on the film properties

Energy Technology Data Exchange (ETDEWEB)

Barbosa, Gustavo P.; Debone, Henrique S. [Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema (Brazil); Severino, Patrícia [Universidade Tiradentes, Instituto de Tecnologia e Pesquisa, Aracaju (Brazil); Souto, Eliana B. [Department of Pharmaceutical Technology, Faculty of Pharmacy, University of Coimbra (FFUC), Pólo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548, Coimbra (Portugal); Center for Neuroscience and Cell Biology & Institute for Biomedical Imaging and Life Sciences (CNC-IBILI), University of Coimbra, Pólo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548, Coimbra (Portugal); Silva, Classius F. da, E-mail: cfsilva@unifesp.br [Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema (Brazil)

2016-03-01

Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance. - Highlights: • Zeolite/chitosan composite films were prepared by casting technique. • Micrographs showed slight difference according to the content and A-type zeolite. • The barrier properties of the films were suitable to the dressing application. • Film characterization suggested that zeolites interacted with the chitosan chain.

Diagnosing the Internal Architecture of Zeolite Ferrierite

Science.gov (United States)

Schmidt, Joel E.; Hendriks, Frank C.; Lutz, Martin; Post, L. Christiaan; Fu, Donglong

2017-01-01

Abstract Large crystals of zeolite ferrierite (FER) are important model systems for spatially resolved catalysis and diffusion studies, though there is considerable variation in crystal habit depending on the chemical composition and employed synthesis conditions. A synergistic combination of techniques has been applied, including single crystal X‐ray diffraction, high‐temperature in situ confocal fluorescence microscopy, fluorescent probe molecules, wide‐field microscopy and atomic force microscopy to unravel the internal architecture of three distinct FER zeolites. Pyrolyzed template species can be used as markers for the 8‐membered ring direction as they are trapped in the terraced roof of the FER crystals. This happens as the materials grow in a layer‐by‐layer, defect‐free manner normal to the large crystal surface, and leads to a facile method to diagnose the pore system orientation, which avoids tedious single crystal X‐ray diffraction experiments. PMID:28809081

Rhodium-catalyzed C-H alkynylation of arenes at room temperature.

Science.gov (United States)

Feng, Chao; Loh, Teck-Peng

2014-03-03

The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bacterial biofilm supported on granular activated carbon and on natural zeolites- an application to wastewater treatment

OpenAIRE

Lameiras, Sandra Raquel de Vasconcelos; Quintelas, C.; Tavares, M. T.

2004-01-01

The removal of many heavy metals from industrial wastewater is one of the most important environmental problems to be solved today. The retention of this contaminants by a biofilm supported on granular activated carbon or on natural zeolites is one of the promising technologies for the reduction of this problem, because it is cheap and it removes a broad range of substances, heavy metals and organic compounds. This study aims the development of a system of two mini-columns in series ...

Effects of ultrasonic irradiation on crystallization and structural properties of EMT-type zeolite nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Ng, Eng-Poh, E-mail: epng@usm.my [School of Chemical Sciences, Universiti Sains Malaysia, USM, 11800 Penang (Malaysia); Awala, Hussein [Laboratoire Catalyse & Spectrochimie, CNRS-ENSICAEN, Université de Caen (France); Ghoy, Jia-Pei [School of Chemical Sciences, Universiti Sains Malaysia, USM, 11800 Penang (Malaysia); Vicente, Aurélie [Laboratoire Catalyse & Spectrochimie, CNRS-ENSICAEN, Université de Caen (France); Ling, Tau Chuan [Institute of Biological Sciences, Faculty of Science, University of Malaya (Malaysia); Ng, Yun Hau [School of Chemical Engineering, The University of New South Wales, Sydney (Australia); Mintova, Svetlana [Laboratoire Catalyse & Spectrochimie, CNRS-ENSICAEN, Université de Caen (France); Adam, Farook, E-mail: farook@usm.my [School of Chemical Sciences, Universiti Sains Malaysia, USM, 11800 Penang (Malaysia)

2015-06-01

Synthesis of EMT zeolite nanocrystals from rice husk ash biomass (RHA) under continuous ultrasonic irradiation is reported. The aging, nucleation and crystallization stages of EMT zeolite in the system were monitored at ambient temperature, and compared with the conventional hydrothermal method. It was found that ultrasonic wave induced rapid crystal growth of the nanosized EMT zeolite. Complete crystallization of EMT nanocrystals was achieved within 24 h which was much faster than conventional hydrothermal synthesis (36 h). Furthermore, XRD and TEM analyses revealed that more nuclei were formed during the nucleation stage, allowing the preparation of smaller zeolite nanocrystals with high crystallinity. The results also showed that sonocrystallization produced EMT zeolite with high yield (ca. 80%). The ultrasound-prepared EMT nanocrystals were also found to have high porosity and high hydrophilicity, making the material promising for water sorption applications including vapor sensing, heat pump and adsorption technologies. - Highlights: • Nanosized EMT zeolites are formed from rice husk ash under ultrasonic irradiation. • The effects of ultrasonic waves in nanosized EMT zeolite synthesis are studied. • Ultrasound induces rapid crystal growth and produces high zeolite yield. • Smaller zeolite nanocrystals with high crystallinity and large defect sites are obtained. • Improved surface hydrophilicity of crystals is beneficial for water sorption applications.

Investigation of Y, FAU-zeolites containing rare earth cations

International Nuclear Information System (INIS)

Gardos, G.; De Jonge, A.; Halmos, F.; Kristof, J.; Redey, A.

1984-01-01

Polycationic zeolites were made of the H (NHsub(4))-Y, FAU form one. The change of Broensted acid sites was followed as a function of the pretreating temperature by infrared spectroscopy for mixed (La, Ce) form zeolites. It was stated that the 3630 cmsup(-1) absorption band can be related to the acidic OH-groups responsible for the catalytic activity in the alkylating reaction of isobutane with 1-butene, while the band at 3510 cmsup(-1) is characteristic of the non-acidic hydroxyl-groups and has no relation with the catalytic activity. (author)

Scalar Relativistic Study of the Structure of Rhodium Acetate

Directory of Open Access Journals (Sweden)

Emily E. Edwards

2004-01-01

Full Text Available Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3. Several combinations of exchange-correlation functionals with relativistic and non-relativistic effective core potentials (ECP were investigated, as were non-relativistic and all electron scalar relativistic methods. The combination of the PW91 exchange and PW91 correlation functional with the Christiansen-Ermler ECP gave the best results: 2.3918 Å compared to the experimental value of 2.3855±0.0005 Å.

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang

2018-04-04

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

2018-01-01

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

Investigating the Influence of Mesoporosity in Zeolite Beta on its Catalytic Performance for the Conversion of Methanol to Hydrocarbons

KAUST Repository

Liu, Zhaohui

2015-08-26

Hierarchically porous zeolite Beta (Beta-MS) synthesized by a soft-templating method contains remarkable intra-crystalline mesoporosity, which reduces the diffusion length in zeolite channels down to several nanometers and alters the distribution of Al among distinct crystallographic sites. When used as a catalyst for the conversion of methanol to hydrocarbons (MTH) at 330 oC, Beta-MS exhibited a 2.7-fold larger conversion capacity, a 2.0-fold faster reaction rate, and a remarkably longer lifetime than conventional zeolite Beta (Beta-C). The superior catalytic performance of Beta-MS is attributed to its hierarchical structure, which offers full accessibility to all catalytic active sites. In contrast, Beta-C was easily deactivated because a layer of coke quickly deposited on the outer surfaces of the catalyst crystals, impeding access to interior active sites. This difference is clearly demonstrated by using electron microscopy combined with electron energy loss spectroscopy to probe the distribution of coke in the deactivated catalysts. At both low and high conversions, ranging from 20% to 100%, Beta-MS gave higher selectivity towards higher aliphatics (C4-C7) but lower ethene selectivity compared to Beta-C. Therefore, we conclude that a hierarchical structure decreases the residence time of methylbenzenes in zeolite micropores, disfavoring the propagation of the aromatic-based catalytic cycle. This conclusion is consistent with a recent report on ZSM-5 and is also strongly supported by our analysis of soluble coke species residing in the catalysts. Moreover, we identified an oxygen-containing compound, 4-methyl-benzaldehyde, in the coke, which has not been observed in the MTH reaction before.  

Investigating the Influence of Mesoporosity in Zeolite Beta on its Catalytic Performance for the Conversion of Methanol to Hydrocarbons

KAUST Repository

Liu, Zhaohui; Dong, Xinglong; Zhu, Yihan; Emwas, Abdul-Hamid M.; Zhang, Daliang; Tian, Qiwei; Han, Yu

2015-01-01

Hierarchically porous zeolite Beta (Beta-MS) synthesized by a soft-templating method contains remarkable intra-crystalline mesoporosity, which reduces the diffusion length in zeolite channels down to several nanometers and alters the distribution of Al among distinct crystallographic sites. When used as a catalyst for the conversion of methanol to hydrocarbons (MTH) at 330 oC, Beta-MS exhibited a 2.7-fold larger conversion capacity, a 2.0-fold faster reaction rate, and a remarkably longer lifetime than conventional zeolite Beta (Beta-C). The superior catalytic performance of Beta-MS is attributed to its hierarchical structure, which offers full accessibility to all catalytic active sites. In contrast, Beta-C was easily deactivated because a layer of coke quickly deposited on the outer surfaces of the catalyst crystals, impeding access to interior active sites. This difference is clearly demonstrated by using electron microscopy combined with electron energy loss spectroscopy to probe the distribution of coke in the deactivated catalysts. At both low and high conversions, ranging from 20% to 100%, Beta-MS gave higher selectivity towards higher aliphatics (C4-C7) but lower ethene selectivity compared to Beta-C. Therefore, we conclude that a hierarchical structure decreases the residence time of methylbenzenes in zeolite micropores, disfavoring the propagation of the aromatic-based catalytic cycle. This conclusion is consistent with a recent report on ZSM-5 and is also strongly supported by our analysis of soluble coke species residing in the catalysts. Moreover, we identified an oxygen-containing compound, 4-methyl-benzaldehyde, in the coke, which has not been observed in the MTH reaction before.  

Removal of paraquat solution onto zeolite material

Science.gov (United States)

Sirival, Rujikarn; Patdhanagul, Nopbhasinthu; Preecharram, Sutthidech; Photharin, Somkuan

2018-04-01

The purpose of this research was to study the adsorption of paraquat herbicides onto zeolite Y materials by the batch method. Three adsorbents material: Zeolite-3, Zeolite-10, and Zeolite-100 were Si/Al ratio at 3.58, 8.57 and 154.37, respectively. The factors for adsorption of paraquat as follows, adsorption time, initial concentrations of paraquat, pH and adsorption isotherm were investigated. The results showed that zeolite-10 had higher adsorption capacity than zeolite-3 and zeolite-100. The appropriate conditions for adsorption were 24 h., Zeolite 0.1 g., Initial paraquat concentration 100 ppm at pH 6. The adsorption isotherm was found to correspond with Langmuir Isotherm and the maximum paraquat adsorption is 26.38 mg/g for zeolite-10, 21.41 mg/g and 9.60 mg/g for zeolite-3 and zeolite-100, respectively. The characterization of zeolite material with XRD, XRF and BET. Furthermore, the zeolite materials applied to remove other organic and inorganic wastewater.

Robotic single-site pelvic lymphadenectomy.

Science.gov (United States)

Tateo, Saverio; Nozza, Arrigo; Del Pezzo, Chiara; Mereu, Liliana

2014-09-01

To examine the feasibility of performing pelvic lymphadenectomy with robotic single site approach. Recent papers described the feasibility of robotic-single site hysterectomy [1-3] for benign and malign pathologies but only with the development of new single site 5mm instruments as the bipolar forceps, robotic single site platform can be safely utilized also for lymphadenectomy. A 65 year-old, multiparous patient with a body mass index of 22.5 and diagnosed with well differentiated adenocarcinoma of the endometrium underwent a robotic single-site peritoneal washing, total hysterectomy, bilateral adnexectomy and pelvic lymphadenectomy. The procedure was performed using the da Vinci Si Surgical System (Intuitive Surgical, Sunnyvale, CA) through a single 2,5 cm umbilical incision, with a multi-channel system and two single site robotic 5mm instruments. A 3-dimensional, HD 8.5mm endoscope and a 5mm accessory instrument were also utilized. Type I lymphonodes dissection for external iliac and obturator regions was performed [4]. Total operative time was 210 min; incision, trocar placement and docking time occurring in 12 min. Total console time was 183 min, estimated blood loss was 50 ml, no intra-operative or post-operative complications occurred. Hospital discharge occurred on post operative day 2 and total number of lymphnodes removed was 33. Difficulties in term of instrument's clashing and awkward motions have been encountered. Robotic single-site pelvic lymphadenectomy using bipolar forceps and monopolar hook is feasible. New developments are needed to improve surgical ergonomics and additional studies should be performed to explore possible benefits of this procedure. Copyright © 2014 Elsevier Inc. All rights reserved.

High resolution NMR in zeolites

International Nuclear Information System (INIS)

Diaz, Anix

1991-01-01

In this work 29 Si and 27 Al NMR spectroscopy was used to study various types of zeolites. The corresponding spectra were used to measure the Si/Al ratios, to follow chemical modifications induced by acid and hydrothermal treatments, to determine non-equivalent crystallographic sites in highly dealuminated mordenites, and to detect modifications of faujasites due to the insertion of titanium atoms in the lattice. (author)

Crystal structures of fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) monohydrate and fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

OpenAIRE

Merola, Joseph S.; Franks, Marion A.

2015-01-01

The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made bet...

{gamma} alumina- and HY zeolite-supported molybdenum catalysts: characterisation of the oxidic and sulfided phases; Catalyseurs a base de molybdene supporte sur alumine {gamma} et zeolithe HY: caracterisation des phases oxydes et sulfures

Energy Technology Data Exchange (ETDEWEB)

Plazenet, G

2001-10-01

Oxidic precursors of hydro-treatment catalysts (Co)Mo/alumina or zeolite were characterised by Raman spectroscopy, NMR and EXAFS at the Mo and Co K-edges. The formation of an Anderson-type alumino-molybdate compound upon impregnation of the support with an ammonium hepta-molybdate solution was confirmed for alumina, and also observed for the HY zeolitic support, with consumption of the amorphous alumina of the zeolite. In absence of the latter, ammonium hepta-molybdate precipitates. The species are conserved upon drying; upon calcination, the alumino-molybdate evolves into a surface aluminium molybdate type phase, whereas the hepta-molybdate transforms into MoO{sub 3}. The species formed upon impregnation are located in the inter-granular porosity whereas MoO{sub 3} vapor-condensation leads to formation of dimers located inside the zeolitic structure. The study of the cobalt-promoted precursors showed that the evolution of the molybdenum is the same in the case of co-impregnation preparation. Impregnation with cobalt-molybdate prevents the formation of the alumino-molybdate anion and thus enables the preservation of the Mo-Co interaction but, whatever the precursor, the leveling effect of the calcination-re-hydration steps was demonstrated. An EXAFS study at different sulfur coverages of the MoS{sub 2} platelets in the alumina-supported sulfided catalysts showed the limitations of EXAFS for size determination of MoS{sub 2} crystallites, a parameter that can be reached by AWAXS, which also conveys information about sheet-stacking. The EXAFS study of sulfided (Co)Mo/HY systems revealed incomplete sulfidation of the samples and the very high dispersion of the active phase. The absence of an observable Mo-Co interaction whatever the preparation of the promoted catalysts is consistent with the absence of promoting effect in toluene hydrogenation. (author)

Hydrogenation of hexene over platinum on alumina vs. platinum in a Na-Y zeolite

International Nuclear Information System (INIS)

Miner, R.S. Jr.; Ione, K.G.; Namba, S.; Turkevich, J.

1978-01-01

In order to study the efficacy of zeolites as supports, several platinum H--Y zeolites were prepared by ion exchanging an H--Y zeolite with Pt(NH 3 ) 4 Cl 2 and reducing these products with hydrazine hydrate (A, B, C). Another preparation was made by adsorbing 32-A platinum sol on the zeolite crystallites (D). These catalysts were studied for hydrogenation and isomerization of hexene-1, ethylene hydrogenation, hydrogen chemisorption, and poison titration. They were compared with monodisperse Pt (32 A diameter) on alumina. A marked difference was found between the behavior of hexene-1 with the platinum-in-zeolite and with the platinum-on-alumina

Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

Science.gov (United States)

Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

2015-01-01

A successive anchoring of Zr(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15-500) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15-500 supported zirconium complexes were characterized by in situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

Redox behavior of transition metal ions in zeolites 6. Reversibility of the reduction reaction in silver zeolites

Energy Technology Data Exchange (ETDEWEB)

Jacobs, P A; Uytterhoeven, J B; Beyer, H K

1977-01-01

Degassing above 573/sup 0/K of Ag-Y or Ag-mordenite previously reduced by hydrogen at 623/sup 0/K resulted in hydrogen evolution, the amount of hydrogen increasing to a maximum at about 873/sup 0/K. No hydrogen was evolved when the zeolite was reduced by hydrazine or hydroxylamine, indicating that hydrogen is formed by reaction between silver metal and hydroxyl groups formed in the reduction step (i.e., the reverse of the reduction step). Consumption of hydroxyl groups was proven by IR studies of pyridine chemisorption which occurs entirely as pyridinium ions on Broensted sites or reduced samples but with increasing formation of pyridine on Lewis acid sites as the degassing temperature increases; formation of silver(I) ions was proven by carbon monoxide complexation. Silver metal outside the zeolite pores was not affected by the degassing, and the amount of hydrogen evolved upon degassing decreased with increasing number of reduction-degassing cycles, probably as a result of dehydroxylation or sintering. Spectra, graphs, tables, and 21 references.

ADSORPSI POLUTAN ION DIKROMAT MENGGUNAKAN ZEOLIT ALAM TERMODIFIKASI AMINA (Adsorption of Dichromate Ions Pollutant Using Ammine Modified-Natural Zeolites

Directory of Open Access Journals (Sweden)

Eko Sri Kunarti

2015-11-01

Full Text Available ABSTRAK Kromium (VI merupakan polutan logam berat berbahaya bagi kesehatan dan lingkungan oleh karena itu pengambilan ion Cr(VI dalam air penting dilakukan untuk mengatasi pencemaran lingkungan. Proses adsorpsi merupakan salah satu teknik sederhana yang dapat digunakan untuk pengambilan ion logam. Pada penelitian ini telah dilakukan kajian adsorpsi ion dikromat sebagai model limbah Cr(VI dalam air menggunakan adsorben zeolit alam termodifikasi amina. Penelitian diawali dengan preparasi adsorben zeolit alam termodifikasi amina. Preparasi dimulai dengan pencucian zeolit alam menggunakan akuades, kemudian refluks zeolit alam menggunakan HCl 3M. Zeolit hasil refluks selanjutnya dimodifikasi menggunakan garam ammonium kuarterner, N-cethyl-N,N,N-trimethylammonium bromide (CTAB dan amina primer, propilamin (PA. Zeolit alam (Z, zeolit teraktivasi asam (ZA dan zeolit hasil modifikasi amina selanjutnya digunakan sebagai adsorben untuk adsorpsi anion dikromat. Karakterisasi adsorben dilakukan dengan mengunakan metode spektroskopi infaramerah dan difraksi sinar-X, sedangkan jumlah anion dikromat yang teradsorpsi dianalisis dengan spektroskopi serapan atom. Hasil penelitian menunjukkan bahwa sampel zeolit mengandung mineral klinoptilolit, mordernit dan kuarsa. Struktur zeolit tidak mengalami kerusakan oleh perlakuan termal dan perlakuan kimia. Modifikasi zeolit meningkatkan efisiensi adsorpsi zeolit alam. Ion dikromat dapat teradsorpsi dengan lebih baik oleh zeolit termodifikasi amina daripada zeolit teraktivasi asam dan zeolit tanpa modifikasi, dengan kemampuan adsorpsi zeolit termodifikasi CTAB (CTAB-Z lebih besar daripada zeolit termodifikasi propilamin (PA-Z. Adsorpsi ion dikromat pada adsorben zeolit berlangsung baik dengan urutan CTAB-Z > PA-Z > ZA > Z, dengan kemampuan adsorpsi masing-masing sebesar 1,96; 1,74; 0,90 dan 0,48 mg/g. Adsorpsi anion dikromat oleh zeolit termodifikasi CTAB merupakan adsorpsi kimia (kemisorpsi dengan energi adsorpsi sebesar

Study of the Cd (II) removal in the presence of methyl orange with a natural zeolite conditioned with iron nanoparticles

International Nuclear Information System (INIS)

Xingu C, E. G.

2015-01-01

This work presents a study on the removal of cadmium and/or methyl-orange dye in aqueous solution, using natural zeolite clinoptilolite, as sodium homo-ionized and impregnated with iron nanoparticles. Iron nanoparticles were synthesized in the presence of the zeolite by chemical reduction. The evaluation of the removal ability was performed in a monocomponent (cadmium or methyl-orange dye) system by varying the contact time and its initial concentration. Removal capacity in a bi-component (cadmium and methyl orange) system was also studied while varying their concentrations. The characterization of the zeolites, before and after the sorption process, was carried out using several analytical techniques. The characteristics of zeolite clinoptilolite and iron particles were observed by scanning electron microscopy. The iron particles showed diameter sizes between 60 and 200 nm, localized on the surface of the zeolite. By IR spectroscopy no structural changes were detected for any of the treatments made to the zeolitic materials. By X-ray diffraction the clinoptilolite crystalline phase was mainly identified, however, it failed to detect any phase of iron in the zeolite impregnated with iron nanoparticles. Moessbauer spectroscopy indeed detected the impregnated iron phase as iron borides. The homo-ionized and iron nanoparticles impregnated zeolite showed no change in the specific surface area, or the isoelectric point, their values were 22.3 m"2/g and ph 9.8, respectively. However, whereas the active site density for the homo-ionized zeolite was 2.87 sites/nm"2, for iron nanoparticles impregnated zeolite was 20.32 sites/nm"2. As a result of the analysis of the isotherms of cadmium, the maximum sorption capacity of the homo-ionized zeolite was 35.03 mg/g and for the iron nanoparticles impregnated zeolite was 36.43 mg/g. These maximum sorption capacities represent up to 85% of removed cadmium from concentrations of 50 to 600 mg/L. For the removal of methyl orange dye

Beyond Creation of Mesoporosity: The Advantages of Polymer-Based Dual-Function Templates for Fabricating Hierarchical Zeolites

KAUST Repository

Tian, Qiwei

2016-02-05

Direct synthesis of hierarchical zeolites currently relies on the use of surfactant-based templates to produce mesoporosity by the random stacking of 2D zeolite sheets or the agglomeration of tiny zeolite grains. The benefits of using nonsurfactant polymers as dual-function templates in the fabrication of hierarchical zeolites are demonstrated. First, the minimal intermolecular interactions of nonsurfactant polymers impose little interference on the crystallization of zeolites, favoring the formation of 3D continuous zeolite frameworks with a long-range order. Second, the mutual interpenetration of the polymer and the zeolite networks renders disordered but highly interconnected mesopores in zeolite crystals. These two factors allow for the synthesis of single-crystalline, mesoporous zeolites of varied compositions and framework types. A representative example, hierarchial aluminosilicate (meso-ZSM-5), has been carefully characterized. It has a unique branched fibrous structure, and far outperforms bulk aluminosilicate (ZSM-5) as a catalyst in two model reactions: conversion of methanol to aromatics and catalytic cracking of canola oil. Third, extra functional groups in the polymer template can be utilized to incorporate desired functionalities into hierarchical zeolites. Last and most importantly, polymer-based templates permit heterogeneous nucleation and growth of mesoporous zeolites on existing surfaces, forming a continuous zeolitic layer. In a proof-of-concept experiment, unprecedented core-shell-structured hierarchical zeolites are synthesized by coating mesoporous zeolites on the surfaces of bulk zeolites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

Science.gov (United States)

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermally grown zeolite crystals

International Nuclear Information System (INIS)

Durrani, S.K.; Qureshi, A.H.; Hussain, M.A.; Qazi, N.K.

2009-01-01

The aluminium-deficient and ferrosilicate zeolite-type materials were synthesized by hydrothermal process at 150-170 degree C for various periods of time from the mixtures containing colloidal reactive silica, sodium aluminate, sodium hydroxide, iron nitrate and organic templates. Organic polycation templates were used as zeolite crystal shape modifiers to enhance relative growth rates. The template was almost completely removed from the zeolite specimens by calcination at 550 degree C for 8h in air. Simultaneous thermogravimetric (TG) and differential thermal analysis (DTA) was performed to study the removal of water molecules and the amount of organic template cations occluded inside the crystal pore of zeolite framework. The 12-13% weight loss in the range of (140-560 degree C) was associated with removal of the (C/sub 3/H/sub 7/)/sub 4/ N+ cation and water molecules. X-ray diffraction (XRD) analysis and scanning electron microscope (SEM) techniques were employed to study the structure, morphology and surface features of hydrothermally grown aluminium-deficient and ferrosilicate zeolite-type crystals. In order to elucidate the mode of zeolite crystallization the crystallinity and unit cell parameters of the materials were determined by XRD, which are the function of Al and Fe contents of zeolites. (author)

Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

Energy Technology Data Exchange (ETDEWEB)

Favre, F.

2000-10-26

Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

Characterization and antibacterial activity of silver exchanged regenerated NaY zeolite from surfactant-modified NaY zeolite

Energy Technology Data Exchange (ETDEWEB)

Salim, Mashitah Mad; Malek, Nik Ahmad Nizam Nik, E-mail: niknizam@fbb.utm.my

2016-02-01

The antibacterial activity of regenerated NaY zeolite (thermal treatment from cetyltrimethyl ammonium bromide (CTAB)-modified NaY zeolite and pretreatment with Na ions) loaded with silver ions were examined using the broth dilution minimum inhibitory concentration (MIC) method against Escherichia coli (E. coli ATCC 11229) and Staphylococcus aureus (S. aureus ATCC 6538). X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and chemical elemental analyses were used to characterize the regenerated NaY and AgY zeolites. The XRD patterns indicated that the calcination and addition of silver ions on regenerated NaY zeolite did not affect the structure of the regenerated NaY zeolite as the characteristic peaks of the NaY zeolite were retained, and no new peaks were observed. The regenerated AgY zeolite showed good antibacterial activity against both bacteria strains in distilled water, and the antibacterial activity of the samples increased with increasing Ag loaded on the regenerated AgY zeolite; the regenerated AgY zeolite was more effective against E. coli than S. aureus. However, the antibacterial activity of the regenerated AgY was not effective in saline solution for both bacteria. The study showed that CTAB-modified NaY zeolite materials could be regenerated to NaY zeolite using thermal treatment (550 °C, 5 h) and this material has excellent performance as an antibacterial agent after silver ions loading. - Highlights: • Thermal treatment was used to regenerate surfactant modified zeolite. • The regenerated NaY zeolite formed was added with different silver loadings. • Regenerated AgY zeolite was tested for antibacterial activity on E. coli and S. aureus. • The antibacterial activity increased with increased of the amount of silver loadings. • The zeolite structure did not change with thermal and modification

Characterization and antibacterial activity of silver exchanged regenerated NaY zeolite from surfactant-modified NaY zeolite

International Nuclear Information System (INIS)

Salim, Mashitah Mad; Malek, Nik Ahmad Nizam Nik

2016-01-01

The antibacterial activity of regenerated NaY zeolite (thermal treatment from cetyltrimethyl ammonium bromide (CTAB)-modified NaY zeolite and pretreatment with Na ions) loaded with silver ions were examined using the broth dilution minimum inhibitory concentration (MIC) method against Escherichia coli (E. coli ATCC 11229) and Staphylococcus aureus (S. aureus ATCC 6538). X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and chemical elemental analyses were used to characterize the regenerated NaY and AgY zeolites. The XRD patterns indicated that the calcination and addition of silver ions on regenerated NaY zeolite did not affect the structure of the regenerated NaY zeolite as the characteristic peaks of the NaY zeolite were retained, and no new peaks were observed. The regenerated AgY zeolite showed good antibacterial activity against both bacteria strains in distilled water, and the antibacterial activity of the samples increased with increasing Ag loaded on the regenerated AgY zeolite; the regenerated AgY zeolite was more effective against E. coli than S. aureus. However, the antibacterial activity of the regenerated AgY was not effective in saline solution for both bacteria. The study showed that CTAB-modified NaY zeolite materials could be regenerated to NaY zeolite using thermal treatment (550 °C, 5 h) and this material has excellent performance as an antibacterial agent after silver ions loading. - Highlights: • Thermal treatment was used to regenerate surfactant modified zeolite. • The regenerated NaY zeolite formed was added with different silver loadings. • Regenerated AgY zeolite was tested for antibacterial activity on E. coli and S. aureus. • The antibacterial activity increased with increased of the amount of silver loadings. • The zeolite structure did not change with thermal and modification

Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

International Nuclear Information System (INIS)

Rao, A.L.J.; Gupta, Usha; Puri, B.K.

1986-01-01

Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

Ultrasound-assisted dealumination of zeolite Y

Indian Academy of Sciences (India)

zeolite Y the Si/Al molar ratio plays an important role in solid acidity .... determined using electron microprobe X-ray analysis. (EMPA) We also ... Surface area (m2/g) Pore Volume (cm3/g) XRD calculation .... for financial support for this work.

Risk assessment for the transportation of radioactive zeolite liners

International Nuclear Information System (INIS)

1982-01-01

The risk is estimated for the shipment of radioactive zeolite liners in support of the Zeolite Vitrification Demonstration Program currently underway at Pacific Northwest Laboratory under the sponsorship of the US Department of Energy. This program will establish the feasibility of zeolite vitrification as an effective means of immobilizing high-specific-activity wastes. In this risk assessment, it is assumed that two zeolite liners, each loaded around July 1, 1981 to 60,000 Ci, will be shipped by truck around January 1, 1982. However, to provide a measure of conservatism, each liner is assumed to initially hole 70,000 Ci, with the major radioisotopes as follow: 90 Sr = 3000 Ci, 134 Cs = 7000 Ci, 137 Cs = 60,000 Ci. Should shipment take place with essentially no delay after initial loading (regardless of loading date), the shipment loading would be only 2.7% higher than that for the assumed six-month delay. This would negligibly affect the overall risk. As a result of this risk assessment, it is concluded that the transport of the radioactive zeolite liners from TMI to PNL by truck can be conducted at an insignificant level of risk to the public

Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

Science.gov (United States)

Piou, Tiffany; Rovis, Tomislav

2015-11-05

Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

Science.gov (United States)

Kondoh, Azusa; Jamison, Timothy F.

2010-01-01

A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

Process for producing zeolite adsorbent and process for treating radioactive liquid waste with the zeolite adsorbent

International Nuclear Information System (INIS)

Motojima, K.; Kawamura, F.

1984-01-01

Zeolite is contacted with an aqueous solution containing at least one of copper, nickel, cobalt, manganese and zinc salts, preferably copper and nickel salts, particularly preferably copper salt, in such a form as sulfate, nitrate, or chloride, thereby adsorbing the metal on the zeolite in its pores by ion exchange, then the zeolite is treated with a water-soluble ferrocyanide compound, for example, potassium ferrocyanide, thereby forming metal ferrocyanide on the zeolite in its pores. Then, the zeolite is subjected to ageing treatment, thereby producing a zeolite adsorbent impregnated with metal ferrocyanide in the pores of zeolite. The adsorbent can selectively recover cesium with a high percent cesium removal from a radioactive liquid waste containing at least radioactive cesium, for example, a radioactive liquid waste containing cesium and such coexisting ions as sodium, magnesium, calcium and carbonate ions at the same time at a high concentration. The zeolite adsorbent has a stable adsorbability for a prolonged time

Rapid synthesis of beta zeolites

Science.gov (United States)

Fan, Wei; Chang, Chun -Chih; Dornath, Paul; Wang, Zhuopeng

2015-08-18

The invention provides methods for rapidly synthesizing heteroatom containing zeolites including Sn-Beta, Si-Beta, Ti-Beta, Zr-Beta and Fe-Beta. The methods for synthesizing heteroatom zeolites include using well-crystalline zeolite crystals as seeds and using a fluoride-free, caustic medium in a seeded dry-gel conversion method. The Beta zeolite catalysts made by the methods of the invention catalyze both isomerization and dehydration reactions.

Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

KAUST Repository

Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

2016-01-01

The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

KAUST Repository

Werghi, Baraa

2016-09-26

The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

Separation of BSA through FAU-type zeolite ceramic composite membrane formed on tubular ceramic support: Optimization of process parameters by hybrid response surface methodology and biobjective genetic algorithm.

Science.gov (United States)

Vinoth Kumar, R; Ganesh Moorthy, I; Pugazhenthi, G

2017-08-09

In this study, Faujasite (FAU) zeolite was coated on low-cost tubular ceramic support as a separating layer through hydrothermal route. The mixture of silicate and aluminate solutions was used to create a zeolitic separation layer on the support. The prepared zeolite ceramic composite membrane was characterized using X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), particle size distribution (PSD), field emission scanning electron microscopy (FESEM), and zeta potential measurements. The porosity of ceramic support (53%) was reduced by the deposition of FAU (43%) zeolite layer. The pore size and water permeability of the membrane were evaluated as 0.179 µm and 1.62 × 10 -7  m 3 /m 2  s kPa, respectively, which are lower than that of the support (pore size of 0.309 µm and water permeability of 5.93 × 10 -7  m 3 /m 2  s kPa). The permeate flux and rejection potential of the prepared membrane were evaluated by microfiltration of bovine serum albumin (BSA). To study the influences of three independent variables such as operating pressure (68.94-275.79 kPa), concentration of BSA (100-500 ppm), and solution pH (2-4) on permeate flux and percentage of rejection, the response surface methodology (RSM) was used. The predicted models for permeate flux and rejection were further subjected to biobjective genetic algorithm (GA). The hybrid RSM-GA approach resulted in a maximum permeate flux of 2.66 × 10 -5  m 3 /m 2  s and BSA rejection of 88.02%, at which the optimum conditions were attained as 100 ppm BSA concentration, 2 pH solution, and 275.79 kPa applied pressure. In addition, the separation efficiency was compared with other membranes applied for BSA separation to know the potential of the fabricated FAU zeolite ceramic composite membrane.

Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production

Energy Technology Data Exchange (ETDEWEB)

Volli, Vikranth; Purkait, M.K., E-mail: mihir@iitg.ernet.in

2015-10-30

Highlights: • Flyash was utilized for zeolites preparation for transesterification. • Single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio of 1:1.2. • Si/Al ratio of 2 resulted in the formation of zeolite X. • At 5 wt% of catalyst loading conversion was 84.6%. • The biodiesel obtained has a calorific value of 37.5 MJ/Kg. - Abstract: This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12 h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity.

Zeolite scaffolds for cultures of human breast cancer cells. Part II: Effect of pure and hybrid zeolite membranes on neoplastic and metastatic activity control.

Science.gov (United States)

Tavolaro, Palmira; Martino, Guglielmo; Andò, Sebastiano; Tavolaro, Adalgisa

2016-11-01

This work is focused on the response of two invasive phenotypes of human breast cancer cells, MCF-7 and MDA-MB-231, grown on synthesized zeolite scaffolds in order to study the influence of those biomaterials in controlled conditions with and without anti-tumoral drug treatments. Our research was directed to the use of doxorubicin (DOX) and bergapten (5-MOP). The former is broadly considered the most active single agent available for the treatment of breast cancer, the second is a natural psoralen with an apoptotic effect. The results indicate that both drugs inhibit the cell viability of all cell lines grown on all zeolite scaffolds and that all Pure Zeolite Membranes are more responsive with respect to all Mixed Matrix Membranes. Moreover, the results after treatment with DOX at a concentration of 7.4μM for 24h, show that the expression of the matrix metalloproteinases (MMP-2 and MMP-9) is greatly reduced in both cell lines, especially in those adherent on Pure Zeolite Scaffolds. Copyright © 2016 Elsevier B.V. All rights reserved.

UTL zeolite and the way beyond

Czech Academy of Sciences Publication Activity Database

Shvets, O. V.; Nachtigall, P.; Roth, Wieslaw Jerzy; Čejka, Jiří

2013-01-01

Roč. 182, DEC 2013 (2013), s. 229-238 ISSN 1387-1811 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : zeolite UTL * synthesis * hydrolysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.209, year: 2013

Synthesis of 4A zeolites from kaolin for obtaining 5A zeolites through ionic exchange for adsorption of arsenic

International Nuclear Information System (INIS)

Resmini Melo, Carolina; Gracher Riella, Humberto; Cabral Kuhnen, Nivaldo; Angioletto, Elidio; Melo, Aline Resmini; Bernardin, Adriano Michael; Rocha, Marcio Roberto da; Silva, Luciano da

2012-01-01

Highlights: ► We synthesize 4A zeolite from kaolin by hydrothermal reaction with sodium hydroxide. ► The 4A zeolite synthesized underwent ion exchange with calcium ions, with different parameters, to obtain 5A zeolites. ► The best 4A zeolite obtained was used as adsorbent material for arsenic ions. ► The results showed that the 5A zeolite material obtained is a good adsorber of heavy ions. - Abstract: The synthesis of adsorbing zeolite materials requires fine control of the processing variables. There are distinct process variable settings for obtaining specific desired types of zeolites. The intent of this study was to obtain 4A zeolites from kaolin in order to obtain 5A zeolites through ionic exchange with the previously synthesized zeolite. This zeolite 5A was used as an adsorbent for arsenic ions. The results obtained were satisfactory.

The Effect of Zeolite on Aggregate Stability Indices

Directory of Open Access Journals (Sweden)

F. Sohrab

2016-02-01

Full Text Available Introduction: Soil structural stability affects the profitability and sustainability of agricultural systems. Particle size distribution (PSD and aggregate stability are the important characteristics of soil. Aggregate stability has a significant impact on the development of the root system, water and carbon cycle and soil resistance against soil erosion. Soil aggregate stability, defined as the ability of the aggregates to remain intact when subject to a given stress, is an important soil property that affects the movement and storage of water, aeration, erosion, biological activity and growth of crops. Dry soil aggregate stability (Mean Weight Diameter (MWD, Geometric Mean Diameter (GMD and Wet Aggregate Stability (WAS are important indices for evaluating soil aggregate stability.To improve soil physical properties, including modifying aggregate, using various additives (organic, inorganic and chemicals, zeolites are among what has been studied.According to traditional definition, zeolites are hydratealuminosilicates of alkaline and alkaline-earth minerals. Their structure is made up of a framework of[SiO4]−4 and [AlO4]−5 tetrahedron linked to each other's cornersby sharing oxygen atoms. The substitution of Si+4 by Al+3 intetrahedral sites results inmore negative charges and a high cation exchange capacity.Zeolites, as natural cation exchangers, are suitable substitutes to remove toxic cations. Among the natural zeolites,Clinoptilolite seems to be the most efficient ion exchanger and ion-selective material forremoving and stabilizing heavy metals.Due to theexisting insufficient technical information on the effects of using different levels of zeolite on physical properties of different types of soils in Iran, the aim of this research was to assess the effects of two different types of zeolite (Clinoptilolite natural zeolite, Z4, and Synthetic zeolite, A4 on aggregate stability indicesof soil. Materials and Methods: In this study at first

Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

International Nuclear Information System (INIS)

Sarah C. Larson; Vicki H. Grassian

2006-01-01

Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO x ) and ammonia (NH 3 ) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO 2 was observed at room temperature in the presence of NH 3 as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO 2 reduction with NH 3 relative to nanocrystalline NaY

Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

OpenAIRE

Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

2017-01-01

Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

Electrode-Modified Zeolites - Electrode Microstructures Contained in and on a Heterogeneous Catalyst

Science.gov (United States)

1988-07-15

zeolite Type Y and Pt supported on gamma-alumina. The electrolytic response of zeolite-supported Pt in the absence of added electrolyte salt for water or...character of metals at sizes where’ bulk metallic properties may not be exhibited. Furthermore, electrolyses are now allowed using loadings of catalysts which...in water until the filtrate tested negatively for Cl with AgNO 3; PtY was then dried a- 135 C. Equilibrium exchnge occurs at these low weight

Snapshot analysis for rhodium fixed incore detector using BEACON methodology

International Nuclear Information System (INIS)

Cha, Kyoon Ho; Choi, Yu Sun; Lee, Eun Ki; Park, Moon Ghu; Morita, Toshio; Heibel, Michael D.

2004-01-01

The purpose of this report is to process the rhodium detector data of the Yonggwang nuclear unit 4 cycle 5 core for the measured power distribution by using the BEACON methodology. Rhodium snapshots of the YGN 4 cycle 5 have been analyzed by both BEACON/SPINOVA and CECOR to compare the results of both codes. By analyzing a large number of snapshots obtained during normal plant operation. Reviewing the results of this analysis, the BEACON/SPNOVA can be used for the snapshot analysis of Korean Standard Nuclear Power (KSNP) plants

Kinetics and thermodynamic for sorption of arsenate by Lanthanum-exchanged zeolite

International Nuclear Information System (INIS)

Mohd Jelas Haron; Saiful Adli Masdan; Mohd Zobir Hussein; Zulkarnain Zainal; Anuar Kassim

2007-01-01

negative values of ΔG degree meant that the sorption of As (V) ions on La-exchanged zeolite was spontaneous, perhaps because the La (III) had high affinity towards the arsenic ion as indicated by a low K sp value of of lanthanum arsenate. A slightly positive entropy change for sorption of As (V) ion on La-exchanged zeolite could be due to fixation of the ions on the La (III) exchange sites that was randomly distributed on the sorbents. The kinetics study showed that the As (V) sorption followed first order kinetic model. The first-order kinetic constants for the sorption are 2.77x10 -3 , 2.25x10 -3 and 1.60x10 -3 min -1 for La-ZX, La-ZSM and La-ZA, respectively. (author)

Light-refractory radiation shielding materials using diatomites and zeolites

International Nuclear Information System (INIS)

Murakami, Hideki

2005-01-01

It has been recently shown that diatomites and zeolites have some useful characteristics for radiation shielding materials. In this study, the availability of these materials for unexpected accidents in the nuclear sites is examined. The diatomites and zeolites, compared to existing shielding materials, have superior characteristics; low density and light weight, low in radiation-induced problem, high-heat resistance, remain unaltered by the addition of an acid except hydrofluoric acid, porous and large specific surface area, and also excellent water-absorbing property. These porous materials could also expand the shielding energy range applied and be used for fast- and thermal-neutrons, and γ ray. In addition, these materials are easy to store for long periods of time against emergency because of their natural rocks. From the examinations, it is cleared that diatomites and zeolites have excellent properties as radiation shielding materials for emergency use. (author)

Site blocking in silver-exchanged zeolite Y by carbon monoxide and ethene using xenon adsorption and 129Xe NMR spectroscopy

Science.gov (United States)

Boddenberg, B.; Watermann, J.

1993-03-01

The adsorption isotherms and 129Xe NMR chemical shifts of xenon in the zeolites NaY, AgY, and in AgY preloaded with ≈ 1 molecule/supercage ethene and carbon monoxide were measured at 25°C. The experimental data reveal the blocking of the silver-cation sites for xenon by the preadsorbed molecules. Ethene and CO are found to block the previously postulated two types of silver-cation species in the supercages of AgY in a different way.

Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

International Nuclear Information System (INIS)

Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

1983-01-01

9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)₂ and surfactants probed by spectroscopic methods.

Science.gov (United States)

Zhou, Li-Mei; Guo, Cai-Hong; Fu, Hai-Yan; Jiang, Xiao-Hui; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun

2012-07-01

The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion. Copyright © 2012 Elsevier B.V. All rights reserved.

The influence of pH on the in vitro permeation of rhodium through human skin.

Science.gov (United States)

Jansen Van Rensburg, Sané; Franken, Anja; Du Plessis, Jeanetta; Du Plessis, Johannes Lodewykus

2017-06-01

Workers in precious metals refineries are at risk of exposure to salt compounds of the platinum group metals through inhalation, as well as through the skin. Rhodium salt permeation through the skin has previously been proven using rhodium trichloride (RhCl 3 ) dissolved in synthetic sweat at a pH of 6.5. However, the skin surface pH of refinery workers may be lower than 6.5. The aim of this study was to investigate the influence of pH 6.5 and 4.5 on the in vitro permeation of rhodium through intact Caucasian skin using Franz diffusion cells. A concentration of 0.3 mg mL -1 rhodium was used and analyses were performed using inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Results indicated a cumulative increase in permeation over 24 h. Rhodium permeation after 12 h was significantly greater at pH 4.5 (1.56 ± 0.24 ng cm -2 ) than at 6.5 (0.85 ± 0.13 ng cm -2 ; p = 0.02). At both pH levels, there was a highly significant difference ( p rhodium remaining in the skin (1428.68 ± 224.67 ng cm -2 at pH 4.5 and 1029.90 ± 115.96 ng cm -2 at pH 6.5) and the mass that diffused through (0.88 ± 0.17 ng cm -2 at pH 4.5 and 0.62 ± 0.10 ng cm -2 at pH 6.5). From these findings, it is evident that an acidic working environment or low skin surface pH may enhance permeation of rhodium salts, contributing to sensitization and adverse health effects.

Design and characterization of chitosan/zeolite composite films--Effect of zeolite type and zeolite dose on the film properties.

Science.gov (United States)

Barbosa, Gustavo P; Debone, Henrique S; Severino, Patrícia; Souto, Eliana B; da Silva, Classius F

2016-03-01

Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance.

Theoretical investigation of layered zeolite frameworks: Interaction between IPC-1P layers derived from zeolite UTL

Czech Academy of Sciences Publication Activity Database

Grajciar, L.; Bludský, Ota; Roth, Wieslaw Jerzy; Nachtigall, P.

2013-01-01

Roč. 204, Apr 15 (2013), s. 15-21 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388963 ; RVO:61388955 Keywords : layered zeolites * density functional theory * hydrogen bonding * structure Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.309, year: 2013

High resolution NMR in zeolites

Energy Technology Data Exchange (ETDEWEB)

Diaz, Anix [INTEVEP, Filial de Petroleos de Venezuela, SA, Caracas (Venezuela). Dept. de Analisis y Evalucion

1992-12-31

In this work {sup 29} Si and {sup 27} Al NMR spectroscopy was used to study various types of zeolites. The corresponding spectra were used to measure the Si/Al ratios, to follow chemical modifications induced by acid and hydrothermal treatments, to determine non-equivalent crystallographic sites in highly dealuminated mordenites, and to detect modifications of faujasites due to the insertion of titanium atoms in the lattice. (author) 7 refs., 7 figs., 2 tabs.

Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

Science.gov (United States)

Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

2018-03-01

The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2

Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

Science.gov (United States)

Lee, Kyong-Hwan

2016-05-01

Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

Thermal behavior of natural zeolites

International Nuclear Information System (INIS)

Bish, D.L.

1993-01-01

Thermal behavior of natural zeolites impacts their application and identification and varies significantly from zeolite to zeolite. Zeolites evolve H 2 0 upon heating, but recent data show that distinct ''types'' of water (e.g., loosely bound or tightly bound zeolitic water) do not exist. Rather water is bound primarily to extra-framework cations with a continuum of energies, giving rise to pseudocontinuous loss of water accompanied by a dynamic interaction between remaining H 2 0 molecules and extra-framework cations. These interactions in the channels of zeolites give rise to dehydration dependent on the extra-framework cation, in addition to temperature and water vapor pressure. The dehydration reaction and the extra-framework cation also affect the thermal expansion/contraction. Most zeolites undergo dehydration-induced contractions that may be anisotropic, although minor thermal expansion can be seen with some zeolites. Such contractions can be partially or completely irreversible if they involve modifications of the tetrahedral framework and/or if rehydration is sluggish. Thermally induced structural modifications are also driven initially by dehydration and the concomitant contraction and migration of extra-framework cations. Contraction is accommodated by rotations of structural units and tetrahedral cation-oxygen linkages may break. Thermal reactions that involve breaking of tetrahedral cation-oxygen bonds markedly irreversible and may be kinetically limited, producing large differences between short- and long-term heating

Kinetic analysis of temperature-induced transformation of zeolite 4A to low-carnegieite

International Nuclear Information System (INIS)

Kosanovic, C.; Subotic, B.; Ristic, A.

2004-01-01

Kinetics of the isothermal amorphization of zeolite 4A and recrystallization of the formed amorphous phase to low-carnegieite at three different temperatures were investigated by powder X-ray diffraction method. Changes in the fractions f A of zeolite 4A, f a of amorphous aluminosilicate and f C of low-carnegieite during heating of zeolite 4A, show that amorphization and recrystallization take place simultaneously. Kinetic analyzes of single processes (amorphization, recrystallization) as well as solution of the population balance of the entire transformation process (simultaneous transformation of zeolite 4A into amorphous aluminosilicate and its recrystallization into low-carnegieite) have shown that: (A) the transformation of zeolite 4A takes place by a random, diffusion-limited agglomeration of the short-range-ordered aluminosilicate subunits formed by thermally induced breaking of Si-O-Si and Si-O-Al bonds between different building units of zeolite framework; and (B) the crystallization of low-carnegieite occurs by homogeneous nucleation of low-carnegieite inside the matrix of amorphous aluminosilicate and diffusion-controlled, one-dimensional growth of the nuclei, thus forming needle-shaped crystals of low-carnegieite

Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

Energy Technology Data Exchange (ETDEWEB)

Lin, Jerry Y.S. [Arizona State Univ., Mesa, AZ (United States)

2013-01-29

Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

Hierarchical porous structured zeolite composite for removal of ionic contaminants from waste streams and effective encapsulation of hazardous waste

Energy Technology Data Exchange (ETDEWEB)

Al-Jubouri, Sama M. [Chemical Engineering & Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Curry, Nicholas A. [Materials Science, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Holmes, Stuart M., E-mail: stuart.holmes@manchester.ac.uk [Chemical Engineering & Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom)

2016-12-15

A hierarchical structured composite made from clinoptilolite supported on date stones carbon is synthesized using two techniques. The composites are manufactured by fixing a natural zeolite (clinoptilolite) to the porous surface of date stones carbon or by direct hydrothermal synthesis on to the surface to provide a supported high surface area ion-exchange material for metal ion removal from aqueous streams. The fixing of the clinoptilolite is achieved using sucrose and citric acid as a binder. The composites and pure clinoptilolite were compared to test the efficacy for the removal of Sr{sup 2+} ions from an aqueous phase. The encapsulation of the Sr{sup 2+} using either vitrification or a geo-polymer addition was tested to ensure that the hazardous waste can be made safe for disposal. The hierarchical structured composites were shown to achieve a higher ion exchange capacity per gram of zeolite than the pure clinoptilolite (65 mg/g for the pure natural clinoptilolite and 72 mg/g for the pure synthesized clinoptilolite) with the synthesized composite (160 mg/g) having higher capacity than the natural clinoptilolite composite (95 mg/g). The rate at which the equilibria were established followed the same trend showing the composite structure facilitates diffusion to the ion-exchange sites in the zeolite.

Carbonyl complexes of rhodium with N-donor ligands: factors determining the formation of terminal versus bridging carbonyls

NARCIS (Netherlands)

Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.

2010-01-01

Cationic rhodium carbonyl complexes supported by a series of different N-3- and N-4-donor ligands were prepared, and their ability to form carbonyl-bridged species was evaluated. Complex [Rh(K3-bpa)(cod)r (1(+)) (bpa = bis(2-picolyBamine, cod = cis,cis-1,5-cyclooctadiene) reacts with I bar of CO to

Rhodium target preparation from homemade chloride plating baths used for the industrial cyclotron production of palladium-L03

International Nuclear Information System (INIS)

Sadeghi, M.; Van den Winkel, P.; Afarideh, H.; Haji-Saeid, M.; Syrafi Nafis, H.

2004-01-01

fitted with a single axial anode, with a bi-directional electromechanical stirrer (1000 rpm, 8/8 sec) and with an isolated resistive circular heating element mounted at the bottom. At the end of the experiment, the plating vessel rinsed abundantly with tap water. Upon removal of the targets, the latter are rinsed with demineralised water and acetone, air-dried and weighed. From this weight, the thickness of the layers is calculated. As Rh-plating to depletion always gives rise to a black coating of the deposit (Rh-black) near the end of the plating, the rhodium layers were cleaned with a scouring suspension (CIF) and a sponge. After rinsing with water and acetone and air-drying, the weight was determined again. Results: From the results it can be concluded: 1. Plating rhodium targets from RhC13 solutions at pH = 1.9 to 2.5 applying a current of 80 to 125 mA per target at 40 degree C, results in (highly) reflective targets requiring no or limited scouring cleaning. Losses during scouring cleaning are then confined to less then 0.5 %; 2. Increasing the current per target to more then 125 mA in the same pH range and at the same temperature, gives rise to increasing losses (up to about 15 % at 200 mA per target) of rhodium during the cleaning process; 3. At lower pH ( 3.0) results in a non-adherent deposit that is completely removed from the Cu-carrier during the cleaning; 4. As far as the thermal shock test is concerned, the deposits satisfies the 250 degree C (= maximum allowable temperature of the rhodium layer during the irradiation) test: quantitative peeling-off and powdering occurs. Conclusions: Electroplated rhodium targets can be prepared from homemade or commercially available chloride baths containing appropriate plating additives. When homemade plating solutions are used, the addition of 1% sulfamic acid is recommended. The pH adjusted to the optimum value (pH = 2) with sodium hydroxide. As plating technique constant current (100 mA/target; 24 hrs) dc

Molecular exchange of n-hexane in zeolite sieves studied by diffusion-diffusion and T{sub 1}-diffusion nuclear magnetic resonance exchange spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Neudert, Oliver; Stapf, Siegfried; Mattea, Carlos, E-mail: carlos.mattea@tu-ilmenau.de [Fachgebiet Technische Physik II/Polymerphysik, Institute of Physics, Technische Universitaet Ilmenau, PO Box 100 565, 98684 Ilmenau (Germany)

2011-03-15

Molecular exchange properties and diffusion of n-hexane embedded in a bimodal pore structure with characteristic length scales in the order of nano and micrometres, respectively, formed by packing of zeolite particles, are studied. Two-dimensional (2D) nuclear magnetic resonance (NMR) diffusion correlation experiments together with relaxation-diffusion correlation experiments are performed at low magnetic field using a single-sided NMR scanner. The exchange time covers a range from 10{sup -3} to 10{sup -1} s. The molecular exchange properties are modulated by transport inside the zeolite particles. Different exchange regimes are observed for molecules starting from different positions inside the porous sample. The influence of the spin-lattice relaxation properties of the fluid molecules inside the zeolite particles on the signal intensity is also studied. A Monte Carlo simulation of the exchange process is performed and is used to support the analysis of the experimental data.

Nanoporous Zeolite Thin Film-Based Fiber Intrinsic Fabry-Perot Interferometric Sensor for Detection of Dissolved Organics in Water

Directory of Open Access Journals (Sweden)

Hai Xiao

2006-08-01

Full Text Available A fiber optic intrinsic Fabry-Perot interferometric (IFPI chemical sensor wasdeveloped by fine-polishing a thin layer of polycrystalline nanoporous MFI zeolitesynthesized on the cleaved endface of a single mode fiber. The sensor operated bymonitoring the optical thickness changes of the zeolite thin film caused by the adsorption oforganic molecules into the zeolite channels. The optical thickness of the zeolite thin filmwas measured by white light interferometry. Using methanol, 2-propanol, and toluene as themodel chemicals, it was demonstrated that the zeolite IPFI sensor could detect dissolvedorganics in water with high sensitivity.

Spin probes of chemistry in zeolites

International Nuclear Information System (INIS)

Werst, D.W.; Trifunac, A.D.

1997-09-01

Electron spin resonance (EPR) studies in zeolites are reviewed in which radiolysis was used to ionize the zeolite lattice, create reactive intermediates, spin label reaction products and to provide a window onto chemistry and transport of adsorbates and matrix control of chemistry. The review examines reactions of radical cations and the influence of the geometry constraints inside the zeolite, explores how zeolite model systems can be used to learn about energy and charge transfer in solids and illustrates the use of radiolysis and EPR for in situ spectroscopic studies of solid-acid catalysis. The various spin probes created inside the zeolite pores report on properties of the zeolites as well as shed light on radiolytic processes

Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

Science.gov (United States)

Kou, K G M; Dong, V M

2015-06-07

Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

Radiochemical and thermal studies of the copper(II)-exchanged form of synthetic zeolite linde sieve A

International Nuclear Information System (INIS)

Banerjee, S.P.

1978-01-01

Synthetic zeolite Linde Sieve A displays a double ion-sieve action. Only small cations can penetrate the single 6-rings into the beta cages. The radiochemical and thermal studies of copper(II)-exchanges form of 4A shows evidence of hydrated copper(II) ions in the zeolite structure. (author)

Characterization and antibacterial activity of silver exchanged regenerated NaY zeolite from surfactant-modified NaY zeolite.

Science.gov (United States)

Salim, Mashitah Mad; Malek, Nik Ahmad Nizam Nik

2016-02-01

The antibacterial activity of regenerated NaY zeolite (thermal treatment from cetyltrimethyl ammonium bromide (CTAB)-modified NaY zeolite and pretreatment with Na ions) loaded with silver ions were examined using the broth dilution minimum inhibitory concentration (MIC) method against Escherichia coli (E. coli ATCC 11229) and Staphylococcus aureus (S. aureus ATCC 6538). X-ray diffraction (XRD), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and chemical elemental analyses were used to characterize the regenerated NaY and AgY zeolites. The XRD patterns indicated that the calcination and addition of silver ions on regenerated NaY zeolite did not affect the structure of the regenerated NaY zeolite as the characteristic peaks of the NaY zeolite were retained, and no new peaks were observed. The regenerated AgY zeolite showed good antibacterial activity against both bacteria strains in distilled water, and the antibacterial activity of the samples increased with increasing Ag loaded on the regenerated AgY zeolite; the regenerated AgY zeolite was more effective against E. coli than S. aureus. However, the antibacterial activity of the regenerated AgY was not effective in saline solution for both bacteria. The study showed that CTAB-modified NaY zeolite materials could be regenerated to NaY zeolite using thermal treatment (550°C, 5h) and this material has excellent performance as an antibacterial agent after silver ions loading. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of hierarchical porosity and phosphorus modification on the catalytic properties of zeolite Y

Energy Technology Data Exchange (ETDEWEB)

Li, Wenlin; Zheng, Jinyu; Luo, Yibin; Da, Zhijian, E-mail: dazhijian.ripp@sinopec.com

2016-09-30

Highlights: • Hierarchical zeolite Y was prepared by citric acid treatment and alkaline treatment with NaOH&TBPH. • The addition of TBPH during desilication process transferred the bridge bonded OH− to the terminal P−OH group. • Moderate Brønsted acid sites could be created with phosphorus modification. • Zeolite with hierarchical porosity and appropriated acidities favored high conversion of 1,3,5-TIPB. - Abstract: The zeolite Y is considered as a leading catalyst for FCC industry. The acidity and porosity modification play important roles in determining the final catalytic properties of zeolite Y. The alkaline treatment of zeolite Y by dealumination and alkaline treatment with NaOH and NaOH&TBPH was investigated. The zeolites were characterized by X-ray diffraction, low-temperature adsorption of nitrogen, transmission electron microscope, NMR, NH{sub 3}-TPD and IR study of acidity. Accordingly, the hierarchical porosity and acidity property were discussed systematically. Finally, the catalytic performance of the zeolites Y was evaluated in the cracking of 1,3,5-TIPB. It was found that desilication with NaOH&TBPH ensured the more uniform intracrystalline mesoporosity with higher microporosity, while preserving higher B/L ratio and moderate Brønsted acidities resulting in catalysts with the most appropriated acidity and then with better catalytic performance.

Remarkably enhanced density and specific activity of active sites in Al-rich Cu-, Fe- and Co-beta zeolites for selective catalytic reduction of NOx

Czech Academy of Sciences Publication Activity Database

Sazama, Petr; Pilař, Radim; Mokrzycki, Lukasz; Vondrová, Alena; Kaucký, Dalibor; Plšek, Jan; Sklenák, Štěpán; Šťastný, Petr; Klein, Petr

2016-01-01

Roč. 189, JUL 2016 (2016), s. 65-74 ISSN 0926-3373 R&D Projects: GA TA ČR(CZ) TH01021259 Institutional support: RVO:61388955 Keywords : SCR-NOx * Al-rich beta zeolite (*BEA) * Cobalt Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.446, year: 2016

Evidence for F-/SiO- anion exchange in the framework of As-synthesized all-silica zeolites

KAUST Repository

Liu, Xiaolong

2011-05-12

Not everything changes: Charge-compensating anions can be exchanged in as-synthesized zeolite frameworks with changes in both the density of defect sites and of the hydrophobic character of the zeolite. The reversible transformation occurs without dissolution/recrystallization of the zeolite and preserves the size and shape of the crystals (see picture). Fluoride removal is not possible in all-silica D4R units, for which fluoride ions play a structure-directing role. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of cesium and strontium with zeolites

Energy Technology Data Exchange (ETDEWEB)

Kanno, T; Hashimoto, H [Tohoku Univ., Sendai (Japan). Research Inst. of Mineral Dressing and Metallurgy

1976-06-01

The basic studies of separation of cesium and strontium were made with specimens of zeolite, which are synthetic zeolites A, X and Y; synthetic mordenite; natural mordenite; and clinoptilolite. Ammonium chloride was used as eluent, because it was considered to be a most appropriate eluent in alkaline chlorides. Cesium was easily eluted from the zeolites A and X by ammonium chloride solution, but it was difficult to elute from the synthetic mordenite, natural mordenite and clinoptilolite by ammonium chloride solution, but it was difficult to elute from the zeolites A and X. The zeolite Y is the only one zeolite among these zeolites from which both of cesium and strontium were easily eluted by ammonium chloride solution. Strontium could be separated from cesium with zeolites by formation of Sr-EDTA chelate at pH above 11. In this process, cesium was only exchanged in zeolite column, but strontium flow out from it.

Separation of cesium and strontium with zeolites

International Nuclear Information System (INIS)

Kanno, Takuji; Hashimoto, Hiroyuki

1976-01-01

The basic studies of separation of cesium and strontium were made with specimens of zeolite, which are synthetic zeolites A, X and Y; synthetic mordenite; natural mordenite; and clinoptilolite. Ammonium chloride was used as eluent, because it was considered to be a most appropriate eluent in alkaline chlorides. Cesium was easily eluted from the zeolites A and X by ammonium chloride solution, but it was difficult to elute from the synthetic mordenite, natural mordenite and clinoptilolite by ammonium chloride solution, but it was difficult to elute from the zeolites A and X. The zeolite Y is the only one zeolite among these zeolites from which both of cesium and strontium were easily eluted by ammonium chloride solution. Strontium could be separated from cesium with zeolites by formation of Sr-EDTA chelate at pH above 11. In this process, cesium was only exchanged in zeolite column, but strontium flow out from it. (auth.)

Immobilization of krypton-85 in zeolite 5A and porous glass

International Nuclear Information System (INIS)

Christensen, A.B.; DelDebbio, J.A.; Knecht, D.A.; Tanner, J.E.; Cossel, S.C.

1981-12-01

This report demonstrates the technical and economic feasibility for immobilizing krypton-85 by high pressure/high temperature encapsulation in zeolite 5A or thirsty Vyco porous glass. Data are presented to show how process conditions affect the encapsulation and how to compact the zeolite beads with glass frit or other additives to form a fused mass with low dispersibility potential. Krypton specific loadings of 30 and 50 m 3 STP gas per m 3 solid are readily achieved at 100 MPa in porous glass at 900 0 C and zeolite 5A at 700 0 C. Krypton is encapsulated by a sintering process where the porous glass and zeolite 5A voids are sealed. With zeolite 5A, the initial water concentration has a catalytic effect on the sintering, resulting in a transition from crystalline zeolite 5A to an amorphous aluminosilicate. Krypton leakage experiments are used to predict leakage rates from glass or zeolite of less than 0.03% and 0.3% for 10-y storage at 300 and 400 0 C, respectively. Heating the loaded zeolite at 600 to 700 0 C for 4 h removes 0.1% of the total krypton which is loosely held and reduces the subsequent leakage rates at 300 to 400 0 C. Zeolite 5A is chosen as the preferred material to immobilize krypton-85. A preconceptual design and cost estimate is given for a facility to encapsulate 110% of the krypton production of a 2000 metric ton of heavy metal per year reprocessing plant, or 230 m 3 of gas containing 19 MCi of krypton-85. A hot isostatic press (HIP) with an isolated work zone of 8 or 16 L capacity is required to operate for 600 or 300 cycles per year, respectively. Existing HIP technology uses work zones from 1 to 3500 L capacity at similar production rates. A preliminary safety evaluation shows that an incredible worst case accident could be contained and the maximum off-site dose would be well below accident protective action guidance levels

Synthesis and Characterization of Zeolite Na−Y and Its Conversion to the Solid Acid Zeolite H−Y

DEFF Research Database (Denmark)

Warner, Terence Edwin; Galsgaard Klokker, Mads; Nielsen, Ulla Gro

2017-01-01

Zeolite Y has an iconic crystal structure, but more importantly, the hydrogen modification zeolite H−Y is the classic example of a solid acid which is used extensively as a catalyst in the oil industry. This metastable compound cannot be synthesized directly, which creates an opportunity to discuss...... various preparative strategies with the students, such as the three-stage procedure described here. Stage I concerns the hydrothermal synthesis of zeolite Na−Y, followed by ion-exchange with an ammonium acetate solution to form zeolite NH4−Y, and the latter is subsequently converted to zeolite H......−Y by thermolysis. Stages II and III may instead be performed using commercially available zeolites, Na−Y and NH4−Y, respectively, which shifts the learning objectives to structural characterization of zeolites. The characterization of the product and intermediate materials gives the students a practical insight...

Removal of pyridine and quinoline by bio-zeolite composed of mixed degrading bacteria and modified zeolite

International Nuclear Information System (INIS)

Bai Yaohui; Sun Qinghua; Xing Rui; Wen Donghui; Tang Xiaoyan

2010-01-01

In the process of the biodegradation of pyridine and quinoline, ammonium is often generated because of the transformation of N from pyridine and quinoline. Zeolite has been proven to be an effective sorbent for the removal of the ammonium. The natural zeolite can be modified to be the macroporous carrier in the biological wastewater treatment process. In this study, a specific bio-zeolite composed of mixed bacteria (a pyridine-degrading bacterium and a quinoline-degrading bacterium) and modified zeolite was used for biodegradation and adsorption in two types of wastewater: sterile synthetic and coking wastewater. The experimental results indicated that pyridine and quinoline could be degraded simultaneously by the mixed bacteria. Furthermore, NH 4 + -N transformed from pyridine and quinoline could be removed by the modified zeolite. In addition, the bacterial community structures of the coking wastewater and the bio-zeolite were monitored by the amplicon length heterogeneity polymerase-chain reaction (LH-PCR) technique. Both LH-PCR results and scanning electron microscope (SEM) observations indicated that the microorganisms, including BW001 and BW003, could be easily attached on the surface of the modified zeolite and that the bio-zeolite could be used in the treatment of wastewater containing pyridine and/or quinoline.

Catalysis with hierarchical zeolites

DEFF Research Database (Denmark)

Holm, Martin Spangsberg; Taarning, Esben; Egeblad, Kresten

2011-01-01

Hierarchical (or mesoporous) zeolites have attracted significant attention during the first decade of the 21st century, and so far this interest continues to increase. There have already been several reviews giving detailed accounts of the developments emphasizing different aspects of this research...... topic. Until now, the main reason for developing hierarchical zeolites has been to achieve heterogeneous catalysts with improved performance but this particular facet has not yet been reviewed in detail. Thus, the present paper summaries and categorizes the catalytic studies utilizing hierarchical...... zeolites that have been reported hitherto. Prototypical examples from some of the different categories of catalytic reactions that have been studied using hierarchical zeolite catalysts are highlighted. This clearly illustrates the different ways that improved performance can be achieved with this family...

Characterization of Zeolite in Zeolite-Geopolymer Hybrid Bulk Materials Derived from Kaolinitic Clays

Directory of Open Access Journals (Sweden)

Hayami Takeda

2013-05-01

Full Text Available Zeolite-geopolymer hybrid materials have been formed when kaolin was used as a starting material. Their characteristics are of interest because they can have a wide pore size distribution with micro- and meso-pores due to the zeolite and geopolymer, respectively. In this study, Zeolite-geopolymer hybrid bulk materials were fabricated using four kinds of kaolinitic clays (a halloysite and three kinds of kaolinite. The kaolinitic clays were first calcined at 700 °C for 3 h to transform into the amorphous aluminosilicate phases. Alkali-activation treatment of the metakaolin yielded bulk materials with different amounts and types of zeolite and different compressive strength. This study investigated the effects of the initial kaolinitic clays on the amount and types of zeolite in the resultant geopolymers as well as the strength of the bulk materials. The kaolinitic clays and their metakaolin were characterized by XRD analysis, chemical composition, crystallite size, 29Si and 27Al MAS NMR analysis, and specific surface area measurements. The correlation between the amount of zeolite formed and the compressive strength of the resultant hybrid bulk materials, previously reported by other researchers was not positively observed. In the studied systems, the effects of Si/Al and crystalline size were observed. When the atomic ratio of Si/Al in the starting kaolinitic clays increased, the compressive strength of the hybrid bulk materials increased. The crystallite size of the zeolite in the hybrid bulk materials increased with decreasing compressive strength of the hybrid bulk materials.

Enhanced water transport and salt rejection through hydrophobic zeolite pores

Science.gov (United States)

Humplik, Thomas; Lee, Jongho; O'Hern, Sean; Laoui, Tahar; Karnik, Rohit; Wang, Evelyn N.

2017-12-01

The potential of improvements to reverse osmosis (RO) desalination by incorporating porous nanostructured materials such as zeolites into the selective layer in the membrane has spurred substantial research efforts over the past decade. However, because of the lack of methods to probe transport across these materials, it is still unclear which pore size or internal surface chemistry is optimal for maximizing permeability and salt rejection. We developed a platform to measure the transport of water and salt across a single layer of zeolite crystals, elucidating the effects of internal wettability on water and salt transport through the ≈5.5 Å pores of MFI zeolites. MFI zeolites with a more hydrophobic (i.e., less attractive) internal surface chemistry facilitated an approximately order of magnitude increase in water permeability compared to more hydrophilic MFI zeolites, while simultaneously fully rejecting both potassium and chlorine ions. However, our results also demonstrated approximately two orders of magnitude lower permeability compared to molecular simulations. This decreased performance suggests that additional transport resistances (such as surface barriers, pore collapse or blockages due to contamination) may be limiting the performance of experimental nanostructured membranes. Nevertheless, the inclusion of hydrophobic sub-nanometer pores into the active layer of RO membranes should improve both the water permeability and salt rejection of future RO membranes (Fasano et al 2016 Nat. Commun. 7 12762).

Enhanced water transport and salt rejection through hydrophobic zeolite pores.

Science.gov (United States)

Humplik, Thomas; Lee, Jongho; O'Hern, Sean; Laoui, Tahar; Karnik, Rohit; Wang, Evelyn N

2017-12-15

The potential of improvements to reverse osmosis (RO) desalination by incorporating porous nanostructured materials such as zeolites into the selective layer in the membrane has spurred substantial research efforts over the past decade. However, because of the lack of methods to probe transport across these materials, it is still unclear which pore size or internal surface chemistry is optimal for maximizing permeability and salt rejection. We developed a platform to measure the transport of water and salt across a single layer of zeolite crystals, elucidating the effects of internal wettability on water and salt transport through the ≈5.5 Å pores of MFI zeolites. MFI zeolites with a more hydrophobic (i.e., less attractive) internal surface chemistry facilitated an approximately order of magnitude increase in water permeability compared to more hydrophilic MFI zeolites, while simultaneously fully rejecting both potassium and chlorine ions. However, our results also demonstrated approximately two orders of magnitude lower permeability compared to molecular simulations. This decreased performance suggests that additional transport resistances (such as surface barriers, pore collapse or blockages due to contamination) may be limiting the performance of experimental nanostructured membranes. Nevertheless, the inclusion of hydrophobic sub-nanometer pores into the active layer of RO membranes should improve both the water permeability and salt rejection of future RO membranes (Fasano et al 2016 Nat. Commun. 7 12762).

Detergent zeolite filtration plant

OpenAIRE

Stanković Mirjana S.; Pezo Lato L.

2003-01-01

The IGPC Engineering Department designed basic projects for detergent zeolite filtration plant, using technology developed in the IGPC laboratories. Several projects were completed: technological, machine, electrical, automation. On the basis of these projects, a production plant with a capacity of 75,000 t/y was manufactured, at "Zeolite Mira", Mira (VE), Italy, in 1997, for increasing detergent zeolite production, from 50,000 to 100,000 t/y. The main goal was to increase the detergent zeoli...

Supported Metal Zeolites as Environmental Catalysts for Reduction of NOx Molecules

International Nuclear Information System (INIS)

May Nwe Win; Tin Tin Aye; Kyaw Myo Naing; Nyunt Wynn; Maung Maung Htay

2005-09-01

The NOx contamination of air is a major pollutant due to its reaction with the volatile organic compounds, which give rise to ground level (tropospheric) ozone. It is a conventional fact that NOx are one of the major components of car exhaust. In view of that fact, to sustain the tropospheric ozone is to reduce the amount of NOx in the air. Therefore, this paper is concerned with the catalytic activity of Fe-loaded zeolite and Cu-loaded zeolite used to decompose NIOx by SCR (selective catalytic reduction) reaction with very high activity have been studied. Their preparations, characterization by XRD, FT-IR and SEM were also studied. Fe and Cu containig were prepared by soild state ion-exchange method under ambient presure and at the temperature of 600C for 4 hours. From this study, selective catalytic reduction rection was observed, showing about 87% conversion of the NOx molecule with the corresponding optimum amount of catalyst (1.0+-0.5)g working under the reactor space volume of 30cm3 at ambient temperature (30-32)C

Synthesis of Zeolite from Fly Ash and Removal of Heavy Metal Ions from Newly Synthesized Zeolite

OpenAIRE

Solanki, Parag; Gupta, Vikal; Kulshrestha, Ruchi

2010-01-01

Coal fly ash was used to synthesize X-type zeolite by alkali fusion followed by hydrothermal treatment. Characteristics of the various Fly ash samples were carried out. Coal proximate analysis was done. Batch experiment was carried out for the adsorption of some heavy metal ions on to synthesized Zeolite. The cost of synthesized zeolite was estimated to be almost one-fifth of that of commercial 13X zeolite available in the market.

Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx

NARCIS (Netherlands)

Deka, U.|info:eu-repo/dai/nl/325811202; Lezcano-Gonzalez, I.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Beale, A.M.|info:eu-repo/dai/nl/325802068

2013-01-01

Cu-exchanged zeolites have demonstrated widespread use as catalyst materials in the abatement of NOx, especially from mobile sources. Recent studies focusing on Cu-exchanged zeolites with the CHA structure have demonstrated them to be excellent catalysts in the ammonia-assisted selective catalytic

Tailoring the porosity of hierarchical zeolites by carbon-templating

DEFF Research Database (Denmark)

Zhu, Kake; Egeblad, Kresten; Christensen, Claus H.

2008-01-01

We report the synthesis and characterization of a series of hierarchical porous zeolite single crystal materials with a range of porosities made available by carbon-templating using differently-sized carbon particles as templates for the additional non-micropore porosity. The materials were...

The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

Science.gov (United States)

Hepburn, Hamish B; Lam, Hon Wai

2014-10-20

Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of carrier-free rhodium isotopes from ruthenium cyclotron targets by the extraction of nitrosylruthenium from hydrochloric acid solution

International Nuclear Information System (INIS)

Haasbroek, F.J.; Strelow, F.W.E.; Van der Walt, T.N.

1981-01-01

A method is presented for the separation of rhodium isotopes from ruthenium cyclotron targets. After bombardment with deuterons and dissolution of the target material, the ruthenium is converted into a nitrosyl complex by treatment with hydroxylammonium chloride. Aluminium and other elements which have been introduced in the dissolution step, are separated by cation exchange. Ruthenium is then separated by extraction with a mixture of tri-n-butyl phosphate and hexane (4:1), leaving the rhodium in the aqueous phase. No ruthenium is found in the rhodium fraction and the recovery of rhodium is better than 90 per cent [af

Zeolites - a high resolution electron microscopy study

International Nuclear Information System (INIS)

Alfredsson, V.

1994-10-01

High resolution transmission electron microscopy (HRTEM) has been used to investigate a number of zeolites (EMT, FAU, LTL, MFI and MOR) and a member of the mesoporous M41S family. The electron optical artefact, manifested as a dark spot in the projected centre of the large zeolite channels, caused by insufficient transfer of certain reflections in the objective lens has been explained. The artefact severely hinders observation of materials confined in the zeolite channels and cavities. It is shown how to circumvent the artefact problem and how to image confined materials in spite of disturbance caused by the artefact. Image processing by means of a Wiener filter has been applied for removal of the artefact. The detailed surface structure of FAU has been investigated. Comparison of experimental micrographs with images simulated using different surface models indicates that the surface can be terminated in different ways depending on synthesis methods. The dealuminated form of FAU (USY) is covered by an amorphous region. Platinum incorporated in FAU has a preponderance to aggregate in the (111) twin planes, probably due to a local difference in cage structure with more spacious cages. It is shown that platinum is intra-zeolitic as opposed to being located on the external surface of the zeolite crystal. This could be deduced from tomography of ultra-thin sections among observations. HRTEM studies of the mesoporous MCM-41 show that the pores have a hexagonal shape and also supports the mechanistic model proposed which involves a cooperative formation of a mesophase including the silicate species as well as the surfactant. 66 refs, 24 figs

THOREX processing and zeolite transfer for high-level waste stream processing blending

International Nuclear Information System (INIS)

Kelly, S. Jr.; Meess, D.C.

1997-07-01

The West Valley Demonstration Project (WVDP) completed the pretreatment of the high-level radioactive waste (HLW) prior to the start of waste vitrification. The HLW originated form the two million liters of plutonium/uranium extraction (PUREX) and thorium extraction (THOREX) wastes remaining from Nuclear Fuel Services' (NFS) commercial nuclear fuel reprocessing operations at the Western New York Nuclear Service Center (WNYNSC) from 1966 to 1972. The pretreatment process removed cesium as well as other radionuclides from the liquid wastes and captured these radioactive materials onto silica-based molecular sieves (zeolites). The decontaminated salt solutions were volume-reduced and then mixed with portland cement and other admixtures. Nineteen thousand eight hundred and seventy-seven 270-liter square drums were filled with the cement-wastes produced from the pretreatment process. These drums are being stored in a shielded facility on the site until their final disposition is determined. Over 6.4 million liters of liquid HLW were processed through the pretreatment system. PUREX supernatant was processed first, followed by two PUREX sludge wash solutions. A third wash of PUREX/THOREX sludge was then processed after the neutralized THOREX waste was mixed with the PUREX waste. Approximately 6.6 million curies of radioactive cesium-137 (Cs-137) in the HLW liquid were removed and retained on 65,300 kg of zeolites. With pretreatment complete, the zeolite material has been mobilized, size-reduced (ground), and blended with the PUREX and THOREX sludges in a single feed tank that will supply the HLW slurry to the Vitrification Facility

MgO encapsulated mesoporous zeolite for the side chain alkylation of toluene with methanol.

Science.gov (United States)

Jiang, Nanzhe; Jin, Hailian; Jeong, Eun-Young; Park, Sang-Eon

2010-01-01

Side chain alkylation of toluene with methanol was studied over mesoporous zeolite supported MgO catalysts. MgO were supported onto the carbon templated mesoporous silicalite-1 by direct synthesis route under microwave conditions. This direct synthesis route yields the majority of MgO highly dispersed into the mesopores of the silicalite-1 crystals. The vapor phase alkylation of toluene with methanol was performed over these catalysts under vapor phase conditions at atmospheric pressure. Mesoporous silicalite-1 supported MgO catalysts gave improved yields towards side chain alkylated products compared to the bulk MgO. The higher activity exhibited by 5% MgO supported on mesoporous silicalite compared to the one with 1% MgO can be attributed to the large number of weak basic sites observed from the CO2 TPD.

Effect of different glasses in glass bonded zeolite

International Nuclear Information System (INIS)

Lewis, M.A.; Ackerman, J.P.; Verma, S.

1995-01-01

A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

Science.gov (United States)

van der Bij, Hendrik E; Weckhuysen, Bert M

2015-10-21

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research.

Immobilization of krypton-85 in zeolite 5A

International Nuclear Information System (INIS)

Christensen, A.B.; Del Debbio, J.A.; Knecht, D.A.; Tanner, J.E.; Cossel, S.C.

1983-01-01

This paper describes the technical feasibility and presents a summary of a preconceptual design and cost estimate for a process to immobilize krypton-85 by sintering in zeolite 5A at 700 0 C and 100 MPa for 2 to 4 h. Krypton loading of 30 to 60 m 3 at STP per m 3 solid can be achieved. The initial water concentration in zeolite 5A has a catalytic effect on the sintering rate and must be kept at about 1 wt% by heating prior to the encapsulation run. High initial water loadings and/or encapsulation times longer than 4 h must be avoided because the sintered zeolite 5A recrystallizes to an anorthite-type feldspar and releases the trapped krypton. Data are presented to show how the process conditions affect krypton encapsulation in zeolie 5A and how to assure the quality of the product. By adding a powdered glass frit to the commercial zeolite 5A 2 mm beads, a solid mass is formed during encapsulation, which can be further compacted using standard hot isotatic pressing techniques at 33 MPa and 600 0 C to form a fused glassy matrix enclosing the amorphous zeolite. A process for encapsulating the annual krypton-85 production at a commercial 2000 metric ton of heavy metal spent fuel reprocessing plant is developed. A hot isostatic press (HIP) with an isolated work zone of 8 or 16 L capacity is required to operate for 600 or 300 cycles per year, respectively. Existing HIP technology uses work zones from 1 to 3500 L capacity at similar production rates. A combined encapsulation/compaction cycle is proposed as an option to most effectively immobilize the krypton and the zeolite. A preconceptual design and cost estimate is given for a commercial-scale Kr encapsulation facility. The facility is designed to withstand a worst case rupture of the HIP. The maximum lease is estimated to result in an off-site dose well below accident protective action guidance levels

Site-Specific Reactivity of Copper Chabazite Zeolites with Nitric Oxide, Ammonia, and Oxygen

DEFF Research Database (Denmark)

Godiksen, Anita; Isaksen, Oliver L.; Rasmussen, Søren B.

2018-01-01

In-situ electron paramagnetic resonance (EPR) spectroscopy was applied to dilute copper chabazite (CHA) zeolites under gas flows relevant for the selective catalytic reduction of NO with ammonia (NH3-SCR). Under both reducing and oxidizing conditions, we observed differences in reactivity between...

In-situ Micro-Spectroscopy on Coke Formation Processes in Zeolites

NARCIS (Netherlands)

Mores, D.

2011-01-01

Zeolite catalysts are used in a large variety of (petro-)chemical conversions. The acid sites in these materials are responsible for the chemical transformation, while their well-defined crystallographic architecture offers unique molecular size and shape selectivity. The finite availability of

Catalytic performance of Metal‐Organic‐Frameworks vs. extra‐large pore zeolite UTL incondensation reactions

Directory of Open Access Journals (Sweden)

Mariya eShamzhy

2013-08-01

Full Text Available Catalytic behavior of isomorphously substituted B‐, Al‐, Ga‐, and Fe‐containing extra‐large pore UTLzeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensationof 1‐naphthol with ethylacetoacetate, and Prins reaction of β‐pinene with formaldehyde andcompared with large‐pore aluminosilicate zeolite BEA and representative Metal‐Organic‐FrameworksCu3(BTC2 and Fe(BTC. The yield of the target product over the investigated catalysts in Knoevenagelcondensation increases in the following sequence: (AlBEA < (AlUTL < (GaUTL < (FeUTL < Fe(BTC <(BUTL < Cu3(BTC2 being mainly related to the improving selectivity with decreasing strength ofactive sites of the individual catalysts. The catalytic performance of Fe(BTC, containing the highestconcentration of Lewis acid sites of the appropriate strength is superior over large‐pore zeolite(AlBEA and B‐, Al‐, Ga‐, Fe‐substituted extra‐large pore zeolites UTL in Prins reaction of β‐pinene withformaldehyde and Pechmann condensation of 1‐naphthol with ethylacetoacetate.

The extraction of rhodium from aqueous nitric acid by dinonylnaphthalene sulphonic acid

International Nuclear Information System (INIS)

Patel, N.M.; Miles, J.H.; Thornback, J.R.

1987-01-01

The extraction of rhodium from aqueous nitric acid using dinonylnaphthalene sulphonic acid has been investigated. The extraction occurs readily from 0.1 M to 1.0 M nitric acid and, since the rhodium is extracted as {Rh(H 2 O) 6 } 3+ into the inverted micelles of the organic solution, equilibration times are less than 5 minutes. Extraction is enhanced by addition of nitrite ion to form {Rh(H 2 O) 5 NO 2 } 2+ as the extracted species. (author)

Two-Dimensional Zeolites: Current Status and Perspectives

Czech Academy of Sciences Publication Activity Database

Roth, Wieslaw Jerzy; Nachtigall, P.; Morris, R. E.; Čejka, Jiří

2014-01-01

Roč. 114, č. 9 (2014), s. 4807-4837 ISSN 0009-2665 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : zeolites * mesoporous molecular sieves * Fischer-Tropsch synthesis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 46.568, year: 2014

Zeolite Encapsulated Nanocrystalline CuO: A Redox Catalyst for the Oxidation of Secondary Alcohols

Directory of Open Access Journals (Sweden)

Sakthivel Vijaikumar

2008-01-01

Full Text Available Zeolite encapsulated nanocrystalline CuO is synthesized and characterized by powder XRD and HRTEM analyses which clearly show that the particles are less than 15 nm and the nanoparticles are highly dispersed. This nano CuO encapsulated CuY zeolite is used as catalyst in the oxidation of aromatic secondary alcohols. CuY zeolite acts as an efficient support for nano CuO, by stabilizing it and preventing its aggregation. Plausible mechanisms for the formation of the various products are also given.

Kinetic Adsorption Study of Silver Nanoparticles on Natural Zeolite: Experimental and Theoretical Models

Directory of Open Access Journals (Sweden)

Alvaro Ruíz-Baltazar

2015-12-01

Full Text Available In this research, the adsorption capacity of Ag nanoparticles on natural zeolite from Oaxaca is presented. In order to describe the adsorption mechanism of silver nanoparticles on zeolite, experimental adsorption models for Ag ions and Ag nanoparticles were carried out. These experimental data obtained by the atomic absorption spectrophotometry technique were compared with theoretical models such as Lagergren first-order, pseudo-second-order, Elovich, and intraparticle diffusion. Correlation factors R2 of the order of 0.99 were observed. Analysis by transmission electron microscopy describes the distribution of the silver nanoparticles on the zeolite outer surface. Additionally, a chemical characterization of the material was carried out through a dilution process with lithium metaborate. An average value of 9.3 in the Si/Al ratio was observed. Factors such as the adsorption behavior of the silver ions and the Si/Al ratio of the zeolite are very important to support the theoretical models and establish the adsorption mechanism of Ag nanoparticles on natural zeolite.

Zeolite ZSM-57

International Nuclear Information System (INIS)

Valyocsik, E.W.; Page, N.M.; Chu, C.T.W.

1989-01-01

This patent describes a synthetic porous crystalline zeolite having a molar ratio of XO 2 ; Y 2 O 3 of at least 4. Wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium. The porous crystalline zeolite having at least the X-ray diffraction lines as set forth in the text

The assessment of pore connectivity in hierarchical zeolites using positron annihilation lifetime spectroscopy: instrumental and morphological aspects.

Science.gov (United States)

Zubiaga, Asier; Warringham, Robbie; Boltz, Marilyne; Cooke, David; Crivelli, Paolo; Gidley, David; Pérez-Ramírez, Javier; Mitchell, Sharon

2016-04-07

Recent studies demonstrated the power of positron annihilation lifetime spectroscopy (PALS) to characterise the connectivity and corresponding effectiveness of hierarchical pore networks in zeolites. This was based on the fractional escape of ortho-positronium (Ps), formed within the micropore framework, to vacuum. To further develop this technique, here we assess the impact of the positron implantation energy and of the zeolite crystal size and the particle morphology. Conventional measurements using fast positrons and beam measurements applying moderated positrons both readily distinguish purely microporous ZSM-5 zeolites comprised of single crystals or crystal aggregates. Unlike beam measurements, however, conventional measurements fail to discriminate model hierarchical zeolites with open or constricted mesopore architectures. Several steps are taken to rationalise these observations. The dominant contribution of Ps diffusion to the PALS response is confirmed by capping the external surface of the zeolite crystals with tetraethylorthosilicate, which greatly enhances the sensitivity to the micropore network. A one-dimensional model is constructed to predict the out-diffusion of Ps from a zeolite crystal, which is validated experimentally by comparing coffin-shaped single crystals of varying size. Calculation of the trends expected on the application of fast or moderated positrons indicates that the distinctions in the initial distribution of Ps at the crystal level cannot explain the limited sensitivity of the former to the mesopore architecture. Instead, we propose that the greater penetration of fast positrons within the sample increases the probability of Ps re-entry from intercrystalline voids into mesopores connected with the external surface of zeolite crystals, thereby reducing their fractional escape.

Synthesis of LTA zeolite on corundum supports: Preliminary assessment for heavy metal removal from waste water

International Nuclear Information System (INIS)

Jacas, A.; Ortega, P.; Velasco, M. J.; Camblor, M. A.; Rodriguez, M. A.

2012-01-01

The effectiveness of materials based on LTA Zeolite as active phase, for their incorporation into systems aimed at the removal of heavy metals on waste water is evaluated in a preliminary way. This type of Zeolite with the main channel of a minimum free diameter of 0,41 nm and a low SiO 2 /Al 2 O 3 ratio is an interesting molecular sieve, which in turn display a high ion exchange capacity. From this point of view, LTA Zeolite crystals were obtained in situ by hydrothermal synthesis and characterized by x ray diffraction (XRD) and scanning electron microscopy (SEM). We have studied the effect of hydrothermal synthesis time at 378 K. Likewise, the removal capacity of heavy metal from the active phase was evaluated in as a first step on diluted solutions of cooper salts at slightly acidic pH (∼ 4,7). (Author) 28 refs.

Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

Science.gov (United States)

Meng, Qingxi; Shen, Wei; Li, Ming

2012-03-01

Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

Co-deposition of rhodium and tungsten films for the first-mirror on ITER

International Nuclear Information System (INIS)

Marot, Laurent; Steiner, Roland; Gantenbein, Markus; Mathys, Daniel; Meyer, Ernst

2011-01-01

The detailed characterizations of rhodium/tungsten films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the tungsten incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using X-ray photoelectron spectroscopy (XPS), reflectivity measurements, X-rays diffraction (XRD) and scanning electron microscopy (SEM). The incorporation of tungsten changes the films crystalline structure i.e. leading to Rh 3 W formation. The reflectivity of the films decreases linearly with the decrease of rhodium concentration. XPS and ultraviolet photoemission spectroscopy (UPS) measurements show a positive shift of the core level binding energy of rhodium which is coupled to a shift of the Rh d-band ΔE d away from the Fermi level. Opposite shifts are observed for tungsten.

Structural properties of small rhodium clusters

Energy Technology Data Exchange (ETDEWEB)

Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization

International Nuclear Information System (INIS)

Barbosa, A.S.; Rodrigues, M.G.F.

2012-01-01

Zeolites are very important materials due to their high specific surface area. Moreover, they are suitable for use as catalyst support. Noble metals supported on zeolites have been widely used as catalysts in the petrochemical industry. This paper was prepared and characterized, a powder aiming its use in heterogeneous catalysis. Support was used as ZSM-5 and the method of incorporation of the metals (Ru-PtNi) was competitive ion exchange. The materials (ZSM-5 and Pt-Ni-Ru/ZSM-5) were characterized by spectrophotometry Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD) and nitrogen physisorption (BET method). Based on the results of X-ray diffraction, it is possible to demonstrate the preservation of the structure of zeolite ZSM-5 after the competitive ion Exchange with metals (Ru-Pt-Ni) and calcination. The dispersion of metals on ZSM-5 did not change the textural characteristics of the zeolite. (author)

Energetics of sodium-calcium exchanged zeolite A.

Science.gov (United States)

Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

2015-05-07

A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 °C are -74.50 ± 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 ± 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water.

Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

Energy Technology Data Exchange (ETDEWEB)

Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

1986-12-03

Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

Biodiesel synthesis via transesterification of lipid Chlorophyta cultivated in walne rich carbon medium using KOH/Zeolite catalyst

Science.gov (United States)

Dianursanti, Hayati, Siti Zahrotul; Putri, Dwini Normayulisa

2017-11-01

Microalgae from the Chlorophyta division such as Nannochloropsis oculata and Chlorella vulgaris are highly potential to be developed as biodiesel feedstocks because they have a high oil content up to 58%. Biodiesel is produced by transesterification of triglycerides and alcohols with the aid of homogeneous catalysts such as KOH. However, the use of KOH catalysts produces soaps in the biodiesel synthesis. Heterogeneous catalysts are known to solve this problem. One of them is natural zeolite. Zeolite can be used as a catalyst and as a support catalyst. Loading KOH on the zeolite surface is expected to increase alkalinity in KOH/Zeolite catalysts so as to increase the activity of KOH/Zeolite catalyst in transesterification of triglyceride with methanol. In this experimental lipid of microalgae will be used for produced biodiesel via transesterification reaction with methanol and KOH/Zeolite as a catalyst heterogeneous at 60 °C for 3h and utilized catalyst modificated KOH/Zeolite with variation 0.5 M, 1 M and 1.5 M KOH. The modified zeolite was then analyzed by XRF, XRD and BET. The result showed that the yield of biodiesel from lipid N.oculata was 81,09% by 0.5KOH/Zeolite catalyst, 86,53% by 1KOH/Zeolite catalyst, 1,5KOH/Zeolite and 88,13% by 1.5KOH/Zeolit, while the biodiesel produced from lipid C.vulgaris was 59.29% by 0.5KOH/Zeolite, 82.27% by 1KOH/Zeolite and 83.72% by 1.5KOH/Zeolite.

Ion-exchange properties of zeolite/glass hybrid materials

International Nuclear Information System (INIS)

Taira, Nobuyuki; Yoshida, Kohei; Fukushima, Takuya

2017-01-01

Hybrid materials were prepared from ground glass powder and various zeolites such as A-type, mordenite, X-type, and Y-type zeolites, and their ion removal effect was investigated. The hybrid materials of A-type, Y-type, and mordenite zeolites showed similar Sr"2"+ removal rates from aqueous solutions. The removal rate of Sr"2"+ ions increased as the amount of zeolite in the hybrid materials increased. Compared with other hybrid materials, the hybrid materials of X-type zeolite showed higher Sr"2"+ removal rates, especially for zeolite content greater than 25%. As the amount of X-type zeolite in the hybrid materials increased, the Sr"2"+ removal rate increased greatly, with a 100% removal rate when the content of X-type zeolite exceeded 62.5%. (author)

Introduction to zeolite theory and modelling

NARCIS (Netherlands)

Santen, van R.A.; Graaf, van de B.; Smit, B.; Bekkum, van H.

2001-01-01

A review. Some of the recent advances in zeolite theory and modeling are present. In particular the current status of computational chem. in Bronsted acid zeolite catalysis, mol. dynamics simulations of mols. adsorbed in zeolites, and novel Monte Carlo technique are discussed to simulate the

Characterization of zeolites by magic-angle-spinning NMR

International Nuclear Information System (INIS)

Brunner, E.; Ernst, H.; Freude, D.; Hunger, M.; Pfeifer, H.

1988-01-01

Magic-angle-spinning nuclear magnetic resonance (MAS NMR) has been used to study structure defects in TPA/ZSM-5, the dealumination process caused by hydrothermal treatment and acid leaching of zeolites, the influence of Lewis sites upon water as a probe molecule, the boron incorporation into the ZSM-5 framework, and the acid sites and structure defects in SAPO-5. The nuclei under study are 1 H, 11 B, 27 Al, 29 Si, and 31 P. 24 refs.; 7 figs.; 1 table

Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

International Nuclear Information System (INIS)

Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su

2014-01-01

The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core

Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

Energy Technology Data Exchange (ETDEWEB)

Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su [FNC Technology Co., Ltd., Yongin (Korea, Republic of)

2014-05-15

The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core.

Characterization of the Cu+ sites in MFI zeolites: combined computational and experimental study

Czech Academy of Sciences Publication Activity Database

Bludský, Ota; Nachtigall, Petr; Čičmanec, P.; Knotek, P.; Bulánek, R.

2005-01-01

Roč. 100, - (2005), 385-389 ISSN 0920-5861 R&D Projects: GA MŠk(CZ) LN00A032 Institutional research plan: CEZ:AV0Z40550506 Keywords : ZSM-5 zeolite * carbon-monoxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.365, year: 2005

PHYSICAL, CHEMICAL, AND STRUCTURAL EVOLUTION OF ZEOLITE-CONTAINING WASTE FORMS PRODUCED FROM METAKAOLINITE AND CALCINED HLW

International Nuclear Information System (INIS)

Pareizs, J. M.; Jantzenm, C.M.

2000-01-01

Natural and synthetic zeolites are extremely versatile materials. They can adsorb a variety of liquids and gases, and also take part in cation exchange reactions. Zeolites have the ability to sequester ions in lattice positions or within their networks of channels and voids. The zeolites can host alkali, alkaline earth and a variety of higher valance cations. As such they may be a viable alternative for immobilization of low activity waste (LAW) salts and calcines. The process for synthesizing zeolites is well documented for pure starting materials. A reactive aluminosilicate is reacted with an alkaline hydroxide at low temperature (<300 C) to form a zeolite. Processing time and temperature and specific reactants determine the type of zeolite formed. Zeolites are easy to make, and can be synthesized from a wide variety of natural and man made materials. However, relatively little is known about the process if one of the starting materials is a poorly characterized complex mixture of oxides (waste) containing nearly every element in the periodic table. The purpose of this work is to develop a clearer understanding of the advantages and limitations of producing a zeolite waste form from radioactive waste. Dr. M. W. Grutzeck at the Pennsylvania State University is investigating the production of a zeolite waste form using nonradioactive simulants. Dr. C. M. Jantzen and J. M. Pareizs at the Savannah River Technology Center will use the results from simulant work as a starting point for producing a zeolite waste form from an actual Savannah River Site radioactive waste stream

Physical, chemical, and structural evolution of zeolite-containing waste forms produced from metakaolinite and calcined HLW

International Nuclear Information System (INIS)

Pareizs, J.M.

2000-01-01

Natural and synthetic zeolites are extremely versatile materials. They can adsorb a variety of liquids and gases, and also take part in cation exchange reactions. Zeolites have the ability to sequester ions in lattice positions or within their networks of channels and voids. The zeolites can host alkali, alkaline earth and a variety of higher valence cations. As such they may be a viable alternative for immobilization of low activity waste (LAW) salts and calcines. The process for synthesizing zeolites is well documented for pure starting materials. A reactive aluminosilicate is reacted with an alkaline hydroxide at low temperature to form a zeolite. Processing time and temperature and specific reactants determine the type of zeolite formed. Zeolites are easy to make, and can be synthesized from a wide variety of natural and man made materials. However, relatively little is known about the process if one of the starting materials is a poorly characterized complex mixture of oxides (waste) containing nearly every element in the periodic table. The purpose of this work is to develop a clearer understanding of the advantages and limitations of producing a zeolite waste form from radioactive waste. Dr. M. W. Grutzeck at the Pennsylvania State University is investigating the production of a zeolite waste form using non-radioactive simulants. Dr. C. M. Jantzen and J. M. Pareizs at the Savannah River Technology Center will use the results from simulant work as a starting point for producing a zeolite waste form from an actual Savannah River Site radioactive waste stream

E.S.R. investigations of γ-irradiated AgNa-Y zeolites

International Nuclear Information System (INIS)

Abou-Kais, A.; Vedrine, J.C.; Naccache, C.

1978-01-01

Five different types of paramagnetic species related to silver nuclei were detected for γ-ray irradiated type Y zeolite in which Na + ions were exchanged by Ag + ions to different extents. One first species was identified as silver atoms almost freely diffusing in water contained in the zeolite cages. The second one corresponded to silver atoms interacting with lattice oxygens yet easily displaced to aluminium sites by slight warming. The unpaired spin delocalization to lattice nuclei was then rather significant at 36.3 and 21.2% respectively. The third species was assigned to Ag 2+ ions of d 9 character whose e.s.r. parameters reversibly depended on dehydration extent, confirming the dynamic properties of ions within zeolite material. The fourth species was attributed to AgH + arising from the action of liberated H atoms on Ag + . Finally, V- and F-type centres were observed, but could not be clearly identified. However, their parameters and their presence, compared to the case of non exchanged Na-Y zeolite sample, show that the electronic properties of framework nuclei are greatly perturbed by silver ions. For hydrated samples OH. radicals were also detected. (author)

Producing zeolites from fly ash

International Nuclear Information System (INIS)

Rayalu, S.; Labhestwar, N.K.; Biniwale, R.B.; Udhoji, J.S.; Meshram, S.U.; Khanna, P.

1998-01-01

Fly ash has virtually become a menace of thermal power generation, leading to its devastating effects on the environment. Development of alternate methods of its disposal - especially those with recourse to recovery of valuable materials-has thus become imperative. This paper deals with the utilisation of fly ash for the production of high value-added products, viz., commercial grade zeolites. The physico-chemical and morphological characteristics of fly ash based Zeolite-A (FAZ-A) compares well with commercial Zeolite-A. High calcium binding capacity, appropriate particle/pore size and other detergency characteristics of FAZ-A brings forth its potential as a substitute for phosphatic detergent builder. The technology is extremely versatile, and other products like Zeolite-X, Zeolite-Y, sodalite and mordenite are also amenable for cost effective production with modifications in certain reaction parameters. Low temperature operations, ready availability of major raw materials, simplicity of process and recycling of unused reactants and process water are special features of the process. (author)

Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

KAUST Repository

Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

2015-01-01

Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

KAUST Repository

Werghi, Baraa

2015-07-17

Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

Human bile sorption by cancrinite-type zeolites

International Nuclear Information System (INIS)

Linares, Carlos F.; Colmenares, Maryi; Ocanto, Freddy; Valbuena, Oscar

2009-01-01

A nitrated cancrinite-type zeolite was synthesized from zeolite X, NaOH and NaNO 3 solutions under autogeneous pressure at 80 deg. C for 48 h. This zeolite was characterized by X-ray diffraction (XRD), FT-IR-spectroscopy, scanning electron microscopy (SEM) and BET surface area. XRD, SEM and FT-IR confirmed the presence of nitrated cancrinite-type zeolite without other collateral phases as sodalite. Then, this sodium zeolite was exchanged with potassium and calcium cations and finally, these modified zeolites were reacted with biliar solutions from human gallbladder. Several factors such as: mass of used cancrinite, nature of the exchanged cation and reaction time of the cancrinite-bile solution interactions were studied. The composition of bile solutions (bile acids, phospholipids and bilirubin) was analyzed before and after the cancrinite-bile solution reaction. Results showed that the components of the bile were notably reduced after the contact with solids. Ca-cancrinite, 120 min of reaction time and 500 mg of solids were the best conditions determined for the bile acid reduction in human bile. When the modified zeolites were compared with the commercial cholestyramine, it was found that zeolites were more active than the latter. These zeolites may be an alternative choice to diminish cholesterol levels in hypercholesterolemic patients

Properties of glass-bonded zeolite monoliths

International Nuclear Information System (INIS)

Lewis, M.A.; Fischer, D.F.; Murphy, C.D.

1994-01-01

It has been shown that mineral waste forms can be used to immobilize waste salt generated during the pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR). Solid, leach resistant monoliths were formed by hot-pressing mixtures of salt-occluded zeolite A powders and glass frit at 990 K and 28 MPa. Additional samples have now been fabricated and tested. Normalized release rates for all elements, including iodide and chloride, were less than 1 g/m 2 d in 28-day tests in deionized water and in brine at 363 K (90 degrees C). Preliminary results indicate that these rates fall with time with both leachants and that the zeolite phase in the glass-bonded zeolite does not function as an ion exchanger. Some material properties were measured. The Poisson ratio and Young's modulus were slightly smaller in glass-bonded zeolite than in borosilicate glass. Density depended on zeolite fraction. The glass-bonded zeolite represents a promising mineral waste form for IFR salt

Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

Science.gov (United States)

Avdeev, Vasilii I.; Bedilo, Alexander F.

2018-03-01

The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

Rhodium coated mirrors deposited by magnetron sputtering for fusion applications

International Nuclear Information System (INIS)

Marot, L.; De Temmerman, G.; Oelhafen, P.; Covarel, G.; Litnovsky, A.

2007-01-01

Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for ITER plasma diagnostics. Any change in the mirror performance, in particular, its reflectivity, due to erosion of the surface by charge exchange neutrals or deposition of impurities will influence the quality and reliability of the detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium appears as an attractive material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different substrates of interest (Mo, stainless steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness and crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch tests demonstrate that adhesion properties increase with substrate hardness. Detailed optical characterizations of Rh-coated mirrors as well as results of erosion tests performed both under laboratory conditions and in the TEXTOR tokamak are presented in this paper

Rhodium-coated mirrors deposited by magnetron sputtering for fusion applications

International Nuclear Information System (INIS)

Marot, L.; Temmermann, G. de; Oelhafen, P.; Mathys, D.; Covarel, G.; Litnovsky, A.

2007-01-01

Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for plasma diagnostics that will be used in ITER. Any change in the mirror performance, in particular its reflectivity, will influence the quality and reliability of detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium may be a good candidate material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different relevant substrates (Mo, Stainless Steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness, crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch test results demonstrate that adhesion properties increase with the substrate hardness. The detailed optical characterizations of Rh coated mirrors as well as the results of erosion tests performed both under laboratory conditions and in TEXTOR will be presented in this paper. (orig.)

High-throughput preparation and testing of ion-exchanged zeolites

International Nuclear Information System (INIS)

Janssen, K.P.F.; Paul, J.S.; Sels, B.F.; Jacobs, P.A.

2007-01-01

A high-throughput research platform was developed for the preparation and subsequent catalytic liquid-phase screening of ion-exchanged zeolites, for instance with regard to their use as heterogeneous catalysts. In this system aqueous solutions and other liquid as well as solid reagents are employed as starting materials and 24 samples are prepared on a library plate with a 4 x 6 layout. Volumetric dispensing of metal precursor solutions, weighing of zeolite and subsequent mixing/washing cycles of the starting materials and distributing reaction mixtures to the library plate are automatically performed by liquid and solid handlers controlled by a single common and easy-to-use programming software interface. The thus prepared materials are automatically contacted with reagent solutions, heated, stirred and sampled continuously using a modified liquid handling. The high-throughput platform is highly promising in enhancing synthesis of catalysts and their screening. In this paper the preparation of lanthanum-exchanged NaY zeolites (LaNaY) on the platform is reported, along with their use as catalyst for the conversion of renewables

Preparation and characterization of new zeolite membranes. Application to gaseous separation; Preparation et caracterisation de nouvelles membranes de zeolithe application a la separation gazeuse

Energy Technology Data Exchange (ETDEWEB)

Anstett, M.

1996-11-25

Zeolites are interesting for the preparation of inorganic membranes which could be used for the continuous separation of gas and liquids by gas permeation and pervaporation. Zeolites membranes are obtained by hydrothermal synthesis and are characterized by XRD, SEM, TDA, IR, chemical analysis, EPMA, NMR, MAS NMR and gas permeation. After some tests of preparation of zeolite CHA and MFI self supporting membranes, the work is turned towards the preparation of zeolite MFI membranes supported by porous disks or {alpha} alumina, glass and tubes of carbon covered with a thin layer or zirconium dioxide. It is shown that the characteristics of the support (reactivity, pores dimensions, ...) strongly influence the quality of the prepared membrane. Two originals preparation processes are finalized. For the alumina disks, a gel precursor of zeolite is firs formed at the surface of the support by immersing successively that support in two non miscible liquids before the crystallisation. The gel is then converted into the zeolite by contact with water vapor. The zeolite layer obtained is localized at the surface of the support and present not only at the outside but also at the inside of the support. The characteristics of the zeolite layer can be controlled and the method can be adapted to various porous supports. The membrane obtained is interesting for hydrocarbons separations, for example the separation of methane and isobutane. In the case of Vycor glass disks, the reactivity of the support is first enhanced by contact with saturated water vapour. The temperature of the synthesis is then chosen relatively low in order to limit the attack of the support. With that method, a basic solution can be used without degradation of the support.The basicity leads to the formation of little crystals whose assembling is compact and homogeneous. The membrane obtained is interesting for example for the separation of normal butane and isobutane. (author) 71 refs.

Chemo- and regioselective homogeneous rhodium-catalyzed hydroamidomethylation of terminal alkenes to N-alkylamides.

Science.gov (United States)

Raoufmoghaddam, Saeed; Drent, Eite; Bouwman, Elisabeth

2013-09-01

A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HOR(F) ) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HOR(F) , the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HOR(F) , in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of 6FDA-durene membrane incorporated with zeolite T and aminosilane grafted zeolite T for CO2/CH4 separation

Science.gov (United States)

Jusoh, Norwahyu; Fong Yeong, Yin; Keong Lau, Kok; Shariff, Azmi Mohd

2017-08-01

In the present work, zeolite T and aminosilane grafted zeolite T are embedded into 6FDA-durene polyimide phase for the fabrication of mixed matrix membranes (MMMs). FESEM images demonstrated that the improvement of interfacial adhesion between zeolite and polymer phases in MMM loaded with aminosilane grafted zeolite T was not significant as compared to zeolite T/6FDA-durene MMM. From the gas permeation test, CO2/CH4 selectivity up to 26.4 was achieved using MMM containing aminosilane grafted zeolite T, while MMM loaded with ungrafted zeolite T showed CO2/CH4 selectivity of 19.1. In addition, MMM incorporated with aminosilane grafted zeolite T particles successfully lies on Robeson upper bound 2008, which makes it an attractive candidate for CO2/CH4 separation.

Probing Gas Adsorption in Zeolites by Variable-Temperature IR Spectroscopy: An Overview of Current Research.

Science.gov (United States)

Garrone, Edoardo; Delgado, Montserrat R; Bonelli, Barbara; Arean, Carlos O

2017-09-15

The current state of the art in the application of variable-temperature IR (VTIR) spectroscopy to the study of (i) adsorption sites in zeolites, including dual cation sites; (ii) the structure of adsorption complexes and (iii) gas-solid interaction energy is reviewed. The main focus is placed on the potential use of zeolites for gas separation, purification and transport, but possible extension to the field of heterogeneous catalysis is also envisaged. A critical comparison with classical IR spectroscopy and adsorption calorimetry shows that the main merits of VTIR spectroscopy are (i) its ability to provide simultaneously the spectroscopic signature of the adsorption complex and the standard enthalpy change involved in the adsorption process; and (ii) the enhanced potential of VTIR to be site specific in favorable cases.

Sorption of Fe{sup 3+} , Co{sup 2+} , Ce{sup 3+} , Cs{sup +} and Ba{sup 2+} in zeolite X.; Sorcion de Hierro (III), Cobalto (II), Cerio (III), Cesio (I), Bario (II) en Zeolita X.

Energy Technology Data Exchange (ETDEWEB)

Martinez M, V

1994-12-31

The sorption behavior of Fe{sup 3+} , Co{sup 2+} , Ce{sup 3+} , Cs{sup +} , and Ba{sup 2+} in aqueous solutions, was studied in presence of zeolite X. Solutions of Fe(NO{sub 3}){sub 3} . 9 H{sub 2} O, Co(NO{sub 3}){sub 2} . 6 H{sub 2} O, Ce(NO{sub 3}){sub 3} . 6 H{sub 2} O, Cs NO{sub 3} and Ba(NO{sub 3}){sub 2} were labelled with the respectively radioactive isotopes Fe{sup 59} , Co{sup 60}, Cs{sup 134}, Ba{sup 139} and Ce{sup 141}. 20 ml. of each solution was left in contact with 200 mg. of zeolite for different periods. Later the zeolites were separated by centrifugation from the aqueous solutions and the radioactivity of the aqueous phases was measured with a NaI(Tl) solid-state well detector coupled to a single-channel Picker analyzer or with a Gel hyper pure solid-state detector coupled to a 2048 channel pulse height analyzer. When Cs{sup +} in the aqueous solutions was left in contact with zeolite X it was found that it does not occupy all cationic sites in the zeolite due to the ionic radium effect. A similar behavior was found for the divalent ions. In all cases, when the pH was not controlled, the zeolite lost part of its crystallinity and when the divalent ions were exchanged again by Na{sup +}, the zeolite recovered completely its crystallinity. During the sorption, the ionic radius, and the charge are important parameters as well as the pH. When the pH of the solution was adjusted between 6.5 - 7.0 the crystallinity was maintained in some cases. For Fe{sup 3+} the crystallinity after the ion exchange was 94 % and when the pH was not adjusted the crystallinity was completely lost. It was found as well that the zeolite X induces the formation of H{sub 3} O{sup +} which competes with the cations for the sites in the zeolite. (Author).

Surfactant modified zeolite as amphiphilic and dual-electronic adsorbent for removal of cationic and oxyanionic metal ions and organic compounds.

Science.gov (United States)

Tran, Hai Nguyen; Viet, Pham Van; Chao, Huan-Ping

2018-01-01

A hydrophilic Y zeolite was primarily treated with sodium hydroxide to enhance its cation exchange capacity (Na-zeolite). The organo-zeolite (Na-H-zeolite) was prepared by a modification process of the external surface of Na-zeolite with a cationic surfactant (hexadecyltrimethylammonium; HDTMA). Three adsorbents (i.e., pristine zeolite, Na-zeolite, and Na-H-zeolite) were characterized with nitrogen adsorption/desorption isotherms, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, cation exchange capacities, and zeta potential. Results demonstrated that HDTMA can be adsorbed on the surface of Na-zeolite to form patchy bilayers. The adsorption capacity of several hazardous pollutants (i.e., Pb 2+ , Cu 2+ , Ni 2+ , Cr 2 O 7 2- , propylbenzene, ethylbenzene, toluene, benzene, and phenol) onto Na-H-zeolite was investigated in a single system and multiple-components. Adsorption isotherm was measured to further understand the effects of the modification process on the adsorption behaviors of Na-H-zeolite. Adsorption performances indicated that Na-H-zeolite can simultaneously adsorb the metal cations (on the surface not covered by HDTMA), oxyanions (on the surface covered by HDTMA). Na-H-zeolite also exhibited both hydrophilic and hydrophobic surfaces to uptake organic compounds with various water solubilities (from 55 to 75,000mg/L). It was experimentally concluded that Na-H-zeolite is a potential dual-electronic and amphiphilic adsorbent for efficiently removing a wide range of potentially toxic pollutants from aquatic environments. Copyright © 2017 Elsevier Inc. All rights reserved.

One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

Science.gov (United States)

Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

2017-04-22

The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of hydroxyl groups and exchange with deuterium on NaHX and NaHY zeolites

International Nuclear Information System (INIS)

Kubelkova, L.; Novakova, J.

1976-01-01

Deammoniation and dehydroxylation of Na(NH 4 )X and Na(NH 4 )Y zeolites were compared. With the X type, both processes overlapped and proceeded more easily than with the Y type. Both H forms contained structural OH groups and hydroxyls denoted as SiOH, to which the 3740 cm -1 band in the IR spectrum was assigned. In addition, the NaHX zeolite contained OH groups characterized by the 3700 and 3600 cm -1 bands. Certain differences in the behaviour of NaHX and NaHY zeolites during deammoniation and dehydroxylation might be attributed to the presence of ''non-localizable'' H atoms. The active sites for the D 2 -OH exchange were probably formed during dehydroxylation. Hydrogen in SiOH groups was replaced by deuterium in both zeolite types more slowly than H atoms in other OH groups, which influenced the kinetic variations in the gaseous phase. The presence of water in the gaseous phase affected the kinetics and could distort the determination of the number of H atoms bound in the zeolites. (author)

Zeolites in poultry and swine production

Directory of Open Access Journals (Sweden)

Aline Félix Schneider

Full Text Available ABSTRACT: Zeolites are minerals that have intriguing properties such as water absorption, ion adsorption and cation exchange capacity. There are approximately 80 species of natural zeolites recognized and hundreds of artificial zeolites, which have been researched in several fields. Due to their chemical characteristics, zeolites have great potential for use in animal production, especially in poultry and swine farms, as food additives, litter amendment and treatment of residues, with direct and indirect effects on performance, yield and quality of carcass, ambience of farm sheds and reduction of environmental pollution.

Diphosphinoazine Rhodium(I) and Iridium(I) Complexes

Czech Academy of Sciences Publication Activity Database

Pošta, Martin; Čermák, Jan; Vojtíšek, P.; Císařová, I.

2006-01-01

Roč. 71, č. 2 (2006), s. 197-206 ISSN 0010-0765 R&D Projects: GA ČR(CZ) GA203/01/0554; GA ČR(CZ) GA203/99/M037 Institutional research plan: CEZ:AV0Z40720504 Keywords : diphosphinoazines * rhodium complexes * iridium complexes Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

Aldol condensation of furfural and acetone on zeolites

Czech Academy of Sciences Publication Activity Database

Kikhtyanin, O.; Kelbichová, V.; Vitvarová, Dana; Kubů, Martin; Kubička, D.

2014-01-01

Roč. 227, MAY 2014 (2014), s. 154-162 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : aldol condensation * oligomerization * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.893, year: 2014

Regioselective nitration of aromatic substrates in zeolite cages

Indian Academy of Sciences (India)

Unknown

... mixture, responsible for the generation of large amounts of wastes, which ... benzene in gas phase over solid catalysts such as SiO2–Al2O3, supported ... selective nitration with a nitrogen dioxide-oxygen-zeolite H-β/HY as a solid inorganic.

Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY.

Science.gov (United States)

Borah, Bhaskar J; Jobic, H; Yashonath, S

2010-04-14

We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime. Activation energy is in the order E(a)(n-pentane)>E(a)(isopentane)>E(a)(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen that D(n-pentane)>D(isopentane)>D(neopentane) and E(a)(n-pentane)single exponential decay for neopentane and isopentane. For n-pentane, a single exponential fit provides a poor fit especially at short times. Cage residence time is largest for n-pentane and lowest for neopentane. For neopentane, the width of the self-part of the dynamic structure factor shows a near monotonic decrease with wavenumber. For n-pentane a minimum is seen near k=0.5 A(-1) suggesting a slowing down of motion around the 12-ring window, the bottleneck for diffusion. Finally, the result that the branched isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

Characterization of Mexican zeolite minerals

International Nuclear Information System (INIS)

Jimenez C, M.J.

2005-01-01

50% of the Mexican territory is formed by volcanic sequences of the Pliocene type, which appear extensively in the northwest states (Sonora, Sinaloa, Chihuahua, Durango) and west of Mexico (Jalisco and Nayarit), in central Mexico (Zacatecas, Guanajuato, San Luis Potosi, Queretaro, Hidalgo) and south of Mexico (Guerrero, Oaxaca); therefore, it is to be expected that in our country big locations of natural zeolites exist in its majority of the clinoptilolite type. The present study was focused toward the characterization of two Mexican natural zeolite rocks presumably of the clinoptilolite and filipsite types, one of them comes from the state of Chihuahua and the other of a trader company of non metallic minerals, due that these materials are not characterized, its are not known their properties completely and therefore, the uses that can be given to these materials. In this investigation work it was carried out the characterization of two Mexican zeolite rocks, one coming from the Arroyo zone, municipality of La Haciendita, in the state of Chihuahua; and the other one was bought to a trader company of non metallic minerals. The two zeolites so much in their natural form as conditioned with sodium; they were characterized by means of X-ray diffraction, scanning electron microscopy of high vacuum and elementary microanalysis (EDS), surface area analysis (BET), thermal gravimetric analysis. To differentiate the heulandite crystalline phase of the other clinoptilolite rock, its were carried out thermal treatments. The quantification of Al, Na, Ca, K, Mg, Fe was carried out in solution, by means of atomic absorption spectroscopy and the quantity of Si was determined by gravimetry. The zeolite rocks presented for the major part the crystalline heulandite and clinoptilolite phases for the most part, and it was found that the zeolite coming from the state of Chihuahua possesses a bigger content of heulandite and the denominated filipsite it is really a zeolite

Experimental Determination of the Molar Absorption Coefficient of n-Hexane Adsorbed on High-Silica Zeolites.

Science.gov (United States)

Gatti, Giorgio; Olivas Olivera, Diana F; Sacchetto, Vittoria; Cossi, Maurizio; Braschi, Ilaria; Marchese, Leonardo; Bisio, Chiara

2017-09-06

Determination of the molar absorption coefficients of the CH 3 bending mode at ν˜ =1380 cm -1 (ϵ 1380 ) of n-hexane adsorbed from the gas phase on two different dealuminated zeolites is derived by a combination of IR spectroscopy and microgravimetric analysis. High-silica zeolite Y (HSZ-Y) and zeolite ZSM-5 (with SiO 2 /Al 2 O 3 ratios of 200 and 280, respectively) with different textural and surface features are selected to evaluate the effect of the pore structure and architecture on the value of ϵ 1380 of the adsorbed n-hexane. Experimental data indicate that the molecule experiences a different adsorption environment inside zeolites; thus resulting in a significant change of the dipole moment and very different ϵ 1380 values: (0.278±0.018) cm μmol -1 for HSZ-Y and (0.491±0.032) cm μmol -1 for ZSM-5. Experimental data are also supported by computational modeling, which confirms the effect of different matrices on the IR absorption intensity. This study reveals that the use of probe molecules for quantitative measurements of surface sites has to be judiciously adopted, especially if adsorption occurs in the restricted spaces of microporous materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acidity in zeolite catalysis

NARCIS (Netherlands)

Santen, van R.A.; Gauw, de F.J.M.M.; Corma, A.; Melo, F.; Mendioroz, S.; Fierro, J.L.G.

2000-01-01

A review with 21 refs. is provided on our current understanding of the activation of hydrocarbons by protonic zeolites. One has to distinguish the proton affinity of a zeolite, measured in an equil. expt., from proton activation that dets. a kinetic catalytic result. The proton affinity depends on

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

Science.gov (United States)

Kassem, Mohammed A.; Amin, Alaa S.

2015-02-01

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

Zeolite Nanoparticles for Selective Sorption of Plasma Proteins.

Science.gov (United States)

Rahimi, M; Ng, E-P; Bakhtiari, K; Vinciguerra, M; Ali Ahmad, H; Awala, H; Mintova, S; Daghighi, M; Bakhshandeh Rostami, F; de Vries, M; Motazacker, M M; Peppelenbosch, M P; Mahmoudi, M; Rezaee, F

2015-11-30

The affinity of zeolite nanoparticles (diameter of 8-12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy.

To Investigate the Absorption, Dynamic Contact Angle and Printability Effects of Synthetic Zeolite Pigments in an Inkjet Receptive Coating

Science.gov (United States)

Jalindre, Swaraj Sunil

Ink absorption performance in inkjet receptive coatings containing synthetic zeolite pigments was studied. Coating pigment pore and particle size distribution are the key parameters that influence in modifying media surface properties, thus affecting the rate of ink penetration and drying time (Scholkopf, et al. 2004). The primary objective of this study was: (1) to investigate the synthetic zeolite pigment effects on inkjet ink absorption, dynamic contact angle and printability, and (2) to evaluate these novel synthetic zeolite pigments in replacing the fumed silica pigments in conventional inkjet receptive coatings. In this research study, single pigment coating formulations (in equal P:B ratio) were prepared using microporous synthetic zeolite pigments (5A, Organophilic and 13X) and polyvinyl alcohol (PVOH) binder. The laboratory-coated samples were characterized for absorption, air permeance, roughness, drying time, wettability and print fidelity. Based on the rheological data, it was found that the synthetic zeolite formulated coatings depicted a Newtonian flow behavior at low shear; while the industry accepted fumed silica based coatings displayed a characteristically high pseudoplastic flow behavior. Our coated samples generated using microporous synthetic zeolite pigments produced low absorption, reduced wettability and accelerated ink drying characteristics. These characteristics were caused due to the synthetic zeolite pigments, which resulted in relatively closed surface structure coated samples. The research suggested that no single selected synthetic zeolite coating performed better than the conventional fumed silica based coatings. Experimental data also showed that there was no apparent relationship between synthetic zeolite pigment pore sizes and inkjet ink absorption. For future research, above coated samples should be evaluated for pore size distribution using Mercury Porosimeter, which quantifies surface porosity of coated samples. This presented

Examination of zeolites by neutron reflection method

International Nuclear Information System (INIS)

Szegedi, S.; Varadi, M.; Boedy, Z.T.; Vas, L.

1991-01-01

Neutron reflection method has been used for the determination of zeolite content in minerals. The basis of this measurement is to observe the large difference between the water content of zeolite and that of other mineralic parts of the sample. The method suggested can be used in a zeolite mine for measuring the zeolite content continuously and controlling the quality of the end products. (author) 5 refs.; 3 figs.; 3 tabs