Science.gov

Sample records for zeolite modification copper

  1. Copper-containing zeolite catalysts

    DOEpatents

    Price, G.L.; Kanazirev, V.

    1996-12-10

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  2. Copper-containing zeolite catalysts

    DOEpatents

    Price, Geoffrey L.; Kanazirev, Vladislav

    1996-01-01

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  3. Chiral modification of copper exchanged zeolite-Y with cinchonidine and its application in the asymmetric Henry reaction.

    PubMed

    Deka, Jogesh; Satyanarayana, L; Karunakar, G V; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2015-12-28

    Chirally modified Cu(2+) exchanged zeolite-Y was synthesized by direct adsorption of cinchonidine under ambient conditions. The chirally modified materials were characterized using various spectrochemical and physicochemical techniques viz. BET, FTIR, MAS ((1)H and (13)C NMR), XPS, SEM, cyclic voltammetry and PXRD. Characteristic peaks of cinchonidine observed in the supported materials confirmed the adsorption of cinchonidine and its coordination with the Cu(2+) active site on copper exchanged zeolite-Y. (13)C SSNMR and XPS analysis however confirmed for the half encapsulation process, only the quinoline ring of cinchonidine gets coordinated to the internal metal sites via the N atom while the quinuclidine moiety extends out of the host surface. Cinchonidine supported Cu(2+)-Y zeolites were found to exhibit good catalytic performance in the asymmetric Henry reaction. (1)H SSNMR studies also confirmed the protonation of the N atom of the quinuclidine ring during the course of the Henry reaction. Heterogeneous chiral catalysts were effective for up to two consecutive cycles. Leaching of cinchonidine after the second cycle was found to have a negative result in the catalytic performance.

  4. Copper-Exchanged Zeolite L Traps Oxygen

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Seshan, Panchalam K.

    1991-01-01

    Brief series of simple chemical treatments found to enhance ability of zeolite to remove oxygen from mixture of gases. Thermally stable up to 700 degrees C and has high specific surface area which provides high capacity for adsorption of gases. To increase ability to adsorb oxygen selectively, copper added by ion exchange, and copper-exchanged zeolite reduced with hydrogen. As result, copper dispersed atomically on inner surfaces of zeolite, making it highly reactive to oxygen, even at room temperature. Reactivity to oxygen even greater at higher temperatures.

  5. Copper cation removal in an electrokinetic cell containing zeolite.

    PubMed

    Elsayed-Ali, Omar H; Abdel-Fattah, Tarek; Elsayed-Ali, Hani E

    2011-01-30

    Zeolites are used in environmental remediation of soil or water to immobilize or remove toxic materials by cation exchange. An experiment was conducted to test the use a low electric field to direct the toxic cations towards the zeolite. An electrokinetic cell was constructed using carbon electrodes. Synthetic Linde Type A (LTA) zeolite was placed in the cell. Copper(II) chloride dissolved in water was used as a contaminant. The Cu(2+) concentration was measured for ten hours with and without an applied electric field. The removal of the Cu(2+) ions was accelerated by the applied field in the first two hours. For longer time, the electric field did not improve the removal rate of the Cu(2+) ions. The presence of zeolite and applied electric field complicates the chemistry near the cathode and causes precipitation of Cu(2+) ions as copper oxide on the surface of the zeolite. With increased electric field the zeolite farther away from the cathode had little cation exchange due to the higher drift velocity of the Cu(2+) ions. The results also show that, in the LTA Zeolite A pellets, the cation exchange of Cu is limited to a shell of several tens of micrometers. PMID:21109348

  6. The stability of copper oxo species in zeolite frameworks

    DOE PAGES

    Vilella, Laia; Studt, Felix

    2016-03-07

    Cu-exchanged zeolites are promising heterogeneous catalysts, as they provide a confined environment to carry out highly selective reactions. Furthermore, the knowledge of how the zeolite framework and the location of Al atoms therein affect the adsorption of copper species is still not well understood. In this work, DFT was used to investigate the adsorption of potential Cu oxo active species suggested in the literature [Cu(η2-O2), Cu(µ-O)Cu, and Cu2O2] into zeolites with different pore sizes and shapes (AFI, CHA, TON, MOR, and MFI). The calculations revealed that both monomeric and dimeric Cu oxo species bind strongly to the O atoms ofmore » the lattice. For the monometallic species similar adsorption energies are obtained with the different zeolite frameworks, whereas an optimum Al–Al distance is required for the dimeric species.« less

  7. Copper removal using bio-inspired polydopamine coated natural zeolites.

    PubMed

    Yu, Yang; Shapter, Joseph G; Popelka-Filcoff, Rachel; Bennett, John W; Ellis, Amanda V

    2014-05-30

    Herein, for the first time, natural clinoptilolite-rich zeolite powders modified with a bio-inspired adhesive, polydopamine (PDA), have been systematically studied as an adsorbent for copper cations (Cu(II)) from aqueous solution. Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) revealed successful grafting of PDA onto the zeolite surface. The effects of pH (2-5.5), PDA treatment time (3-24h), contact time (0 to 24h) and initial Cu(II) ion concentrations (1 to 500mgdm(-3)) on the adsorption of Cu(II) ions were studied using atomic absorption spectroscopy (AAS) and neutron activation analysis (NAA). The adsorption behavior was fitted to a Langmuir isotherm and shown to follow a pseudo-second-order reaction model. The maximum adsorption capacities of Cu(II) were shown to be 14.93mgg(-1) for pristine natural zeolite and 28.58mgg(-1) for PDA treated zeolite powders. This impressive 91.4% increase in Cu(II) ion adsorption capacity is attributed to the chelating ability of the PDA on the zeolite surface. Furthermore studies of recyclability using NAA showed that over 50% of the adsorbed copper could be removed in mild concentrations (0.01M or 0.1M) of either acid or base. PMID:24731937

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

    NASA Astrophysics Data System (ADS)

    Li, Wenlin; Zheng, Jinyu; Luo, Yibin; Da, Zhijian

    2016-09-01

    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, NH3-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.

  9. Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes.

    PubMed

    Wulfers, M J; Teketel, S; Ipek, B; Lobo, R F

    2015-03-14

    This communication reports the discovery of several small-pore Cu-zeolites and zeotypes that produce methanol from methane and water vapor, and produce more methanol per copper atom than Cu-ZSM-5 and Cu-mordenite. The new materials include Cu-SSZ-13, Cu-SSZ-16, Cu-SSZ-39, and Cu-SAPO-34. PMID:25679753

  10. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature.

    PubMed

    Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly; Román-Leshkov, Yuriy

    2016-06-22

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C-H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

  11. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

    PubMed Central

    2016-01-01

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

  12. Zeolites

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco

  13. Surface modification of ultra thin PES-zeolite using thermal annealing to increase flux and rejection of produced water treatment

    NASA Astrophysics Data System (ADS)

    Kusworo, T. D.; Widayat, Pradini, A. W.; Armeli, Y. P.

    2015-12-01

    Membrane technology is an alternative of water treatment based on filtration that is being developed. Surface Modification using heat treatment has been investigated to improve the performance of ultra thin PES-Zeolite nanocomposite membrane for produced water treatment from Pertamina Balongan. Two types of membranes with surface modification and without modification were prepared to study the effect of surface modification on its permeation properties. Asymmetric ultra thin PES-Zeolite nanocomposite membrane for produced water treatment was casted using the dry/wet phase inversion technique from dope solutions containing polyethersulfone, N-methyl-2-pyrrolidone (NMP) as a solvent and zeolite as a filler. Experimental results showed that the heat treatment at near glass transition temperature was increase the rejection of COD, Turbidity and ion Ca2+. The better adherence of zeolite particles in the polymer matrix combined with formation of charge transfer complexes (CTCs) and cross-linking might be the main factors to enhance the percent of rejection. Field emission scanning electron microscopy (FESEM) micrographs showed that the selective layer and the substructure of PES-zeolite membrane became denser and more compact after the heat treatment. The FESEM micrographs also showed that the heat treatment was increased the adherence of zeolite particle and polymer. Membranes treated at 180 °C for 15 seconds indicated increase the rejection and small decrease in flux for produced water treatment..

  14. Surface modification of ultra thin PES-zeolite using thermal annealing to increase flux and rejection of produced water treatment

    SciTech Connect

    Kusworo, T. D. Widayat,; Pradini, A. W.; Armeli, Y. P.

    2015-12-29

    Membrane technology is an alternative of water treatment based on filtration that is being developed. Surface Modification using heat treatment has been investigated to improve the performance of ultra thin PES-Zeolite nanocomposite membrane for produced water treatment from Pertamina Balongan. Two types of membranes with surface modification and without modification were prepared to study the effect of surface modification on its permeation properties. Asymmetric ultra thin PES-Zeolite nanocomposite membrane for produced water treatment was casted using the dry/wet phase inversion technique from dope solutions containing polyethersulfone, N-methyl-2-pyrrolidone (NMP) as a solvent and zeolite as a filler. Experimental results showed that the heat treatment at near glass transition temperature was increase the rejection of COD, Turbidity and ion Ca{sup 2+}. The better adherence of zeolite particles in the polymer matrix combined with formation of charge transfer complexes (CTCs) and cross-linking might be the main factors to enhance the percent of rejection. Field emission scanning electron microscopy (FESEM) micrographs showed that the selective layer and the substructure of PES-zeolite membrane became denser and more compact after the heat treatment. The FESEM micrographs also showed that the heat treatment was increased the adherence of zeolite particle and polymer. Membranes treated at 180 °C for 15 seconds indicated increase the rejection and small decrease in flux for produced water treatment.

  15. Kinetics of Copper Adsorption from Effluent Stream by ZeoliteNaX

    NASA Astrophysics Data System (ADS)

    Singh, Surinder; Sambi, S. S.; Sharma, S. K.; Pandey, Pankaj Kumar

    2010-06-01

    The batch experiments were conducted to study the copper (II) removal by ZeoliteNaX at temperature of 288+1 K, adsorbent dose of 2 g/L and contact time of 24 hour. Effects of pH, temperature, contact time and Cu (II) ion concentration by the adsorbent were investigated. The data were analyzed using the Langmuir, Freundlich and Temkin isotherms. Freundlich isotherm was found to correlate the adsorption of Cu (II) better and the mono-layer adsorption capacity for Cu (II) removal was 41.6 mg/g. The adsorbed amounts of Cu (II) reached equilibrium within 150 minutes. The four adsorption kinetic models namely, the first order equation, second order equations, pseudo-first order equation and pseudo second-order equations were also tested to fit the data. The pseudo-first-order equation was found to fit best for the experimental data. Thermodynamic analysis indicated the spontaneous and endothermic nature of the adsorption of Cu (II) by ZeoliteNaX.

  16. Tailoring the Transport Properties of Zeolitic Imidazolate Frameworks by Post-Synthetic Thermal Modification.

    PubMed

    Zhang, Chen; Koros, William J

    2015-10-28

    Understanding how to control transport properties of zeolitic imidazolate frameworks (ZIFs) is critical to extend ZIF-based membranes and adsorbents to a wide spectrum of gas and vapor separations. In this work, we report a facile post-synthetic thermal modification (PSTM) technique to tailor ZIFs' transport properties by balancing diffusivity and diffusion selectivity. With controllable dissociation of framework methyl groups from a precursor ZIF (ZIF-8), we have prepared thermally modified ZIFs showing substantially increased n-butane diffusivity and attractive n/iso-butane diffusion selectivity. Hybrid ZIF/polymer mixed-matrix membranes formed using these thermally modified ZIFs are expected to deliver attractive butane isomer separation performance. Membranes based on such materials can potentially be used to retrofit refinery alkylation units for producing premium gasoline blending stocks. PMID:26451850

  17. Stable copper-zeolite filter media for bacteria removal in stormwater.

    PubMed

    Li, Ya L; McCarthy, David T; Deletic, Ana

    2014-05-30

    Cu(2+)-exchanged zeolite (ZCu) as antibacterial media shows great potential for bacteria removal from stormwater, but its stability in high salinity water needs attention. In this study, stable antibacterial media were developed by modifying ZCu through calcination and in situ Cu(OH)2 coating. Their stability and Escherichia coli removal efficiency along with impact of salinity were examined in gravity-fed columns. While copper leaching from ZCu was 20mg/L in test water of salinity 250μS/cm, it was reduced by over 97% through Cu(OH)2 coating and/or calcination. ZCu coated with Cu(OH)2 followed by heat treatment at 180°C (ZCuCuO180) exhibited more consistent E. coli removal (1.7-2.7 log) than ZCu (1.2-3.3 log) in test water of varied salinity but constant contact time 22min. ZCu calcined at 400°C (ZCu400) effectively inactivated removed bacteria during 24h drying period. In the presence of native microbial communities, new sand filters, particularly those having ZCu400 at the top to inactivate bacteria during drying periods and ZCuCuO180 midway to capture and inactivate microbes during wet events, provided the best bacterial removal (1.7 log, contact time 9min). Copper leaching from this design was 9μg/L, well below long-term irrigation standard of 200μg/L.

  18. The leading role of association in framework modification of highly siliceous zeolites with adsorbed methylamine.

    PubMed

    Han, Ai-Jie; Guo, Juan; Yu, Hui; Zeng, Yu; Huang, Yue-Fang; He, He-Yong; Long, Ying-Cai

    2006-03-13

    Affinity index (AT value), adsorption heat, X-ray diffraction (XRD), and 13C and 29Si magic-angle spinning (MAS) NMR, FTIR, and Raman spectroscopies were used to study the interaction of highly siliceous MFI-, FAU-, and FER-type zeolites with adsorbed methylamine (MA). Compared with the data for methanol, the much higher AT values and adsorption heats, and significant changes in XRD patterns, 29Si MAS NMR spectra, and FTIR spectra for the zeolites after adsorption of MA, revealed a strong hydrogen-bonding interaction between the perfect framework of the zeolites and the adsorbed MAs. This interaction results from the fact that the H atom of the amine group attacks the [Si-O] framework to form a Si-OHN bond, which leads to the appearance of Si-N bonds in the zeolites at 323 K. Therefore, the zeolite framework can be modified with MA under mild conditions. The highly siliceous MFI zeolite and the H-ZSM-5 zeolite with SiO2/Al2O3=31:1 were modified with MA and investigated by temperature-programmed desorption of CO2. The modified zeolites exhibited greatly enhanced basic properties in comparison with those of the raw materials. The influence of defects in the zeolite on the adsorption and the interaction with MA is discussed.

  19. Enhanced photocatalytic activity of supported TiO2 by selective surface modification of zeolite Y

    NASA Astrophysics Data System (ADS)

    Guesh, Kiros; Márquez-Álvarez, Carlos; Chebude, Yonas; Díaz, Isabel

    2016-08-01

    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 TiO2 (20 wt%) led to a final photocatalyst. The samples were characterized by X-ray diffraction (XRD), elemental analysis (ICP-OES), N2 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 TiO2/treated zeolite sample yielded 92% photocatalytic degradation of 10 ppm methyl orange (MO), a model pollutant, while the TiO2/parent zeolite converted only 7.6%. The mass normalized turnover rate (TORm) of the treated zeolite loaded with TiO2 was about 12 times higher than that of the parent zeolite loaded with the same amount of TiO2 precursor. This higher photocatalytic activity of the TiO2 supported on treated zeolite can be attributed to a more efficient interaction of the TiO2 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.

  20. Optimizing anti-coking abilities of zeolites by ethylene diamine tetraacetie acid modification on catalytic fast pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Zhong, Zhaoping; Song, Zuwei; Ding, Kuan; Chen, Paul; Ruan, Roger

    2015-12-01

    In order to minimize coke yield during biomass catalytic fast pyrolysis (CFP) process, ethylene diamine tetraacetie acid (EDTA) chemical modification method is carried out to selectively remove the external framework aluminum of HZSM-5 catalyst. X-ray diffraction (XRD), nitrogen (N2)-adsorption and ammonia-temperature programmed desorption (NH3-TPD) techniques are employed to investigate the porosity and acidity characteristics of original and modified HZSM-5 samples. Py-GC/MS and thermo-gravimetric analyzer (TGA) experiments are further conducted to explore the catalytic effect of modified HZSM-5 samples on biomass CFP and to verify the positive effect on coke reduction. Results show that EDTA treatment does not damage the crystal structure of HZSM-5 zeolites, but leads to a slight increase of pore volume and pore size. Meanwhile, the elimination of the strong acid peak indicates the dealumination of outer surface of HZSM-5 zeolites. Treatment time of 2 h (labeled EDTA-2H) is optimal for acid removal and hydrocarbon formation. Among all modified catalysts, EDTA-2H performs the best for deacidification and can obviously increase the yields of positive chemical compositions in pyrolysis products. Besides, EDTA modification can improve the anti-coking properties of HZSM-5 zeolites, and EDTA-2H gives rise to the lowest coke yield.

  1. Corrosion resistance properties of superhydrophobic copper surfaces fabricated by one-step electrochemical modification process

    NASA Astrophysics Data System (ADS)

    Huang, Ying; Sarkar, D. K.; Gallant, Danick; Chen, X.-Grant

    2013-10-01

    Superhydrophobic copper surfaces have been prepared by a one-step electrochemical modification process in an ethanolic stearic acid solution. In this work, the corrosion properties of hydrophobic copper surface and superhydrophobic copper surfaces were analyzed by means of electrochemical analyses and compared with that of as-received bare copper substrate. The decrease of corrosion current density (icorr) as well as the increase of polarization resistance (Rp) obtained from potentiodynamic polarization curves revealed that the superhydrophobic film on the copper surfaces improved the corrosion resistance performance of the copper substrate.

  2. Ag-Promoted ZrBEA Zeolites Obtained by Post-Synthetic Modification for Conversion of Ethanol to Butadiene.

    PubMed

    Sushkevich, Vitaly L; Ivanova, Irina I

    2016-08-23

    1,3-Butadiene was synthesized from ethanol using zirconium-containing zeolite beta (ZrBEA) catalysts doped with 1 wt % silver. The Zr was planted using post-synthesis modification by dealumination of the parent zeolite followed by treatment with ZrOCl2 in a DMSO solution. FTIR and NMR spectroscopy were used to investigate the planting process by preparing materials with different Si/Al ratios and crystal sizes. The results showed preferential grafting of Zr to the terminal silanols present on the external surface of the zeolite crystals instead of incorporation of Zr into silanol nests. The grafting yielded highly accessible Zr(OSi)3 OH open sites with high Lewis acidity, as confirmed by FTIR spectroscopy of adsorbed CO. These sites are shown to be extremely active for the conversion of ethanol to butadiene. Ag/ZrBEA catalysts prepared using the post-synthesis method showed significant advantages compared with Ag/ZrBEA catalysts synthesized using a conventional hydrothermal procedure. The best catalyst performance in terms of butadiene formation rate (3 μmol g(-1)  s(-1) ) was observed over Ag/Zr(3.5)BEA(75) (containing 3.5 wt % Zr), which had the smallest crystal size and the highest content of Zr open sites of the prepared catalysts. PMID:27467567

  3. Unveiling the adsorption mechanism of zeolitic imidazolate framework-8 with high efficiency for removal of copper ions from aqueous solutions.

    PubMed

    Zhang, Yujie; Xie, Zhiqiang; Wang, Zhuqing; Feng, Xuhui; Wang, Ying; Wu, Aiguo

    2016-08-01

    Among the heavy metal ions, copper(ii) can cause eye and liver damage at high uptake. The existence of copper ions (Cu(2+)) even with an ultralow concentration of less than 0.1 μg g(-1) can be toxic to living organisms. Thus, it is highly desirable to develop efficient adsorbents to remove Cu(2+) from aqueous solutions. In this work, without any surface functionalization or pretreatment, a water-stable zeolitic imidazolate framework (ZIF-8) synthesized at room temperature is directly used as a highly efficient adsorbent for removal of copper ions from aqueous solutions. To experimentally unveil the adsorption mechanism of Cu(2+) by using ZIF-8, we explore various effects from a series of important factors, such as pH value, contact time, temperature and initial Cu(2+) concentration. As a result, ZIF-8 nanocrystals demonstrate an unexpected high adsorption capacity of Cu(2+) and high removal efficiency for both high and low concentrations of Cu(2+) from water. Moreover, ZIF-8 nanocrystals possess fast kinetics for removing Cu(2+) with the adsorption time of less than 30 min. In addition, the pH of the solution ranging from 3 to 6 shows little effect on the adsorption of Cu(2+) by ZIF-8. The adsorption mechanism is proposed for the first time and systematically verified by various characterization techniques, such as TEM, FTIR, XPS, XRD and SEM. PMID:27396854

  4. Modification of surface properties of copper-refractory metal alloys

    DOEpatents

    Verhoeven, J.D.; Gibson, E.D.

    1993-10-12

    The surface properties of copper-refractory metal (CU-RF) alloy bodies are modified by heat treatments which cause the refractory metal to form a coating on the exterior surfaces of the alloy body. The alloys have a copper matrix with particles or dendrites of the refractory metal dispersed therein, which may be niobium, vanadium, tantalum, chromium, molybdenum, or tungsten. The surface properties of the bodies are changed from those of copper to that of the refractory metal.

  5. DDR-type zeolite membrane synthesis, modification and gas permeation studies

    DOE PAGES

    Yang, Shaowei; Cao, Zishu; Arvanitis, Antonios; Sun, Xinhui; Xu, Zhi; Dong, Junhang

    2016-01-22

    DDR-type zeolite membrane was synthesized on porous α-alumina substrate by hydrothermal treatment of a ball-milled Sigmal-1 crystal seed layer in an aluminum-free precursor solution containing 1-Adamantylamine as the structure directing agent (SDA). The as-synthesized DDR zeolite membranes were defect-free but the supported zeolite layers were susceptible to crack development during the subsequent high-temperature SDA removal process. The cracks were effectively eliminated by the liquid phase chemical deposition method using tetramethoxysilane as the precursor for silica deposits. The modified membrane was extensively studied for H2, He, O2, N2, CO2, CH4, and i-C4H10 pure gas permeation and CO2/CH4 mixture separation. At 297more » K and 2-bar feed gas pressure, the membrane achieved a CO2/CH4 separation factor of ~92 for a feed containing 90% CO2, which decreased to 62 for a feed containing 10% CO2 with the CO2 permeance virtually unchanged at ~1.8×10–7 mol/m• sup>2 s • Pa regardless of the feed composition. It also exhibited an O2/N2 permselectivity of 1.8 at 297 K. Furthermore, the gas permeation behaviors of the current aluminum-containing DDR type zeolite membrane are generally in good agreement with the findings in both experimental and theoretical studies on the pure-silica DDR membranes in recent literature.« less

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

    PubMed

    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.

  7. Ion distribution in copper exchanged zeolites by using Si-29 spin lattice relaxation analysis

    NASA Astrophysics Data System (ADS)

    Palamara, Joseph; Seidel, Karsten; Moini, Ahmad; Prasad, Subramanian

    2016-06-01

    Transition metal-containing zeolites, particularly those with smaller pore size, have found extensive application in the selective catalytic reduction (SCR) of environmental pollutants containing nitrogen oxides. We report these zeolites have dramatically faster silicon-29 (Si-29) spin lattice relaxation times (T1) compared to their sodium-containing counterparts. Paramagnetic doping allows one to acquire Si-29 MAS spectra in the order of tens of seconds without significantly affecting the spectral resolution. Moreover, relaxation times depend on the method of preparation and the next-nearest neighbor silicon Qn(mAl) sites, where n = 4 and m = 0-4, respectively. A clear trend is noted between the effectiveness of Cu exchange and the Si-29 NMR relaxation times. It is anticipated that the availability of this tool, and the enhanced understanding of the nature of the active sites, will provide the means for designing improved SCR catalysts.

  8. Ion distribution in copper exchanged zeolites by using Si-29 spin lattice relaxation analysis.

    PubMed

    Palamara, Joseph; Seidel, Karsten; Moini, Ahmad; Prasad, Subramanian

    2016-06-01

    Transition metal-containing zeolites, particularly those with smaller pore size, have found extensive application in the selective catalytic reduction (SCR) of environmental pollutants containing nitrogen oxides. We report these zeolites have dramatically faster silicon-29 (Si-29) spin lattice relaxation times (T1) compared to their sodium-containing counterparts. Paramagnetic doping allows one to acquire Si-29 MAS spectra in the order of tens of seconds without significantly affecting the spectral resolution. Moreover, relaxation times depend on the method of preparation and the next-nearest neighbor silicon Qn(mAl) sites, where n=4 and m=0-4, respectively. A clear trend is noted between the effectiveness of Cu exchange and the Si-29 NMR relaxation times. It is anticipated that the availability of this tool, and the enhanced understanding of the nature of the active sites, will provide the means for designing improved SCR catalysts. PMID:27055207

  9. Copper stabilization by zeolite synthesis in polluted soils treated with coal fly ash

    SciTech Connect

    Roberto Terzano; Matteo Spagnuolo; Luca Medici; Bart Vekemans; Laszlo Vincze; Koen Janssens; Pacifico Ruggiero

    2005-08-15

    This paper reports on the process of zeolite formation in an agricultural soil artificially polluted by high amounts of Cu (15 mg of Cu/g of soil dry weight) and treated with fused coal fly ash at 30 and 60 C and how this process affects the mobility and availability of the metal. As a consequence of the treatment, the amount of dissolved Cu, and thus its mobility, was strongly reduced, and the percentage of the metal stabilized in the solid phase increased over time, reaching values of 30% at 30{sup o}C and 40% at 60{sup o}C. The physicochemical phenomena responsible for Cu stabilization in the solid phase have been evaluated by EDTA sequential extractions and synchrotron radiation based X-ray microanalytical techniques. These techniques were used for the visualization of the spatial distribution and the speciation of Cu in and/or on the neo-formed zeolite particles. In particular, micro XRF (X-ray fluorescence) tomography showed direct evidence that Cu can be entrapped as clusters inside the porous zeolitic structures while -{mu}XANES (X-ray absorption near edge structure) spectroscopy determinations revealed Cu to be present mainly as Cu(II) hydroxide and Cu(II) oxide. The reported results could be useful as a basic knowledge for planning new technologies for the on-site physicochemical stabilization of heavy metals in heavily polluted soils. 32 refs., 5 figs.

  10. Natrolite zeolite supported copper nanoparticles as an efficient heterogeneous catalyst for the 1,3-diploar cycloaddition and cyanation of aryl iodides under ligand-free conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Khalaj, Mehdi

    2015-09-01

    In this paper, we report the preparation of Natrolite zeolite supported copper nanoparticles as a heterogeneous catalyst for 1,3-diploar cycloaddition and synthesis aryl nitriles from aryl iodides under ligand-free conditions. The catalyst was characterized using XRD, SEM, TEM, EDS and TG-DTA. The experimental procedure is simple, the products are formed in high yields and the catalyst can be recycled and reused several times without any significant loss of catalytic activity.

  11. Investigation of PCDD/F emissions from mobile source diesel engines: impact of copper zeolite SCR catalysts and exhaust aftertreatment configurations.

    PubMed

    Liu, Z Gerald; Wall, John C; Barge, Patrick; Dettmann, Melissa E; Ottinger, Nathan A

    2011-04-01

    This study investigated the impact of copper zeolite selective catalytic reduction (SCR) catalysts and exhaust aftertreatment configurations on the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from mobile source diesel engines. Emissions of PCDD/Fs, reported as the weighted sum of 17 congeners called the toxic equivalency quotient (TEQ), were measured using a modified EPA Method 0023A in the absence and presence of exhaust aftertreatment. Engine-out emissions were measured as a reference, while aftertreatment configurations included various combinations of diesel oxidation catalyst (DOC), diesel particulate filter (DPF), Cu-zeolite SCR, Fe-zeolite SCR, ammonia oxidation catalyst (AMOX), and aqueous urea dosing. In addition, different chlorine concentrations were evaluated. Results showed that all aftertreatment configurations reduced PCDD/F emissions in comparison to the engine-out reference, consistent with reduction mechanisms such as thermal decomposition or combined trapping and hydrogenolysis reported in the literature. Similarly low PCDD/F emissions from the DOC-DPF and the DOC-DPF-SCR configurations indicated that PCDD/F reduction primarily occurred in the DOC-DPF with no noticeable contribution from either the Cu- or Fe-zeolite SCR systems. Furthermore, experiments performed with high chlorine concentration provided no evidence that chlorine content has an impact on the catalytic synthesis of PCDD/Fs for the chlorine levels investigated in this study.

  12. Local ammonia storage and ammonia inhibition in a monolithic copper-beta zeolite SCR catalyst

    SciTech Connect

    Auvray, Xavier P; Partridge Jr, William P; Choi, Jae-Soon; Pihl, Josh A; Yezerets, Alex; Kamasamudram, Krishna; Currier, Neal; Olsson, Louise

    2012-01-01

    Selective catalytic reduction of NO with NH{sub 3} was studied on a Cu-beta zeolite catalyst, with specific focus on the distributed NH{sub 3} capacity utilization and inhibition. In addition, several other relevant catalyst parameter distributions were quantified including the SCR zone, or catalyst region where SCR occurs, and NO and NH{sub 3} oxidation. We show that the full NH{sub 3} capacity (100% coverage) is used within the SCR zone for a range of temperatures. By corollary, unused NH{sub 3} capacity exists downstream of the SCR zone. Consequently, the unused capacity relative to the total capacity is indicative of the portion of the catalyst unused for SCR. Dynamic NH{sub 3} inhibition distributions, which create local transient conversion inflections, are measured. Dynamic inhibition is observed where the gas phase NH{sub 3} and NO concentrations are high, driving rapid NH{sub 3} coverage buildup and SCR. Accordingly, we observe dynamic inhibition at low temperatures and in hydrothermally aged states, but predict its existence very near the catalyst front in higher conversion conditions where we did not specifically monitor its impact. While this paper addresses some general distributed SCR performance parameters including Oxidation and SCR zone, our major new contributions are associated with the NH{sub 3} capacity saturation within the SCR zone and dynamic inhibition distributions and the associated observations. These new insights are relevant to developing accurate models, designs and control strategies for automotive SCR catalyst applications.

  13. Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II).

    PubMed

    Zhan, Yanhui; Lin, Jianwei; Li, Jia

    2013-04-01

    A novel composite material, i.e., surfactant-modified hydroxyapatite/zeolite composite, was used as an adsorbent to remove humic acid (HA) and copper(II) from aqueous solution. Hydroxyapatite/zeolite composite (HZC) and surfactant-modified HZC (SMHZC) were prepared and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscope. The adsorption of HA and copper(II) on SMHZC was investigated. For comparison purposes, HA adsorption onto HZC was also investigated. SMHZC exhibited much higher HA adsorption capacity than HZC. The HA adsorption capacity for SMHZC decreased slightly with increasing pH from 3 to 8 but decreased significantly with increasing pH from 8 to 12. The copper(II) adsorption capacity for SMHZC increased with increasing pH from 3 to 6.5. The adsorption kinetic data of HA and copper(II) on SMHZC obeyed a pseudo-second-order kinetic model. The adsorption of HA and copper(II) on SMHZC took place in three different stages: fast external surface adsorption, gradual adsorption controlled by both film and intra-particle diffusions, and final equilibrium stage. The equilibrium adsorption data of HA on SMHZC better fitted to the Langmuir isotherm model than the Freundlich isotherm model. The equilibrium adsorption data of copper(II) on SMHZC could be described by the Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. The presence of copper(II) in solution enhanced HA adsorption onto SMHZC. The presence of HA in solution enhanced copper(II) adsorption onto SMHZC. The mechanisms for the adsorption of HA on SMHZC at pH 7 may include electrostatic attraction, organic partitioning, hydrogen bonding, and Lewis acid-base interaction. The mechanisms for the adsorption of copper(II) on SMHZC at pH 6 may include surface complexation, ion exchange, and dissolution-precipitation. The obtained results indicate that SMHZC can be used as an effective adsorbent to simultaneously remove HA and

  14. Localized corrosion effects and modifications of acidic and alkaline slurries on copper chemical mechanical polishing

    NASA Astrophysics Data System (ADS)

    Tsai, Tzu-Hsuan; Yen, Shi-Chern

    2003-04-01

    This study demonstrates the CMP performance can be enhanced by modifying the corrosion effects of acidic and alkaline slurries on copper. A corrosion test-cell with a polishing platform is connected with the potentiostat to investigate the corrosion behaviors of copper CMP in various alumina slurries. Experiments show that the slurry needs to be maintained in acidic pH<4.56 or alkaline pH>9.05 surroundings and thus better dispersion of alumina particles and less residual contaminant on copper surface can be obtained. The surface defects after copper CMP using acidic and alkaline slurries are described by pitting corrosion mechanisms, and these mechanisms can be regarded as a basis to modify their corrosion effects. Experimental results indicate that it is necessary to modify the dissolution of HNO 3 and oxidization of NH 4OH for copper CMP slurries. Consequently, the slurries of 5 wt.% HNO 3 by adding 0.1 wt.% BTA or 5 wt.% KNO 3 by adding 1 wt.% NH 4OH achieve good CMP performance for copper with higher CMP efficiency factor (CMPEF), 1460 and 486, and lower surface roughness ( Rq), 4.019 and 3.971 nm, respectively. It is found that AFM micrographs can support the effectiveness of corrosion modifications for copper CMP in various slurry chemistries.

  15. Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

    PubMed

    Gan, Patrick; Foord, John S; Compton, Richard G

    2015-10-01

    Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

  16. Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

    PubMed Central

    Gan, Patrick; Foord, John S; Compton, Richard G

    2015-01-01

    Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

  17. Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

    PubMed

    Gan, Patrick; Foord, John S; Compton, Richard G

    2015-10-01

    Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

  18. Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3.

    PubMed

    Ren, Limin; Zhu, Longfeng; Yang, Chengguang; Chen, Yanmei; Sun, Qi; Zhang, Haiyan; Li, Caijin; Nawaz, Faisal; Meng, Xiangju; Xiao, Feng-Shou

    2011-09-21

    Low-cost copper-amine complex was rationally designed to be a novel template for one-pot synthesis of Cu-SSZ-13 zeolites. Proper confirmation and appropriate size make this complex fit well with CHA cages as an efficient template. The products exhibit superior catalytic performance on NH(3)-SCR reaction. PMID:21625721

  19. Conversion of trypsin to a copper enzyme: tyrosinase/catechol oxidase by chemical modification.

    PubMed

    Okutucu, Burcu; Zeytunluoglu, Ali; Zihnioglu, Figen

    2010-01-01

    New active sites can be introduced into naturally occurring enzymes by the chemical modification of specific amino acid residues in concert with genetic techniques. Chemical strategies have had a significant impact in the field of enzyme design such as modifying the selectivity and catalytic activity which is very different from those of the corresponding native enzymes. Thus, chemical modification has been exploited for the incorporation of active site binding analogs onto protein templates and for atom replacement in order to generate new functionality such as the conversion of a hydrolase into a peroxidase. The introduction of a coordination complex into a substrate binding pocket of trypsin could probably also be extended to various enzymes of significant therapeutic and biotechnological importance. The aim of this study is the conversion of trypsin into a copper enzyme: tyrosinase by chemical modification. Tyrosinase is a biocatalyst (EC.1.14.18.1) containing two atoms of copper per active site with monooxygenase activity. The active site of trypsin (EC 3.4.21.4), a serine protease was chemically modified by copper (Cu(+2)) introduced p-aminobenzamidine (pABA- Cu(+2): guanidine containing schiff base metal chelate) which exhibits affinity for the carboxylate group in the active site as trypsin-like inhibitor. Trypsin and the resultant semisynthetic enzyme preparation was analysed by means of its trypsin and catechol oxidase/tyrosinase activity. After chemical modification, trypsin-pABA-Cu(+2) preparation lost 63% of its trypsin activity and gained tyrosinase/catechol oxidase activity. The kinetic properties (K(cat), K(m), K(cat)/K(m)), optimum pH and temperature of the trypsin-pABA-Cu(+2) complex was also investigated. PMID:20024799

  20. High-adhesion Cu patterns fabricated by nanosecond laser modification and electroless copper plating

    NASA Astrophysics Data System (ADS)

    Lv, Ming; Liu, Jianguo; Zeng, Xiaoyan; Du, Qifeng; Ai, Jun

    2015-10-01

    Adhesion strength is a crucial factor for the performance and reliability of metallic patterns on insulator substrates. In this study, we present an efficient technique for selective metallization of alumina ceramic with high adhesion strength by using nanosecond laser modification and electroless copper plating. Specifically, a 355 nm Nd:YVO4 ultraviolet (UV) laser was employed not only to decompose palladium chloride film locally for catalyzing the electroless reaction, but also to modify the ceramic surface directly using its high fluence. An orthogonal experiment was undertaken to study the effects of processing parameters including laser fluence, scanning speed and scanning line interval on adhesion strength. The adhesion strength was measured by pulling a metallic wire soldered into the copper coating perpendicular to the substrate using a pull tester. The results have shown that a strong adhesion between the copper coating and the alumina ceramic, higher than the tensile strength of tin-lead solder was obtained. Surface and interface characteristics were investigated to understand that, whose results have shown that the high-aspect-ratio microstructures formed by the laser modification is the major reason for the improvement of adhesion.

  1. Production of oxidized lipids during modification of low-density lipoprotein by macrophages or copper.

    PubMed Central

    Carpenter, K L; Wilkins, G M; Fussell, B; Ballantine, J A; Taylor, S E; Mitchinson, M J; Leake, D S

    1994-01-01

    The oxidation of low-density lipoprotein (LDL) is implicated in atherosclerosis. Lipids and oxidized lipids were analysed by gas chromatography and gas chromatography-mass spectrometry in human LDL incubated with mouse peritoneal macrophages (MPM) or copper (II) sulphate in Ham's F-10 medium or medium alone (control). MPM-modification and copper-catalysed oxidation of LDL resulted in the formation of oxysterols, mainly cholest-5-en-3 beta,7 beta-diol (7 beta-OH-CHOL); 7%-19% of the initial cholesterol was converted to 7 beta-OH-CHOL in 24 h. 7 beta-OH-CHOL levels in control LDL were very low. The increase in 7 beta-OH-CHOL in MPM and copper-oxidized LDL was accompanied by decreases in linoleate and arachidonate and increases in the electrophoretic mobility and degradation of LDL protein by 'target' macrophages. The concerted occurrence of these processes and their similarity in both MPM-modification and copper-catalysed oxidation of LDL were suggested by the highly significant cross-correlations. The fall in polyunsaturated fatty acid (PUFA) was accompanied by a directly proportional increase in electrophoretic mobility of the LDL. Production of 7 beta-OH-CHOL and protein degradation by macrophages showed modest elevations during the initial steep fall in PUFA, and showed their greatest increases as the levels of PUFA slowly approached zero. The levels of 7 beta-OH-CHOL and the degradation of LDL by macrophages were directly proportional. The degradation of LDL by macrophages increased rapidly as the electrophoretic mobility of LDL was slowly approaching its maximum level. PMID:7999000

  2. Spin-resolved NOCV analysis of the zeolite framework influence on the interaction of NO with Cu(I/II) sites in zeolites.

    PubMed

    Kozyra, Paweł; Piskorz, Witold

    2015-05-28

    In the present work the function of a zeolite framework in modifying the properties of copper sites has been studied. The [Al(OH)4CuNO](0/+) systems were studied by applying the analysis of the electron density flows - contributions to deformation density between two interacting fragments. The systems were divided in the following partition scheme: the first fragment, [Al(OH)4](-) (tagged T1), and the second one, [CuNO](+/2+). The analysis allowed us to elucidate the function of the zeolite fragment in modification of the cation properties towards activating the NO molecule. For both [(T1)CuNO](0/+) systems several channels showing the role of the zeolite framework have been identified. The geometry of the adducts influences either the efficiency of the channels or spin polarization. The two most important channels, zeolites-cations, influence the flow of electrons between the copper site and the antibonding NO orbitals. One channel favors the π-backdonation in the plane perpendicular to the Cu-N-O plane while the other contribution influences the π-backdonation in the C-N-O plane. The first one is found only in the system with copper(I) and it is essential for facilitating the π-backdonation and activating the NO molecule. The second channel is spin sensitive for both copper(I) and copper(II) sites. In the case of the system with copper(i) the second channel favors the π-backdonation while in the system containing copper(ii) the direction of these flows is opposite for α and β electrons.

  3. Zealous zeolites

    SciTech Connect

    Hairston, D.W.

    1996-07-01

    Zeolites have made significant inroads in fluid cracking catalysts for gasoline and have pushed phosphates out of laundry detergents. But these crystalline aluminosilicate structures are just beginning to make their mark in chemical processes and environmental applications. Ideally suited for work as molecular sieves and catalysts, zeolites sport uniform surface pores and channels that are receptive only to molecules of a specific size and shape. This high selectivity makes zeolites a good alterative to some of the conventional products used for chemical reaction and filtration. One of the most potentially lucrative markets for zeolites is chemical catalyst replacements for liquid acids, such as hydrofluoric acid and sulfuric acid, and aluminum chloride in a number of alkylation and acrylation reactions. Zeolites are also being considered for oligomerization,isomerization, amination and condensation processes for the manufacture of chemical intermediates. The paper discusses the market and manufacturers of zeolites, justifying the cost of converting to zeolite catalysts, and natural zeolites.

  4. Copper(I)-Y Zeolite-Catalyzed Regio- and Stereoselective [2 + 2 + 2] Cyclotrimerization Cascade: An Atom- and Step-Economical Synthesis of Pyrimido[1,6-a]quinoline.

    PubMed

    Ramanathan, Devenderan; Pitchumani, Kasi

    2015-10-16

    An elegant copper(I)-Y zeolite-catalyzed tandem process, involving ketenimine-based termolecular [2 + 2 + 2]/[NC + CC + NC] cycloaddition, using sulfonyl azide, alkyne, and quinoline, to prepare pyrimido[1,6-a]quinolines is reported. In this straightforward, highly atom- and step-economical protocol, copper(I) promotes for azide-alkyne [3 + 2] cycloaddition which is followed by ring-rearrangement/ketenimine formation/regio- and stereoselective [2 + 2 + 2] termolecular cycloaddition and dehydrogenation cascade to yield selectively the E-isomer of pyrimido[1,6-a]quinoline. PMID:26390020

  5. On the enantioselectivity of aziridination of styrene catalysed by copper triflate and copper-exchanged zeolite Y: consequences of the phase behaviour of enantiomeric mixtures of N-arene-sulfonyl-2-phenylaziridines.

    PubMed

    Jeffs, Laura; Arquier, Damien; Kariuki, Benson; Bethell, Donald; Page, Philip C Bulman; Hutchings, Graham J

    2011-02-21

    By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), catalysed by copper(II) triflate in CH(3)CN solution or heterogeneously by CuHY, has predominantly an R-configuration. The enantioselectivity of the aziridination of styrene by [N-arenesulfonylimino]-phenyliodinanes catalysed by copper-exchanged zeolite Y (CuHY), in conjunction with a chiral bis-oxazoline ligand, has been re-examined. In the case of PhINNs, it is shown that the product mixture of enantiomeric aziridines, on treatment with hexane, gives rise to a solid phase of low enantiomeric excess (ee) and a solution phase of high ee. Separation of the solid phase and recrystallisation afforded a true racemate (racemic compound), which has been confirmed by X-ray crystallography. The aziridine obtained from the solution phase could be recrystallised to produce the pure enantiomer originally in excess. A consequence of the new findings is that previous reports on the enantioselectivity of copper-catalysed aziridination, both in heterogeneous and homogeneous conditions, should be regarded with caution if the analytical procedure involved HPLC with injection of the enantiomeric mixture in a hexane-rich solvent. Such a method has been used in previous work from this laboratory, but has also been used elsewhere, following the procedure developed by Evans and co-workers when the (homogeneous) copper-catalysed aziridination by PhINTs was first discovered. Evidently, the change of substituent in the benzenesulfonyl group reduces the solubility in hexane, affording a solution phase of enhanced ee. PMID:21186395

  6. Tailored zeolites for the removal of metal oxyanions: overcoming intrinsic limitations of zeolites.

    PubMed

    Figueiredo, Hugo; Quintelas, Cristina

    2014-06-15

    This review aims to present a global view of the efforts conducted to convert zeolites into efficient supports for the removal of heavy metal oxyanions. Despite lacking affinity for these species, due to inherent charge repulsion between zeolite framework and anionic species, zeolites have still received considerable attention from the scientific community, since their versatility allowed tailoring them to answer specific requirements. Different processes for the removal and recovery of toxic metals based on zeolites have been presented. These processes resort to modification of the zeolite surface to allow direct adsorption of oxyanions, or by combination with reducing agents for oxyanions that allow ion-exchange with the converted species by the zeolite itself. In order to testify zeolite versatility, as well as covering the wide array of physicochemical constraints that oxyanions offer, chromium and arsenic oxyanions were selected as model compounds for a review of treatment/remediation strategies, based on zeolite modification.

  7. Position-dependent performance of copper phthalocyanine based field-effect transistors by gold nanoparticles modification.

    PubMed

    Luo, Xiao; Li, Yao; Lv, Wenli; Zhao, Feiyu; Sun, Lei; Peng, Yingquan; Wen, Zhanwei; Zhong, Junkang; Zhang, Jianping

    2015-01-21

    A facile fabrication and characteristics of copper phthalocyanine (CuPc)-based organic field-effect transistor (OFET) using the gold nanoparticles (Au NPs) modification is reported, thereby achieving highly improved performance. The effect of Au NPs located at three different positions, that is, at the SiO2/CuPc interface (device B), embedding in the middle of CuPc layer (device C), and on the top of CuPc layer (device D), is investigated, and the results show that device D has the best performance. Compared with the device without Au NPs (reference device A), device D displays an improvement of field-effect mobility (μ(sat)) from 1.65 × 10(-3) to 5.51 × 10(-3) cm(2) V(-1) s(-1), and threshold voltage decreases from -23.24 to -16.12 V. Therefore, a strategy for the performance improvement of the CuPc-based OFET with large field-effect mobility and saturation drain current is developed, on the basis of the concept of nanoscale Au modification. The model of an additional electron transport channel formation by FET operation at the Au NPs/CuPc interface is therefore proposed to explain the observed performance improvement. Optimum CuPc thickness is confirmed to be about 50 nm in the present study. The device-to-device uniformity and time stability are discussed for future application.

  8. Position-dependent performance of copper phthalocyanine based field-effect transistors by gold nanoparticles modification.

    PubMed

    Luo, Xiao; Li, Yao; Lv, Wenli; Zhao, Feiyu; Sun, Lei; Peng, Yingquan; Wen, Zhanwei; Zhong, Junkang; Zhang, Jianping

    2015-01-21

    A facile fabrication and characteristics of copper phthalocyanine (CuPc)-based organic field-effect transistor (OFET) using the gold nanoparticles (Au NPs) modification is reported, thereby achieving highly improved performance. The effect of Au NPs located at three different positions, that is, at the SiO2/CuPc interface (device B), embedding in the middle of CuPc layer (device C), and on the top of CuPc layer (device D), is investigated, and the results show that device D has the best performance. Compared with the device without Au NPs (reference device A), device D displays an improvement of field-effect mobility (μ(sat)) from 1.65 × 10(-3) to 5.51 × 10(-3) cm(2) V(-1) s(-1), and threshold voltage decreases from -23.24 to -16.12 V. Therefore, a strategy for the performance improvement of the CuPc-based OFET with large field-effect mobility and saturation drain current is developed, on the basis of the concept of nanoscale Au modification. The model of an additional electron transport channel formation by FET operation at the Au NPs/CuPc interface is therefore proposed to explain the observed performance improvement. Optimum CuPc thickness is confirmed to be about 50 nm in the present study. The device-to-device uniformity and time stability are discussed for future application. PMID:25548878

  9. Sorption Kinetics Of Selected Heavy Metals Adsorption To Natural And Fe(III) Modified Zeolite Tuff Containing Clinoptilolite Mineral

    NASA Astrophysics Data System (ADS)

    Sirotiak, Maroš; Lipovský, Marek; Bartošová, Alica

    2015-06-01

    In the research described in this paper, studied was sorption capacity of natural and ferric modification of zeolite tuff containing mineral clinoptilolite from the Nižný Hrabovec deposit to remove potentially toxic metals (ionic forms of chromium, nickel, copper and aluminium) from their water solutions. We reported that the Fe (III) zeolite has an enhanced ability to sorption of Cu (II), and a slight improvement occurs in the case of Cr (VI) and Ni (II). On the other hand, the deterioration was observed in the case of Al (III) adsorption.

  10. A novel cysteine sensor based on modification of carbon paste electrode by Fe(II)-exchanged zeolite X nanoparticles.

    PubMed

    Hashemi, Habibeh-Sadat; Nezamzadeh-Ejhieh, Alireza; Karimi-Shamsabadi, Maryam

    2016-01-01

    An electrochemical sensor based on carbon paste electrode (CPE) modified with iron(II) doped into a synthesized nano-particles of zeolite X (Fe(II)-NX/ZCME) was constructed, which is highly sensitive for detection of cysteine (Cys). The modified electrode showed an excellent electro-activity for oxidation of Cys in phosphate buffer at pH7.4. It has been found that anodic peak potential of Cys oxidation, compared with the unmodified CPE (UCPE), was shifted towards negative values at the surface of the modified electrode under the optimum condition. The peak current increased linearly with the Cys concentration in the wide range of 5.0 × 10(-9)-3.0 × 10(-3) mol L(-1). The very low detection limit was obtained to be 1.5 × 10(-10) mol L(-1). Finally, the modified electrode was used as a selective, simple and precise new electrochemical sensor for the determination of Cys in the real samples, such as pharmaceutical and biological fluids.

  11. Can Dynamics Be Responsible for the Complex Multipeak Infrared Spectra of NO Adsorbed to Copper(II) Sites in Zeolites?

    PubMed

    Göltl, Florian; Sautet, Philippe; Hermans, Ive

    2015-06-26

    Copper-exchanged SSZ-13 is a very efficient material in the selective catalytic reduction of NO(x) using ammonia (deNO(x)-SCR) and characterizing the underlying distribution of copper sites in the material is of prime importance to understand its activity. The IR spectrum of NO adsorbed to divalent copper sites are modeled using ab initio molecular dynamics simulations. For most sites, complex multi-peak spectra induced by the thermal motion of the cation as well as the adsorbate are found. A finite temperature spectrum for a specific catalyst was constructed, which shows excellent agreement with previously reported data. Additionally these findings allow active and inactive species in deNO(x)-SCR to be identified. To the best of our knowledge, this is the first time such complex spectra for single molecules adsorbed to single active centers have been reported in heterogeneous catalysis, and we expect similar effects to be important in a large number of systems with mobile active centers. PMID:25966680

  12. Determining copper and lead binding in Larrea tridentata through chemical modification and X-ray absorption spectroscopy

    SciTech Connect

    Polette, L.; Gardea-Torresdey, J.L.; Chianelli, R.; Pickering, I.J.; George, G.N.

    1997-12-31

    Metal contamination in soils has become a widespread problem. Emerging technologies, such as phytoremediation, may offer low cost cleanup methods. The authors have identified a desert plant, Larrea tridentata (creosote bush), which naturally grows and uptakes copper and lead from a contaminated area near a smelting operation. They determined, through chemical modification of carboxyl groups with methanol, that these functional groups may be responsible for a portion of copper(II) binding. In contrast, lead binding was minimally affected by modification of carboxyl groups. X-ray absorption spectroscopy studies conducted at Stanford Synchrotron Radiation Laboratory (SSRL) further support copper binding to oxygen-coordinated ligands and also imply that the binding is not solely due to phytochelatins. The EXAFS data indicate the presence of both Cu-O and Cu-S back scatters, no short Cu-Cu interactions, but with significant Cu-Cu back scattering at 3.7 {angstrom} (unlike phytochelatins with predominantly Cu-S coordination and short Cu-Cu interactions at 2.7 {angstrom}). Cu EXAFS of roots and leaves also vary depending on the level of heavy metal contamination in the environment from which the various creosote samples were obtained. In contrast, Pb XANES data of roots and leaves of creosote collected from different contaminated sites indicate no difference in valence states or ligand coordination.

  13. The antibrowning agent sulfite inactivates Agaricus bisporus tyrosinase through covalent modification of the copper-B site.

    PubMed

    Kuijpers, Tomas F M; Gruppen, Harry; Sforza, Stefano; van Berkel, Willem J H; Vincken, Jean-Paul

    2013-12-01

    Sulfite salts are widely used as antibrowning agents in food processing. Nevertheless, the exact mechanism by which sulfite prevents enzymatic browning has remained unknown. Here, we show that sodium hydrogen sulfite (NaHSO3) irreversibly blocks the active site of tyrosinase from the edible mushroom Agaricus bisporus, and that the competitive inhibitors tropolone and kojic acid protect the enzyme from NaHSO3 inactivation. LC-MS analysis of pepsin digests of NaHSO3 -treated tyrosinase revealed two peptides showing a neutral loss corresponding to the mass of SO3 upon MS(2) fragmentation. These peptides were found to be homologous peptides containing two of the three histidine residues that form the copper-B-binding site of mushroom tyrosinase isoform PPO3 and mushroom tyrosinase isoform PPO4, which were both present in the tyrosinase preparation used. Peptides showing this neutral loss behavior were not found in the untreated control. Comparison of the effects of NaHSO3 on apo-tyrosinase and holo-tyrosinase indicated that inactivation is facilitated by the active site copper ions. These data provide compelling evidence that inactivation of mushroom tyrosinase by NaHSO3 occurs through covalent modification of a single amino-acid residue, probably via addition of HSO3(-) to one of the copper-coordinating histidines in the copper-B site of the enzyme.

  14. The antibrowning agent sulfite inactivates Agaricus bisporus tyrosinase through covalent modification of the copper-B site.

    PubMed

    Kuijpers, Tomas F M; Gruppen, Harry; Sforza, Stefano; van Berkel, Willem J H; Vincken, Jean-Paul

    2013-12-01

    Sulfite salts are widely used as antibrowning agents in food processing. Nevertheless, the exact mechanism by which sulfite prevents enzymatic browning has remained unknown. Here, we show that sodium hydrogen sulfite (NaHSO3) irreversibly blocks the active site of tyrosinase from the edible mushroom Agaricus bisporus, and that the competitive inhibitors tropolone and kojic acid protect the enzyme from NaHSO3 inactivation. LC-MS analysis of pepsin digests of NaHSO3 -treated tyrosinase revealed two peptides showing a neutral loss corresponding to the mass of SO3 upon MS(2) fragmentation. These peptides were found to be homologous peptides containing two of the three histidine residues that form the copper-B-binding site of mushroom tyrosinase isoform PPO3 and mushroom tyrosinase isoform PPO4, which were both present in the tyrosinase preparation used. Peptides showing this neutral loss behavior were not found in the untreated control. Comparison of the effects of NaHSO3 on apo-tyrosinase and holo-tyrosinase indicated that inactivation is facilitated by the active site copper ions. These data provide compelling evidence that inactivation of mushroom tyrosinase by NaHSO3 occurs through covalent modification of a single amino-acid residue, probably via addition of HSO3(-) to one of the copper-coordinating histidines in the copper-B site of the enzyme. PMID:24112416

  15. Inactivation of high and low pathogenic avian influenza virus H5 subtypes by copper ions incorporated in zeolite-textile materials.

    PubMed

    Imai, Kunitoshi; Ogawa, Haruko; Bui, Vuong Nghia; Inoue, Hiroshi; Fukuda, Jiro; Ohba, Masayoshi; Yamamoto, Yu; Nakamura, Kikuyasu

    2012-02-01

    The effect of cotton textiles containing Cu(2+) held by zeolites (CuZeo-textile) on the inactivation of H5 subtype viruses was examined. Allantoic fluid (AF) containing a virus (AF virus) (0.1 ml) was applied to the textile (3×3-cm), and incubated for a specific period at ambient temperature. After each incubation, 0.9 ml of culture medium was added followed by squeezing to recover the virus into the medium. The recovered virus was titrated using Madin-Darby canine kidney (MDCK) cells or 10-day-old embryonated chicken eggs. The highly pathogenic H5N1 and the low pathogenic H5N3 viruses were inactivated on the CuZeo-textile, even after short incubation. The titer of A/chicken/Yamaguchi/7/04 (H5N1) in MDCK cells and in eggs declined by >5.0 log(10) and 5.0 log(10), respectively, in 30 s. The titer of A/whooper swan/Hokkaido/1/08 (H5N1) in MDCK cells declined by 2.3 and 3.5 in 1 and 5 min, respectively. When A/whistling swan/Shimane/499/83 (H5N3) was treated on the CuZeo-textile for 10 min, the titer declined by >5.0 log(10) in MDCK cells and by >3.5 log(10) in eggs. In contrast, no decrease in the titers was observed on cotton textiles containing zeolites alone (Zeo-textile). Neither cytopathic effects nor NP antigens were detected in MDCK cells inoculated with the H5N1 virus treated on the CuZeo-textile. The viral genes (H5, N1, M, and NP) were amplified from the virus treated on the CuZeo-textile by RT-PCR. The hemagglutinating activity of the CuZeo-textile treated virus was unaffected, indicating that virus-receptor interactions were maintained. Electron microscopic analysis revealed a small number of particles with morphological abnormalities in the H5N3 virus samples recovered immediately from the CuZeo-textile, while no particles were detectable in the 10-min treated sample, suggesting the rapid destruction of virions by the Cu(2+) in the CuZeo-textile. The loss of infectivity of H5 viruses could, therefore, be due to the destruction of virions by Cu(2

  16. Modification of soil microbial activity and several hydrolases in a forest soil artificially contaminated with copper

    NASA Astrophysics Data System (ADS)

    Bellas, Rosa; Leirós, Mā Carmen; Gil-Sotres, Fernando; Trasar-Cepeda, Carmen

    2010-05-01

    Soils have long been exposed to the adverse effects of human activities, which negatively affect soil biological activity. As a result of their functions and ubiquitous presence microorganisms can serve as environmental indicators of soil pollution. Some features of soil microorganisms, such as the microbial biomass size, respiration rate, and enzyme activity are often used as bioindicators of the ecotoxicity of heavy metals. Although copper is essential for microorganisms, excessive concentrations have a negative influence on processes mediated by microorganisms. In this study we measured the response of some microbial indicators to Cu pollution in a forest soil, with the aim of evaluating their potential for predicting Cu contamination. Samples of an Ah horizon from a forest soil under oakwood vegetation (Quercus robur L.) were contaminated in the laboratory with copper added at different doses (0, 120, 360, 1080 and 3240 mg kg-1) as CuCl2×2H2O. The soil samples were kept for 7 days at 25 °C and at a moisture content corresponding to the water holding capacity, and thereafter were analysed for carbon and nitrogen mineralization capacity, microbial biomass C, seed germination and root elongation tests, and for urease, phosphomonoesterase, catalase and ß-glucosidase activities. In addition, carbon mineralization kinetics were studied, by plotting the log of residual C against incubation time, and the metabolic coefficient, qCO2, was estimated. Both organic carbon and nitrogen mineralization were lower in polluted samples, with the greatest decrease observed in the sample contaminated with 1080 mg kg-1. In all samples carbon mineralization followed first order kinetics; the C mineralization constant was lower in contaminated than in uncontaminated samples and, in general, decreased with increasing doses of copper. Moreover, it appears that copper contamination not only reduced the N mineralization capacity, but also modified the N mineralization process, since in

  17. Simultaneous SO{sub 2}/NO{sub x} abatement using zeolite-supported copper. Progress report, April 1--June 30, 1995

    SciTech Connect

    Mitchell, M.B.; White, M.G.

    1995-12-31

    Several catalysts for NO decomposition have been reported in the literature to include the following: Cu/ZSM-5; Cu/Zeolite-Y; Cu/mordenite; Cu/{beta} zeolite; Cu/alumina; and Cu/silica which have been studied less than Cu/ZSM-5. The catalytic properties for NO conversion are found to be different on these samples with the ZSM-5 supported catalysts showing the highest activity in a dry environment free from sulfur oxides. One of the goals of this study is to have a better fundamental understanding on the different roles of Cu and the support in the catalytic reaction. The authors use stable, cationic metal complexes in non-aqueous solvents as sources of the Cu ions in producing model catalysts for which the fate of the source molecule is known and is controlled during the ion exchange/impregnation. Molecular models of these systems can be used to identify the possible configurations of the metal complexes within the zeolite support. The authors compare the performance of the model catalysts to one prepared by aqueous impregnation of ZSM-5 zeolite. The performance of the dinuclear metal complex on silica is compared to the same complex in ZSM-5 and Y-zeolites.

  18. Copper retention, calcium release and ultrastructural evidence indicate specific Cuprolinic Blue uptake and peculiar modifications in mineralizing aortic valves.

    PubMed

    Ortolani, F; Tubaro, F; Petrelli, L; Gandaglia, A; Spina, M; Marchini, M

    2002-01-01

    Previously, reactions with copper phthalocyanines at 0.05 M critical electrolyte concentration were found to cause demineralization in calcifying porcine aortic valves after subdermal implantation in rat, as well as simultaneous visualization of peculiar phthalocyanine-positive layers around cells and cell-derived matrix vesicles. In the present investigation, an appraisal was made of the mechanism and specificity of reactions with Cuprolinic Blue by comparing quantitatively calcium release and copper retention by calcified aortic valves reacted with this phthalocyanine under different critical electrolyte concentration conditions, and the corresponding ultrastructural patterns. It was found that (i) decalcifying properties are inversely proportional to salt molarity; (ii) reactivity to Cuprolinic Blue is critical electrolyte concentration-dependent, since the greatest copper retention occurred in 0.05 M critical electrolyte concentration Cuprolinic Blue-reacted samples, the only ones that also exhibited phthalocyanine-positive layers; (iii) the appearance of phthalocyanine-positive layers depends on Cuprolinic Blue uptake, revealing pericellular clustering of calcium-binding, anionic molecules; and (iv) minor Cuprolinic Blue uptake occurs by residual proteoglycans which still remain in the extracellular matrix after 6-week-long subdermal implantation. The present results indicate that this method is appropriate for the study of mineralized tissues and illustrate peculiar tissue modifications occurring at least in the experimental conditions used here.

  19. Copper

    Integrated Risk Information System (IRIS)

    Copper ; CASRN 7440 - 50 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

  20. Copper(i)-Y zeolite catalyzed N-sulfonylketenimine mediated annulation of hydroxynaphthoquinones: syntheses of naphtho[2,1-b]furan-2,5-diones and benzo[de]chromene-2,6-diones.

    PubMed

    Ramanathan, Devenderan; Namitharan, Kayambu; Pitchumani, Kasi

    2016-06-28

    An efficient one pot synthesis for the construction of novel naphtho[2,1-b]furan-2,5-diones and benzo[de]chromene-2,6-diones using copper(i)-Y zeolite catalyzed reaction of N-sulfonylketenimine with 2-hydroxy-1,4-naphthoquinone and 5-hydroxy-1,4-naphthoquinone followed by the elimination of p-toluenesulfonamide is reported. The intermediate N-sulfonylketenimine, generated by (3+2) cycloaddition/ring-opening reaction/retro-Wolff rearrangement, cascade, and annulation, promotes the reaction involving the inter- and intramolecular nucleophilic addition/dehydration followed by hydrolysis and elimination of p-toluenesulfonamide to afford the target products in good yield. PMID:27305854

  1. Investigation of the possibility of intermediate formation of allyl alcohol in the process of oxidative acetoxylation of propylene on a palladium-copper zeolite catalyst

    SciTech Connect

    Minachev, K.M.; Chizhov, O.S.; Kadentsev, V.I.; Kharlamov, V.V.; Nefedov, O.M.; Rodin, A.N.

    1985-12-10

    The formation of allyl acetate in reactions of oxidative acetoxylation of propylene by labeled acetic acid and esterification of labeled acetic acid by allyl alcohol on a Pd, Cu-zeolite catalyst occur with complete conservation of the labeled oxygen of the original labeled acetic acid in the reaction product. The authors propose a reaction scheme for the oxidative acetoxylation of propylene, providing for the formation of allyl alcohol as an intermediate compound, present in a chemisorbed state in the form of a complex with a Pd atom. The gas-phase oxidative acetoxylation of propylene is an industrial method of producing allyl acetate.

  2. An improved performance of copper phthalocyanine OFETs with channel and source/drain contact modifications

    NASA Astrophysics Data System (ADS)

    Huanqin, Dang; Xiaoming, Wu; Xiaowei, Sun; Runqiu, Zou; Ruochuan, Zhang; Shougen, Yin

    2015-10-01

    We report an effective method to improve the performance of p-type copper phthalocyanine (CuPc) based organic field-effect transistors (OFETs) by employing a thin para-quaterphenyl (p-4p) film and simultaneously applying V2O5 to the source/drain regions. The p-4p layer was inserted between the insulating layer and the active layer, and V2O5 layer was added between CuPc and Al in the source-drain (S/D) area. As a result, the field-effect saturation mobility and on/off current ratio of the optimized device were improved to 5 × 10-2 cm2/(V·s) and 104, respectively. We believe that because p-4p could induce CuPc to form a highly oriented and continuous film, this resulted in the better injection and transport of the carriers. Moreover, by introducing the V2O5 electrode's modified layers, the height of the carrier injection barrier could be effectively tuned and the contact resistance could be reduced. Project supported by the National Natural Science Foundation of China (No. 60676051), the National High Technology Research and Development Program of China (No. 2013A A014201), the Scientific Developing Foundation of Tianjin Education Commission (No. 2011ZD02), the Key Science and Technology Support Program of Tianjin (No. 14ZCZDGX00006), and the Foundation of Key Discipline of Material Physics and Chemistry of Tianjin.

  3. Simultaneous SO{sub 2}/NO{sub x} abatement using zeolite-supported copper. Progress report, October 1, 1993--September 30, 1994

    SciTech Connect

    Mitchell, M.B.; White, M.G.

    1994-12-31

    The goals of this project have evolved from an investigation of ways of preparing Li and Hall`s Cu-ZSM-5 catalyst using new methods to yield a more robust catalyst, into an investigation of modified Cu-ZSM-5 catalysts for the simultaneous reduction of NO and oxidation of SO{sub 2}. This was not a conscious effort or decision on the part of the investigators, but resulted from a natural evolution of the project. The authors have developed a zeolite synthesis and characterization capability in the group and have prepared impregnated test materials for the investigation of different catalyst precursors. They have prepared different vanadium-impregnated aluminas, for evaluation of the impregnation method, and have succeeded in reproducing the results of Li and Hall`s Cu-ZSM-5 catalyst. This report reviews the progress during the first three quarters of the year, and includes progress from the last quarter. Results are discussed for the Raman spectroscopy of precursors; infrared spectroscopy of vanadium-impregnated alumina; zeolite overlayer on cordierite; reactivity of Cu-ZSM-5; and impregnation of vanadyl acetylacetonate on alumina.

  4. Relative importance of calcium and magnesium in hardness-based modification of copper toxicity

    SciTech Connect

    Welsh, P.G.; Lipton, J.; Chapman, G.A.; Podrabsky, T.L.

    2000-06-01

    Because of the relationship between water hardness and the toxicity of many metals, total hardness is used as a model parameter to calculate ambient water quality criteria for copper and other metals. However, the relative contribution of the Ca and Mg components of total hardness as modifiers of metals toxicity is not considered in the water quality criteria. Acute Cu toxicity was measured in rainbow trout (Oncorhynchus mykiss) and chinook salmon (O. tshawytscha) swim-up fry in laboratory waters that were formulated to have similar total hardness and alkalinity but different Ca and Mg concentrations. Experiments were performed at nominal total hardness values of 40 and 90 mg/L (as CaCO{sub 3}). In four paired toxicity tests, acute Cu toxicity was significantly lower, i.e., 96-h LC50s were higher, in laboratory waters containing proportionately more Ca (Ca:Mg molar ratios of 1.5--5.2) than in waters containing less Ca (Ca:Mg molar ratios of 0.2--0.8). the relative increase in the 96-h Cu LC50 at higher Ca concentrations, but similar total hardness concentrations, was between 29 and 86% when the low Ca treatment was similar to American Society for Testing and Materials laboratory water. Failure to account for differences in Ca when matching or adjusting for total hardness thus exerts an important influence on the prediction of metal toxicity. These differences must be addressed in water-effect ratio testing in which paired tests with laboratory and site waters are conducted.

  5. Modification research on in wall of capillary copper tube with Norland optical adhesive 68 in a double stereo PCR microfluidic chip.

    PubMed

    Wu, J; Wang, F J; Wang, C Y; Yu, K X; Ma, Y; Chen, T; Li, Y H; Zheng, Y

    2015-01-01

    In this study, a Norland optical adhesive 68 (NOA68) film, approximately 2.2 μm thick, was manufactured using ultraviolet solidified NOA68 in apparatus manufacturing film on the inwall of a capillary copper pipe, developed in our laboratory. The roughness of the inwall of capillary copper pipe was improved from Ra = 0.766 to 0.204 μm and the contact angle was improved from approximately 96° to 55°, increasing hydrophilicity. Polymerase chain reaction experiments indicated that the ratio of work pressure in the microfluidic chip before modification to that after modification was 2.71/1, indicating that the extension efficiency increased. Our results provide a basis for the construction of a microform chip based on function integration. PMID:26535674

  6. Simultaneous SO{sub 2}/NO{sub x} abatement using zeolite-supported copper. Quarterly progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Mitchell, M.B.; White, M.G.

    1995-12-01

    We have significantly improved on our earlier results with a copper-impregnated alumina, obtaining reproducible results for the impregnation procedure and linear behavior with solution concentration of the precursor. The copper acetylacetonate precursor is adsorbed molecularly onto the alumina surface, with no noticeable decomposition. The adsorbed complex appears to form layers on the alumina surface, similar to results found using the same complex with a silica substrate. The materials start out as light blue powders, and after oxidation are light green. Using infrared spectroscopy, we have examined the in situ adsorption and oxidation of SO{sub 2} on the oxidized sorbent, which is dispersed copper oxide supported on aluminum oxide, and have observed that the initial species formed correspond to aluminum sulfate and aluminum sulfate. The sulfate is formed at temperatures much lower than similar experiments studying SO{sub 2} adsorption on alumina and sodium-doped alumina. As a result of oxidation, the adsorbed sulfur species, which begin as aluminum sulfate and sulfate, are converted to copper sulfate.

  7. Preparation of a Versatile Bifunctional Zeolite for Targeted Imaging Applications

    PubMed Central

    Ndiege, Nicholas; Raidoo, Renugan; Schultz, Michael K.; Larsen, Sarah

    2011-01-01

    Bifunctional zeolite Y was prepared for use in targeted in vivo molecular imaging applications. The strategy involved functionalization of the external surface of zeolite Y with chloropropyltriethoxysilane followed by reaction with sodium azide to form azide-functionalized NaY, which is amenable to copper(1) catalyzed click chemistry. In this study, a model alkyne (4-pentyn-1-ol) was attached to the azide-terminated surface via click chemistry to demonstrate feasibility for attachment of molecular targeting vectors (e.g., peptides, aptamers) to the zeolite surface. The modified particle efficiently incorporates the imaging radioisotope gallium-68 (68Ga) into the pores of the azide-functionalized NaY zeolite to form a stable bifunctional molecular targeting vector. The result is a versatile “clickable” zeolite platform that can be tailored for future in vivo molecular targeting and imaging modalities. PMID:21306141

  8. ZEOLITES: EFFECTIVE WATER PURIFIERS

    EPA Science Inventory

    Zeolites are known for their adsorption, ion exchange and catalytic properties. Various natural zeolites are used as odor and moisture adsorbents and water softeners. Due to their acidic nature, synthetic zeolites are commonly employed as solid acid catalysts in petrochemical ind...

  9. Metal Oxide/Zeolite Combination Absorbs H2S

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1989-01-01

    Mixed copper and molybdenum oxides supported in pores of zeolite found to remove H2S from mixture of gases rich in hydrogen and steam, at temperatures from 256 to 538 degree C. Absorber of H2S needed to clean up gas streams from fuel processors that incorporate high-temperature steam reformers or hydrodesulfurizing units. Zeolites chosen as supporting materials because of their high porosity, rigidity, alumina content, and variety of both composition and form.

  10. Zeolite catalysis: technology

    SciTech Connect

    Heinemann, H.

    1980-07-01

    Zeolites have been used as catalysts in industry since the early nineteen sixties. The great majority of commercial applications employ one of three zeolite types: zeolite Y; Mordenite; ZSM-5. By far the largest use of zeolites is in catalytic cracking, and to a lesser extent in hydrocracking. This paper reviews the rapid development of zeolite catalysis and its application in industries such as: the production of gasoline by catalytic cracking of petroleum; isomerization of C/sub 5/ and C/sub 6/ paraffin hydrocarbons; alkylation of aromatics with olefins; xylene isomerization; and conversion of methanol to gasoline.

  11. Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

    SciTech Connect

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2011-02-01

    Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

  12. Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

    SciTech Connect

    Rolllins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2012-07-24

    Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

  13. Mechanochemical approach for selective deactivation of external surface acidity of ZSM-5 zeolite catalyst.

    PubMed

    Inagaki, Satoshi; Sato, Koki; Hayashi, Shunsuke; Tatami, Junichi; Kubota, Yoshihiro; Wakihara, Toru

    2015-03-01

    The acid sites associated with the external surface of zeolite particles are responsible for undesirable consecutive reactions, such as isomerization, alkylation, and oligomerization, resulting in a lower selectivity to a target product; therefore, the selective modification (deactivation) of the external surface of zeolite particles has been an important issue in zeolite science. Here, a new method for surface deactivation of zeolite catalyst was tested via a mechanochemical approach using powder composer. Postsynthetic mechanochemical treatment of ZSM-5 zeolite causes a selective deactivation of catalytically active sites existing only on the external surface, as a potentially useful catalyst for highly selective production of p-xylene.

  14. Zeolite membranes from kaolin

    SciTech Connect

    Karle, B.G.; Brinker, C.J. |; Phillips, M.L.F.

    1996-07-01

    Zeolite films are sought as components of molecular sieve membranes. Different routes used to prepare zeolite composite membranes include growing zeolite layers from gels on porous supports, depositing oriented zeolites on supports, and dispersing zeolites in polymeric membranes. In most cases, it is very difficult to control and avoid the formation of cracks and/or pinholes. The approach to membrane synthesis is based on hydrothermally converting films of layered aluminosilicates into zeolite films. The authors have demonstrated this concept by preparing zeolite A membranes on alumina supports from kaolin films. The authors have optimized the process parameters not only for desired bulk properties, but also for preparing thin (ca. 5 {micro}m), continuous zeolite A films. Scanning electron microscopy shows highly intergrown zeolite A crystals over most of the surface area of the membrane, but gas permeation experiments indicate existence of mesoporous defects and/or intercrystalline gaps. It has been demonstrated that the thickness of the final zeolite A membrane can be controlled by limiting the amount of precursor kaolin present in the membrane.

  15. A theoretical study of nitric oxide adsorption and dissociation on copper-exchanged zeolites SSZ-13 and SAPO-34: the impact of framework acid-base properties.

    PubMed

    Uzunova, Ellie L; Mikosch, Hans

    2016-04-28

    The adsorption of nitric oxide as dinitrosyls and the deNOx proton-mediated reaction mechanism are assessed using electronic structure methods and transition state theory. Dinitrosyls bind to copper cations either via a N-atom or via an O-atom, with N-binding being more stable. In their ground states, dinitrosyls reach a planar configuration with the metal cation. The two nitric oxide molecules are kept together in O-bonded dinitrosyls by the N-N bond and the adsorption complex obtains a cyclic planar structure, while N-bonded dinitrosyls have out-of-plane conformations with low energy barriers. An asymmetric structure ZCu(ON)(NO) with one N-bonded nitrosyl and the other O-bonded is of the lowest stability. The cyclic hyponitrite ZCu(ON)2 adsorption complex undergoes O-N bond breaking upon protonation of one oxygen atom and this lowers the energy barrier of the first reaction step of nitric oxide dissociation to yield N2O and a hydroxylated copper site ZCu(OH) by 45 kJ mol(-1) for Cu-SAPO-34 and by 46 kJ mol(-1) for Cu-SSZ-13. The more stable N-bonded dinitrosyl ZCu(NO)2 provides less favorable reaction which passes through the asymmetric ZCu(ON)(NO) intermediate structure. Brønsted acid sites facilitate the reversal of one nitrosyl group. The role of proton transfer from a Brønsted acid site to dinitrosyls is not limited to the initial step of facilitating the N-O bond cleavage, but it also contributes to the stabilization of intermediate oxygen species formed at the copper site as hydroxide ZCu(OH) and hydroperoxide, ZCuOOH. Without protonation, the unstable ZCuO intermediate causes structural deformation with strongly lengthened T-O bonds in the framework. The rate determining step is N2O decomposition to N2 and O2, whether starting with a ZCu(NO)2 or a ZCu(ON)2 adsorption complex, and Cu-SSZ-13 has a clear advantage with an energy barrier of 195 kJ mol(-1)vs. 265 kJ mol(-1) for Cu-SAPO-34. In the final step the Brønsted acid site is restored by proton

  16. A theoretical study of nitric oxide adsorption and dissociation on copper-exchanged zeolites SSZ-13 and SAPO-34: the impact of framework acid-base properties.

    PubMed

    Uzunova, Ellie L; Mikosch, Hans

    2016-04-28

    The adsorption of nitric oxide as dinitrosyls and the deNOx proton-mediated reaction mechanism are assessed using electronic structure methods and transition state theory. Dinitrosyls bind to copper cations either via a N-atom or via an O-atom, with N-binding being more stable. In their ground states, dinitrosyls reach a planar configuration with the metal cation. The two nitric oxide molecules are kept together in O-bonded dinitrosyls by the N-N bond and the adsorption complex obtains a cyclic planar structure, while N-bonded dinitrosyls have out-of-plane conformations with low energy barriers. An asymmetric structure ZCu(ON)(NO) with one N-bonded nitrosyl and the other O-bonded is of the lowest stability. The cyclic hyponitrite ZCu(ON)2 adsorption complex undergoes O-N bond breaking upon protonation of one oxygen atom and this lowers the energy barrier of the first reaction step of nitric oxide dissociation to yield N2O and a hydroxylated copper site ZCu(OH) by 45 kJ mol(-1) for Cu-SAPO-34 and by 46 kJ mol(-1) for Cu-SSZ-13. The more stable N-bonded dinitrosyl ZCu(NO)2 provides less favorable reaction which passes through the asymmetric ZCu(ON)(NO) intermediate structure. Brønsted acid sites facilitate the reversal of one nitrosyl group. The role of proton transfer from a Brønsted acid site to dinitrosyls is not limited to the initial step of facilitating the N-O bond cleavage, but it also contributes to the stabilization of intermediate oxygen species formed at the copper site as hydroxide ZCu(OH) and hydroperoxide, ZCuOOH. Without protonation, the unstable ZCuO intermediate causes structural deformation with strongly lengthened T-O bonds in the framework. The rate determining step is N2O decomposition to N2 and O2, whether starting with a ZCu(NO)2 or a ZCu(ON)2 adsorption complex, and Cu-SSZ-13 has a clear advantage with an energy barrier of 195 kJ mol(-1)vs. 265 kJ mol(-1) for Cu-SAPO-34. In the final step the Brønsted acid site is restored by proton

  17. Modifications of laccase activities of copper efflux oxidase, CueO by synergistic mutations in the first and second coordination spheres of the type I copper center.

    PubMed

    Kataoka, Kunishige; Kogi, Hiroki; Tsujimura, Seiya; Sakurai, Takeshi

    2013-02-15

    The redox potential of type I copper in the Escherichia coli multicopper oxidase CueO was shifted in the positive or negative direction as a result of the single, double, and triple mutations in the first and second coordination spheres: the formation of the NH···S(-)(Cys500 ligand) hydrogen bond, the breakdown of the NH(His443 ligand)···O(-)(Asp439) hydrogen bond, and the substitution of the Met510 ligand for the non-coordinating Leu or coordinating Gln. Laccase activities of CueO were maximally enhanced 140-fold by virtue of the synergistic effect of mild mutations at and at around the ligand groups to type I copper.

  18. The removal of heavy metals from aqueous solution using natural Jordanian zeolite

    NASA Astrophysics Data System (ADS)

    Taamneh, Yazan; Sharadqah, Suhail

    2016-02-01

    In this article, the adsorption process of cadmium and copper using natural Jordanian (NJ) zeolite as adsorbent has been experimentally estimated. The samples of NJ zeolite were obtained from Al Mafraq discrete, north east of Jordan. The influence of the bulk concentration (C o), contact time (t) and different adsorbent masses (m) of NJ zeolite on the removal of heavy metal were evaluated. These variables had a considerable function in promoting the sorption process of heavy metal using the NJ zeolite. The initial concentration of heavy metals in the stock solution was extended between 80 and 600 mg/L. The batch adsorption method was employed to investigate the adsorption process. The experimental data were correlated using Freundlich and Langmuir empirical formula. The ability of NJ zeolite to eliminate cadmium and copper was estimated according to Langmuir isotherm empirical formula and found 25.9 and 14.3 mg/g for cadmium and copper, respectively. The kinetics of adsorption of cadmium and copper have been analyzed and correlated by first-order and second-order reaction model. It was noticed that adsorption of cadmium and copper was better correlated with pseudo-second-order kinetic model. The results presented that NJ zeolite is practical adsorbent for removing cadmium and copper ion metal.

  19. Hierarchical zeolites overcome all obstacles: next stop industrial implementation.

    PubMed

    Verboekend, Danny; Mitchell, Sharon; Pérez-Ramírez, Javier

    2013-01-01

    This review emphasizes key recent accomplishments towards the industrial exploitation of hierarchically structured zeolites in catalytic processes. A major milestone comprises the demonstration that affordable post-synthetic modifications enable the transformation of any conventional zeolite into hierarchical analogues with tunable porosity and functionality. Through specific examples, belonging to the transformation of fossil fuel and renewable feedstocks, we quantitatively illustrate the spectacular benefits attained upon application of hierarchical zeolite catalysts due to improved accessibility or modification of the type and distribution of active sites. A crucial step for these exciting lab-designed materials to be implemented in industrial processes is to shape them into technical forms. Accordingly, we studied the synthesis, characterization, and catalytic evaluation of millimeter-sized hierarchical zeolite bodies, enriching the fundamental understanding on scale-up and representing an additional solid step towards the commercial application of these materials.

  20. Nano- and microsized zeolites as a perspective material for potentiometric biosensors creation.

    PubMed

    Soldatkin, Oleksandr O; Shelyakina, Margaryta K; Arkhypova, Valentyna N; Soy, Esin; Kirdeciler, Salih Kaan; Ozansoy Kasap, Berna; Lagarde, Florence; Jaffrezic-Renault, Nicole; Akata Kurç, Burcu; Soldatkin, Alexei P; Dzyadevych, Sergei V

    2015-01-01

    A number of potentiometric biosensors based on coimmobilization of enzymes with different types of zeolite on pH-ion-sensitive field-effect transistor (ISFET) have been developed. Their working characteristics have been determined and compared. It was shown that clinoptilolite and zeolite Beta polymorph A (BEA) are more promising for creating biosensors than zeolite A. Changing the concentration of zeolite BEA in membranes, it is possible to extend the biosensor linear measurement range. The two-layer method of deposition of the enzyme with clinoptilolite was found to provide a significant increase in the biosensor sensitivity to substrates, whereas thermal modification of the zeolite BEA crystals can improve analytical characteristics of potentiometric biosensors for detection of toxic substances. These results show that it is possible to regulate the ISFET characteristics for different enzyme-based biosensors by tailoring the electrode surfaces via different zeolites. This makes zeolites strong candidates for integration into biosensors as ISFET modifiers.

  1. Application of diffuse discharges of atmospheric pressure formed by runaway electrons for modification of copper and stainless steel surface

    SciTech Connect

    Tarasenko, V. F. Shulepov, M. A.; Erofeev, M. V.

    2015-12-15

    The results of studies devoted to the influence of a runaway electron pre-ionized diffuse discharge (REP DD) formed in air and nitrogen at atmospheric pressure on the surface of copper and stainless steel are presented. Nanosecond high-voltage pulses were used to obtain REP DD in different gases at high pressures in a chamber with a flat anode and a cathode possessing a small radius of curvature. This mode of discharge was implemented owing to the generation of runaway electrons and X-rays. The conditions under which the surface of copper and stainless steel was cleaned from carbon and oxidized are described.

  2. Application of diffuse discharges of atmospheric pressure formed by runaway electrons for modification of copper and stainless steel surface

    NASA Astrophysics Data System (ADS)

    Tarasenko, V. F.; Shulepov, M. A.; Erofeev, M. V.

    2015-12-01

    The results of studies devoted to the influence of a runaway electron pre-ionized diffuse discharge (REP DD) formed in air and nitrogen at atmospheric pressure on the surface of copper and stainless steel are presented. Nanosecond high-voltage pulses were used to obtain REP DD in different gases at high pressures in a chamber with a flat anode and a cathode possessing a small radius of curvature. This mode of discharge was implemented owing to the generation of runaway electrons and X-rays. The conditions under which the surface of copper and stainless steel was cleaned from carbon and oxidized are described.

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

    PubMed

    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.

  4. Removal of Ca2+ and Zn2+ from aqueous solutions by zeolites NaP and KP.

    PubMed

    Yusof, Alias Mohd; Malek, Nik Ahmad Nizam Nik; Kamaruzaman, Nurul Asyikin; Adil, Muhammad

    2010-01-01

    Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal). PMID:20232677

  5. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  6. An innovative zinc oxide-coated zeolite adsorbent for removal of humic acid

    EPA Science Inventory

    Zinc oxide (ZnO)-coated zeolite adsorbents were developed by both nitric acid modification and Zn(NO3)2•6H2O functionalization of zeolite. The developed adsorbents were used for the removal of humic acid (HA) from aqueous solutions. The adsorption capacity of the adsorbents at 21...

  7. Zeolites: Exploring Molecular Channels

    SciTech Connect

    Arslan, Ilke; Derewinski, Mirek

    2015-05-22

    Synthetic zeolites contain microscopic channels, sort of like a sponge. They have many uses, such as helping laundry detergent lather, absorbing liquid in kitty litter, and as catalysts to produce fuel. Of the hundreds of types of zeolites, only about 15 are used for catalysis. PNNL catalysis scientists Ilke Arslan and Mirek Derewinksi are studying these zeolites to understand what make them special. By exploring the mystery of these microscopic channels, their fundamental findings will help design better catalysts for applications such as biofuel production.

  8. Diagram of Zeolite Crystals

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP) in Cambridge, MA, a NASA-sponsored Commercial Space Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Depicted here is one of the many here complex geometric shapes which make them highly absorbent. Zeolite experiments have also been conducted aboard the International Space Station

  9. Composite zeolite membranes

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Ashley, Carol S.; Reed, Scott T.

    2002-01-01

    A new class of composite zeolite membranes and synthesis techniques therefor has been invented. These membranes are essentially defect-free, and exhibit large levels of transmembrane flux and of chemical and isotopic selectivity.

  10. Lithium modified zeolite synthesis for conversion of biodiesel-derived glycerol to polyglycerol

    SciTech Connect

    Ayoub, Muhammad; Abdullah, Ahmad Zuhairi; Inayat, Abrar

    2014-10-24

    Basic zeolite has received significant attention in the catalysis community. These zeolites modified with alkaline are the potential replacement for existing zeolite catalysts due to its unique features with added advantages. The present paper covers the preparation of lithium modified zeolite Y (Li-ZeY) and its activity for solvent free conversion of biodiesel-derived glycerol to polyglycerol via etherification process. The modified zeolite was well characterized by X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and Nitrogen Adsorption. The SEM images showed that there was no change in morphology of modified zeolite structure after lithium modification. XRD patterns showed that the structure of zeolite was sustained after lithium modification. The surface properties of parent and modified zeolite was also observed N{sub 2} adsortion-desorption technique and found some changes in surface area and pore size. In addition, the basic strength of prepared materials was measured by Hammet indicators and found that basic strength of Li-ZeY was highly improved. This modified zeolite was found highly thermal stable and active heterogamous basic catalyst for conversion of solvent free glycerol to polyglycerol. This reaction was conducted at different temperatures and 260 °C was found most active temperature for this process for reaction time from 6 to 12 h over this basic catalyst in the absence of solvent.

  11. Regenerative Cu/La zeolite supported desulfurizing sorbents

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E. (Inventor); Sharma, Pramod K. (Inventor)

    1991-01-01

    Efficient, regenerable sorbents for removal of H2S from fluid hydrocarbons such as diesel fuel at moderate condition comprise a porous, high surface area aluminosilicate support, suitably a synthetic zeolite, and most preferably a zeolite having a free lattice opening of at least 6 Angstroms containing from 0.1 to 0.5 moles of copper ions, lanthanum ions or their mixtures. The sorbent removes sulfur from the hydrocarbon fuel in high efficiency and can be repetitively regenerated without loss of activity.

  12. Hydraulic conductivity of compacted zeolites.

    PubMed

    Oren, A Hakan; Ozdamar, Tuğçe

    2013-06-01

    Hydraulic conductivities of compacted zeolites were investigated as a function of compaction water content and zeolite particle size. Initially, the compaction characteristics of zeolites were determined. The compaction test results showed that maximum dry unit weight (γ(dmax)) of fine zeolite was greater than that of granular zeolites. The γ(dmax) of compacted zeolites was between 1.01 and 1.17 Mg m(-3) and optimum water content (w(opt)) was between 38% and 53%. Regardless of zeolite particle size, compacted zeolites had low γ(dmax) and high w(opt) when compared with compacted natural soils. Then, hydraulic conductivity tests were run on compacted zeolites. The hydraulic conductivity values were within the range of 2.0 × 10(-3) cm s(-1) to 1.1 × 10(-7) cm s(-1). Hydraulic conductivity of all compacted zeolites decreased almost 50 times as the water content increased. It is noteworthy that hydraulic conductivity of compacted zeolite was strongly dependent on the zeolite particle size. The hydraulic conductivity decreased almost three orders of magnitude up to 39% fine content; then, it remained almost unchanged beyond 39%. Only one report was found in the literature on the hydraulic conductivity of compacted zeolite, which is in agreement with the findings of this study.

  13. Effect of surface stresses and morphology modification on cupric oxide nanowire growth in the thermal oxidation of copper

    NASA Astrophysics Data System (ADS)

    Mema, Rediola

    Exerting in-plane tensile surface stress or modifying the morphology of the metal surface by forcibly propelling a stream of abrasive material into the surface (sandblasting) enhances nanowire growth by increasing the density of nanowires in the case of tensile stress, and increasing the density and length of nanowires in the case of sandblasting. This improved nanowire growth is attributed to the decreased size of the oxide grains and as a result, the increased number of grain boundaries in the underlying oxide layers, thus resulting in a facilitated outward diffusion of Cu ions for enhanced nanowire growth. These two very simple methods offer easy and inexpensive ways to generate dense, ultra-long CuO nanowires with larger aspect ratios, as well as shed more light on the growth mechanism of nanowires in the thermal oxidation of copper, which has been greatly debated thus far.

  14. Peptide linkers lead to modification of liver metabolism and improved tumor targeting of copper-67-labeled antibody fragments.

    PubMed

    Novak-Hofer, I; Zimmermann, K; Schubiger, P A

    2001-12-01

    In order to determine if tumor/nontarget tissue ratios of 67Cu-labeled antibody fragments can be improved, modifying the DO3A copper chelate with tripeptide linkers was investigated. The peptide-linked chelates 1,4,7,10-tetraazacyclodecane-N,N',N",N"'-tetraacetate (DOTA)-triglycyl-L-p-isothiocyanato-phenylalanine (DOTA-R1-NCS), DOTA-glycyl-phenylalanyl-glycyl-L-p-isothiocyanato-phenylalanine (DOTA-R2-NCS), DOTA-glycyl-prolyl-glycyl-L-p-isothiocyanato-phenylalanine (DOTA-R3-NCS) and DOTA-glycyl-L-p-isothiocyanato-phenylalanine (DOTA-R4-NCS) were synthesized and coupled to F(ab')2 fragments of anti-colon carcinoma mAb35. In vitro, the 67Cu-labeled antibody fragments were fully immunoreactive and stable in human serum. In vivo in nude mice bearing human colon carcinoma xenografts the conjugates R1 and R3 showed improved tumor uptake and lower levels of radioactivity in the liver compared with the other conjugates. Biodistributions of the DOTA-R2-F(ab')2 showed at early time points after injection higher levels of radioactivity in the liver, lower levels of activity persisting in the blood and lower accumulation of activity in the tumor. When liver homogenates were analyzed 30 min post injection by SDS-PAGE or FPLC gel chromatography, it was found that radioactivity was released more slowly from the triglycine (R1)-F(ab')2 than from the immunoconjugates with the R2 or the R4 linker. The main radioactive metabolites were protein bands at 66 kD, 31 kD and low molecular weight fragments. The results show that the rate of cleavage of the copper complex from F(ab')2 fragments in vivo can be influenced by the amino acid sequence close to the complex, with significant consequences on biodistributions.

  15. Study of zeolite influence on analytical characteristics of urea biosensor based on ion-selective field-effect transistors

    PubMed Central

    2014-01-01

    A possibility of the creation of potentiometric biosensor by adsorption of enzyme urease on zeolite was investigated. Several variants of zeolites (nano beta, calcinated nano beta, silicalite, and nano L) were chosen for experiments. The surface of pH-sensitive field-effect transistors was modified with particles of zeolites, and then the enzyme was adsorbed. As a control, we used the method of enzyme immobilization in glutaraldehyde vapour (without zeolites). It was shown that all used zeolites can serve as adsorbents (with different effectiveness). The biosensors obtained by urease adsorption on zeolites were characterized by good analytical parameters (signal reproducibility, linear range, detection limit and the minimal drift factor of a baseline). In this work, it was shown that modification of the surface of pH-sensitive field-effect transistors with zeolites can improve some characteristics of biosensors. PMID:24636423

  16. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M.; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P.

    2014-08-19

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  17. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Furukawa, Hiroyasu; Wang, Bo

    2013-07-09

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  18. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P

    2012-11-20

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  19. Rapid synthesis of beta zeolites

    SciTech Connect

    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.

  20. The removal of bacteria by modified natural zeolites.

    PubMed

    Milán, Z; de Las Pozas, C; Cruz, M; Borja, R; Sánchez, E; Ilangovan, K; Espinosa, Y; Luna, B

    2001-01-01

    The removal effect of natural and modified zeolites containing different heavy metals (Ni2+, Zn2+, Fe3+ and Cu2+) on pure cultures of Escherichia coli and Staphylococcus aureus in a solid medium was evaluated in this work. These experiments were carried out in a continuous mode treating municipal wastewater. Faecal coliform species and Pseudomonas aeruginosa were identified. The rate constants of heavy metal lixiviation were determined using a first order kinetic model. The removal effect of modified natural zeolites in both a solid medium and in continuous mode showed an increased elimination of the bacterial population. The results established a decreasing order of the removal effect as follows: Cu2+ > Fe3+ > Zn2+ > Ni2+. The best performance of columns was obtained for inlet bacterial concentrations below 10(6) cells/100 ml. Most of the identified bacterial species were affected by copper modified zeolites, although Serratia marcescens presented the highest sensitivity and Klebsiella pneumoniae the greatest resistance. PMID:11501306

  1. The removal of bacteria by modified natural zeolites.

    PubMed

    Milán, Z; de Las Pozas, C; Cruz, M; Borja, R; Sánchez, E; Ilangovan, K; Espinosa, Y; Luna, B

    2001-01-01

    The removal effect of natural and modified zeolites containing different heavy metals (Ni2+, Zn2+, Fe3+ and Cu2+) on pure cultures of Escherichia coli and Staphylococcus aureus in a solid medium was evaluated in this work. These experiments were carried out in a continuous mode treating municipal wastewater. Faecal coliform species and Pseudomonas aeruginosa were identified. The rate constants of heavy metal lixiviation were determined using a first order kinetic model. The removal effect of modified natural zeolites in both a solid medium and in continuous mode showed an increased elimination of the bacterial population. The results established a decreasing order of the removal effect as follows: Cu2+ > Fe3+ > Zn2+ > Ni2+. The best performance of columns was obtained for inlet bacterial concentrations below 10(6) cells/100 ml. Most of the identified bacterial species were affected by copper modified zeolites, although Serratia marcescens presented the highest sensitivity and Klebsiella pneumoniae the greatest resistance.

  2. An innovative zinc oxide-coated zeolite adsorbent for removal of humic acid.

    PubMed

    Wang, Lingling; Han, Changseok; Nadagouda, Mallikarjuna N; Dionysiou, Dionysios D

    2016-08-01

    Zinc oxide (ZnO)-coated zeolite adsorbents were developed by both nitric acid modification and Zn(NO3)2·6H2O functionalization of zeolite 4A. The developed adsorbents were used for the removal of humic acid (HA) from aqueous solutions. The synthesized materials were characterized by porosimetry analysis, scanning electron microscopy, X-Ray diffraction analysis, and high resolution transmission electron microscopy. The maximum adsorption capacity of the adsorbents at 21±1°C was about 60mgCg(-1). The results showed that the positive charge density of ZnO-coated zeolite adsorbents was proportional to the amount of ZnO coated on zeolite and thus, ZnO-coated zeolite adsorbents exhibited a greater affinity for negatively charged ions. Furthermore, the adsorption capacity of ZnO-coated zeolite adsorbents increased markedly after acid modification. Adsorption experiments demonstrated ZnO-coated zeolite adsorbents possessed high adsorption capacity to remove HA from aqueous solutions mainly due to strong electrostatic interactions between negative functional groups of HA and the positive charges of ZnO-coated zeolite adsorbents.

  3. Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

    PubMed

    Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

    2007-03-01

    Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1. PMID:17021877

  4. Modification of algae with zinc, copper and silver ions for usage as natural composite for antibacterial applications.

    PubMed

    Mahltig, B; Soltmann, U; Haase, H

    2013-03-01

    Nanometer sized metal particles are used in many applications as antimicrobial materials. However in public discussion nanoparticular materials are a matter of concern due to potential health risks. Hence there is a certain demand for alternative antimicrobial acting materials. For this, the aim of this work is to realize an antimicrobial active material based on the release of metal ions from a natural depot. By this, the use of elemental metal particles or metal oxide particles in nanometer or micrometer scale is avoided. As natural depot four different algae materials (gained from Ascophyllum nodosum, Fucus vesicolosus, Spirulina platensis and Nannochloropsis) are used and loaded by bioabsorption with metal ions Ag(+), Cu(2+) and Zn(2+). The amount of metal bound by biosorption differs strongly in the range of 0.8 to 5.4 mg/g and depends on type of investigated algae material and type of metal ion. For most samples a smaller release of biosorbed Ag(+) and Cu(2+) is observed compared to a strong release of Zn(2+). The antibacterial activity of the prepared composites is investigated with Escherichia coli. Algae material without biosorbed metal has only a small effect on E. coli. Also by modification of algae with Zn(2+) only a small antibacterial property can be observed. Only with biosorption of Ag(+), the algae materials gain a strong bactericidal effect, even in case of a small amount of released silver ions. These silver modified algae materials can be used as highly effective bactericidal composites which may be used in future applications for the production of antimicrobial textiles, papers or polymer materials. PMID:25427514

  5. X-ray photoelectron spectroscopy and x-ray absorption near edge structure study of copper sites hosted at the internal surface of ZSM-5 zeolite: A comparison with quantitative and energetic data on the CO and NH3 adsorption

    NASA Astrophysics Data System (ADS)

    Bolis, V.; Maggiorini, S.; Meda, L.; D'Acapito, F.; Palomino, G. Turnes; Bordiga, S.; Lamberti, C.

    2000-11-01

    The oxidation state of Cu species dispersed in a Cu-ZSM-5 zeolite obtained by a nonconventional gas-phase CuCl exchange, and nominally containing only Cu(I) species, was studied by x-ray photoelectron spectroscopy (XPS) and x-ray absorption near edge structure (XANES) analyses. The oxidation of Cu(I) species to Cu(II) by simple exposure to the atmosphere and subsequent reduction by thermal activation in vacuo was monitored. The quantitative and energetic aspects of the formation of carbonyl-like and amino-complexes at the metallic sites was studied by means of adsorption microcalorimetry. CO and NH3 were used as probe molecules in order to assess the coordinative unsaturation of the Cu(I) cations. Adsorption heats comprised in the 130-40 kJ mol-1 interval were obtained for the formation of both type of complexes. The perturbation induced on the Cu centers and/or on the zeolite matrix by the adsorption of the probe molecules was monitored by parallel experiments of XPS, IR, and XANES. A significant fraction of CO and NH3 molecules are irreversibly held on Cu(I) sites even after outgassing at room temperature (RT) at a final dynamic vacuum of 10-5 Torr. On the contrary, no evidence of Cu(I)/CO or of Cu(I)/NH3 complexes was observed by XPS, indicating that such adducts are totally destroyed upon outgassing at 10-9 Torr. This fact implies a reconsideration of what was previously considered as a "stable adduct." XPS allowed to reveal the existence of ammonia adsorbed on defective Al(III) species, and to explain the chemical nature of species formed at the earliest stages of NH3 dosage and characterized by a heat of adsorption as high as 180 kJ mol-1. By comparing the quantitative XPS and volumetric-calorimetric data it was inferred that a significant gradient of defects amount is present in the system. Finally, from the whole set of XPS measurements here reported and from parallel blank experiments on the ZSM-5 zeolite before Cu-exchange, a calibration scale for the N(1

  6. Zeolite crystal growth in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Thompson, Robert W.; Dixon, Anthony G.

    1991-01-01

    The growth of large, uniform zeolite crystals in high yield in space can have a major impact on the chemical process industry. Large zeolite crystals will be used to improve basic understanding of adsorption and catalytic mechanisms, and to make zeolite membranes. To grow large zeolites in microgravity, it is necessary to control the nucleation event and fluid motion, and to enhance nutrient transfer. Data is presented that suggests nucleation can be controlled using chemical compounds (e.g., Triethanolamine, for zeolite A), while not adversely effecting growth rate. A three-zone furnace has been designed to perform multiple syntheses concurrently. The operating range of the furnace is 295 K to 473 K. Teflon-lined autoclaves (10 ml liquid volume) have been designed to minimize contamination, reduce wall nucleation, and control mixing of pre-gel solutions on orbit. Zeolite synthesis experiments will be performed on USML-1 in 1992.

  7. Association of structural modifications with bioactivity in three new copper(II) complexes of Schiff base ligands derived from 5-chlorosalicylaldehyde and amino acids.

    PubMed

    Li, Ang; Liu, Ya-Hong; Yuan, Ling-Zhi; Ma, Zhong-Ying; Zhao, Chun-Lai; Xie, Cheng-Zhi; Bao, Wei-Guo; Xu, Jing-Yuan

    2015-05-01

    Three novel structurally associated copper(II) complexes [Cu(II)(SalCl-Gly)(H2O)2] (1), [Cu(II)(SalCl-Ala)(H2O)] (2) and [Cu(II)(SalCl-Gly)(bipy)]·0.5H2O (3) (SalCl-Gly=5-chloro-2-hydroxybenzylidene-glycine, SalCl-Ala=5-chloro-2-hydroxybenzylidene-alanine, bipy=2,2'-bipyridine) have been synthesized and characterized by X-ray crystallography, elemental analysis, IR and fluorescence spectroscopy. Single-crystal diffraction reveals that complex 1 is an infinite 1D zigzag chain in which SalCl-Gly serves as both a chelating and a bridging ligand, while complexes 2 and 3 are mononuclear. Cu(II) ions in complexes 1-3 exhibit distorted quasi-hexacoordinated octahedral, tetracoordinated square planar, and pentacoordinated square pyramid geometry, respectively. Their interactions with calf thymus DNA (CT-DNA) have been investigated by viscosity measurements and fluorescence spectroscopy. The apparent binding constant (Kapp) values for 1-3 are 1.02×10(5), 0.98×10(5) and 1.57×10(5)M(-1), respectively. All complexes displayed efficient oxidative cleavage of supercoiled DNA in the presence of H2O2. Complex 2, whose ligand can be regarded as a methyl-modification of SalCl-Gly of 1, showed a reduced DNA cleavage activity and a little-changed DNA-binding ability compared with 1. While attaching a 2,2'-bipyridine group to 1, the resulting complex 3 was conferred an enhanced intercalation into DNA. Moreover, cytotoxicity studies of three complexes against HepG-2 (human liver hepatocellular carcinoma) and NCI-H460 (human large-cell lung carcinoma) cells indicated that, thereto, complex 3 possessed the highest inhibition on viability of tested cells. PMID:25771239

  8. Zeolite exposure and associated pneumoconiosis

    SciTech Connect

    Casey, K.R.; Shigeoka, J.W.; Rom, W.N.; Moatamed, F.

    1985-06-01

    Naturally occurring zeolite minerals are aluminum silicates widespread in the earth's crust. Several of these minerals have fibrous forms and have been implicated as a possible cause of benign and malignant diseases of the lung and pleura in Turkey. This report describes a patient, living in an area of Nevada rich in zeolites, who presented with idiopathic pleural thickening and pulmonary fibrosis associated with extensive pulmonary deposition of zeolites.

  9. Novel modified zeolites for energy-efficient hydrocarbon separations.

    SciTech Connect

    Arruebo, Manuel; Dong, Junhang; Anderson, Thomas (Burns and McDonnell, Kansas City, MO); Gu, Xuehong; Gray, Gary (Goodyear Chemical Company, Akron, OH); Bennett, Ron (Goodyear Chemical Company, Akron, OH); Nenoff, Tina Maria; Kartin, Mutlu; Johnson, Kaylynn (Goodyear Chemical Company, Akron, OH); Falconer, John; Noble, Richard

    2006-11-01

    We present synthesis, characterization and testing results of our applied research project, which focuses on the effects of surface and skeletal modification of zeolites for significant enhancements in current hydrocarbon (HC) separations. Zeolites are commonly used by the chemical and petroleum industries as catalysts and ion-exchangers. They have high potential for separations owing to their unique pore structures and adsorption properties and their thermal, mechanical and chemical properties. Because of zeolites separation properties, low cost, and robustness in industrial process, they are natural choice for use as industrial adsorbents. This is a multidisciplinary effort to research, design, develop, engineer, and test new and improved materials for the separation of branched vs. linear organic molecules found in commercially important HC streams via adsorption based separations. The focus of this project was the surface and framework modification of the commercially available zeolites, while tuning the adsorption properties and the selectivities of the bulk and membrane separations. In particular, we are interested with our partners at Goodyear Chemical, on how to apply the modified zeolites to feedstock isoprene purification. For the characterization and the property measurements of the new and improved materials powder X-ray diffraction (PXRD), Residual Gas Analyzer-Mass Spectroscopy (RGA-MS), Electron Microscopy (SEM/EDAX), temperature programmed desorption (TPD) and surface area techniques were utilized. In-situ carbonization of MFI zeolite membranes allowed for the maximum separation of isoprene from n-pentane, with a 4.1% enrichment of the binary stream with n-pentane. In four component streams, a modified MFI membrane had high selectivities for n-pentane and 1-3-pentadiene over isoprene but virtually no separation for the 2-methyl-2-butene/isoprene pair.

  10. [Adsorption of phenol chemicals by surfactant-modified zeolites].

    PubMed

    Xie, Jie; Wang, Zhe; Wu, De-Yi; Li, Chun-Jie

    2012-12-01

    Two kinds of zeolites were prepared from fly ash and modified by surfactant subsequently. Surfactant-modified zeolites were studied for adsorption of phenol chemicals (phenol, p-chlorphenol, bisphenol A). It showed that the adsorption affinity of zeolite to phenol chemicals was significantly improved after surfactant modification. The adsorption isotherms of phenol chemicals were well fitted by the Langmuir isotherm. For the two surfactant-surfactant modified zeolites, the maximum adsorption amounts of phenol, p-chlorphenol, and bisphenol A calculated from the Langmuir equation were 37.7, 52.36, 90.9 mg x g(-1) and 10.7, 22.83, 56.8 mg x g(-1), respectively. When pH values of solutions were higher than the pK(a) values of phenol chemicals, the removal efficiencies were getting higher with the increase of pH values. The octanol/water partition coefficient (K(ow)) was also found to be an important factor affecting adsorption of phenol chemicals by the modified zeolites. Higher K(ow) value, which means the greater hydrophobicity of the chemicals, resulted in a higher removal.

  11. Orthophosphoric acid interactions with ultrastable zeolite Y: Infrared and NMR studies

    SciTech Connect

    Corma, A.; Fornes, V.; Kolodziejski, W.; Martinez-Triguero, L.J. )

    1994-01-01

    Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.

  12. Improved zeolitic isocracking catalysts

    SciTech Connect

    Dahlberg, A.J.; Habib, M.M.; Moore, R.O.; Law, D.V.; Convery, L.J.

    1995-09-01

    Chevron Research Company introduced the first low pressure, low temperature catalytic hydrocracking process--ISOCRACKING--in 1959. Within the last four years, Chevron has developed and commercialized three new zeolitic ISOCRACKING catalysts. ICR 209 is Chevron`s latest noble metal ISOCRACKING catalyst. It offers improved liquid yield stability, longer life, and superior polynuclear aromatics control compared to its predecessor. ICR 209`s high hydrogenation activity generates the highest yields of superior quality jet fuel of any zeolitic ISOCRACKING catalyst. The second new ISOCRACKING catalyst, ICR 208, is a base metal catalyst which combines high liquid selectivity and high light naphtha octane in hydrocrackers operating for maximum naphtha production. ICR 210 is another new base metal catalyst which offers higher liquid yields and longer life than ICR 208 by virtue of a higher hydrogenation-to-acidity ratio. Both ICR 208 and ICR 210 have been formulated to provide higher liquid yield throughout the cycle and longer cycle length than conventional base metal/zeolite catalysts. This paper will discuss the pilot plant and commercial performances of these new ISOCRACKING catalysts.

  13. Effect of zeolite on toxicity of ammonia in freshwater sediments: Implications for toxicity identification evaluation procedures

    SciTech Connect

    Besser, J.M.; Ingersoll, C.G.; Leonard, E.N.; Mount, D.R.

    1998-11-01

    Techniques for reducing ammonia toxicity in freshwater sediments were investigated as part of a project to develop toxicity identification and evaluation (TIE) procedures for whole sediments. Although ammonia is a natural constituent of freshwater sediments, pollution can lead to ammonia concentrations that are toxic to benthic invertebrates, and ammonia can also contribute to the toxicity of sediments that contain more persistent contaminants. The authors investigated the use of amendments of a natural zeolite mineral, clinoptilolite, to reduce concentrations of ammonia in sediment pore water. Zeolites have been widely used for removal of ammonia in water treatment and in aqueous TIE procedures. The addition of granulated zeolite to ammonia-spiked sediments reduced pore-water ammonia concentrations and reduced ammonia toxicity to invertebrates. Amendments of 20% zeolite (v/v) reduced ammonia concentrations in pore water by {ge}70% in spiked sediments with ammonia concentrations typical of contaminated freshwater sediments. Zeolite amendments reduced toxicity of ammonia-spiked sediments to three taxa of benthic invertebrates (Hyalella azteca, Lumbriculus variegatus, and Chironomus tentans), despite their widely differing sensitivity to ammonia toxicity. In contrast, zeolite amendments did not reduce acute toxicity of sediments containing high concentrations of cadmium or copper or reduce concentrations of these metals in pore waters. These studies suggest that zeolite amendments, used in conjunction with toxicity tests with sensitive taxa such as H. azteca, may be an effective technique for selective reduction of ammonia toxicity in freshwater sediments.

  14. Effect of zeolite on toxicity of ammonia in freshwater sediments: Implications for toxicity identification evaluation procedures

    USGS Publications Warehouse

    Besser, J.M.; Ingersoll, C.G.; Leonard, E.N.; Mount, D.R.

    1998-01-01

    Techniques for reducing ammonia toxicity in freshwater sediments were investigated as part of a project to develop toxicity identification and evaluation (TIE) procedures for whole sediments. Although ammonia is a natural constituent of freshwater sediments, pollution can lead to ammonia concentrations that are toxic to benthic invertebrates, and ammonia can also contribute to the toxicity of sediments that contain more persistent contaminants. We investigated the use of amendments of a natural zeolite mineral, clinoptilolite, to reduce concentrations of ammonia in sediment pore water. Zeolites have been widely used for removal of ammonia in water treatment and in aqueous TIE procedures. The addition of granulated zeolite to ammonia-spiked sediments reduced pore-water ammonia concentrations and reduced ammonia toxicity to invertebrates. Amendments of 20% zeolite (v/v) reduced ammonia concentrations in pore water by ???70% in spiked sediments with ammonia concentrations typical of contaminated freshwater sediments. Zeolite amendments reduced toxicity of ammonia-spiked sediments to three taxa of benthic invertebrates (Hyalella azteca, Lumbriculus variegatus, and Chironomus tentans), despite their widely differing sensitivity to ammonia toxicity. In contrast, zeolite amendments did not reduce acute toxicity of sediments containing high concentrations of cadmium or copper or reduce concentrations of these metals in pore waters. These studies suggest that zeolite amendments, used in conjunction with toxicity tests with sensitive taxa such as H. azteca, may be an effective technique for selective reduction of ammonia toxicity in freshwater sediments.

  15. Metallo-hydrazone complexes immobilized in zeolite Y: Synthesis, identification and acid violet-1 degradation

    NASA Astrophysics Data System (ADS)

    Ahmed, Ayman H.; Thabet, M. S.

    2011-12-01

    Copper(II), cobalt(II) and nickel(II) complexes of hydrazone ligand (SAPH) derived from salicylaldehyde and phenylhydrazine have been encapsulated in zeolite-Y super cages via ship-in-a-bottle synthesis. Detailed characterization of the intrazeolitic complexes were performed by elemental analysis, spectral (FT-IR, UV-Vis.) studies, magnetic measurements and X-ray diffraction. Furthers, surface texture and thermal analysis (TG, DTG, DTA) have provided further evidence for successful immobilization of the metal complexes inside zeolite Y. Investigation of the stereochemistry of these incorporated chelates pointed out that, SAPH ligand is capable to coordinate with the central metal through the (C dbnd N), phenolic (OH) and (NH) groups forming polynuclear structures. The involvement of zeolite oxygen in coordination was postulated in the hybrid materials. The intrazeolitic copper, cobalt and nickel-SAPH complexes have distorted tetrahedral, octahedral and square-pyramidal configurations, respectively. The zeolite encapsulated complexes are thermally stable up to 800 °C except Cu(II) sample which is thermally stable up to midpoint 428 °C. The assessment of the catalytic activity was performed by the use of the photo-degradation of acid violet-1 dye as a probe reaction in presence of H 2O 2 as an oxidant. Decolorization of acid violet-1 dye was examined under the same conditions whereas the unpromoted zeolite and Cu II, Co II, Ni II-hydrazone complexes supported on zeolite showed 13% and 76%, 53%, 43% color removal, respectively. The results revealed that, the zeolite encapsulated Cu(II) complex generally exhibited better catalytic efficiency (76%) compared with other investigated zeolite encapsulated metal-hydrazone samples.

  16. Sorption of Cu(II) Ions on Chitosan-Zeolite X Composites: Impact of Gelling and Drying Conditions.

    PubMed

    Djelad, Amal; Morsli, Amine; Robitzer, Mike; Bengueddach, Abdelkader; di Renzo, Francesco; Quignard, Françoise

    2016-01-01

    Chitosan-zeolite Na-X composite beads with open porosity and different zeolite contents were prepared by an encapsulation method. Preparation conditions had to be optimised in order to stabilize the zeolite network during the polysaccharide gelling process. Composites and pure reference components were characterized using X-ray diffraction (XRD); scanning electron microscopy (SEM); N₂ adsorption-desorption; and thermogravimetric analysis (TG). Cu(II) sorption was investigated at pH 6. The choice of drying method used for the storage of the adsorbent severely affects the textural properties of the composite and the copper sorption effectiveness. The copper sorption capacity of chitosan hydrogel is about 190 mg·g(-1). More than 70% of this capacity is retained when the polysaccharide is stored as an aerogel after supercrititcal CO₂ drying, but nearly 90% of the capacity is lost after evaporative drying to a xerogel. Textural data and Cu(II) sorption data indicate that the properties of the zeolite-polysaccharide composites are not just the sum of the properties of the individual components. Whereas a chitosan coating impairs the accessibility of the microporosity of the zeolite; the presence of the zeolite improves the stability of the dispersion of chitosan upon supercritical drying and increases the affinity of the composites for Cu(II) cations. Chitosan-zeolite aerogels present Cu(II) sorption properties. PMID:26797593

  17. Sorption of Cu(II) Ions on Chitosan-Zeolite X Composites: Impact of Gelling and Drying Conditions.

    PubMed

    Djelad, Amal; Morsli, Amine; Robitzer, Mike; Bengueddach, Abdelkader; di Renzo, Francesco; Quignard, Françoise

    2016-01-19

    Chitosan-zeolite Na-X composite beads with open porosity and different zeolite contents were prepared by an encapsulation method. Preparation conditions had to be optimised in order to stabilize the zeolite network during the polysaccharide gelling process. Composites and pure reference components were characterized using X-ray diffraction (XRD); scanning electron microscopy (SEM); N₂ adsorption-desorption; and thermogravimetric analysis (TG). Cu(II) sorption was investigated at pH 6. The choice of drying method used for the storage of the adsorbent severely affects the textural properties of the composite and the copper sorption effectiveness. The copper sorption capacity of chitosan hydrogel is about 190 mg·g(-1). More than 70% of this capacity is retained when the polysaccharide is stored as an aerogel after supercrititcal CO₂ drying, but nearly 90% of the capacity is lost after evaporative drying to a xerogel. Textural data and Cu(II) sorption data indicate that the properties of the zeolite-polysaccharide composites are not just the sum of the properties of the individual components. Whereas a chitosan coating impairs the accessibility of the microporosity of the zeolite; the presence of the zeolite improves the stability of the dispersion of chitosan upon supercritical drying and increases the affinity of the composites for Cu(II) cations. Chitosan-zeolite aerogels present Cu(II) sorption properties.

  18. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  19. Modification of surface layers of copper under the action of the volumetric discharge initiated by an avalanche electron beam in nitrogen and CO2 at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Shulepov, M. A.; Akhmadeev, Yu. Kh.; Tarasenko, V. F.; Kolubaeva, Yu. A.; Krysina, O. V.; Kostyrya, I. D.

    2011-05-01

    The results of experimental investigations of the action of the volumetric discharge initiated by an avalanche electron beam on the surface of copper specimens are presented. The volumetric (diffuse) discharge in nitrogen and CO2 at atmospheric pressure was initiated by applying high voltage pulses of nanosecond duration to a tubular foil cathode. It has been found that the treatment of a copper surface by this type of discharge increases the hardness of the surface layer due to oxidation.

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

    PubMed

    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 La(3+) in sodalite cage is much better than that of AE(2+) and about 12 La(3+) 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 La(3+) is more suitable for the catalytic cracking of cyclohexane than that of AE(2+). 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

  1. Potential of sustainable hierarchical zeolites in the valorization of α-pinene.

    PubMed

    Nuttens, Nicolas; Verboekend, Danny; Deneyer, Aron; Van Aelst, Joost; Sels, Bert F

    2015-04-13

    In the valorization of α-pinene, which is an important biomass intermediate derived from turpentine oil, hierarchical (mesoporous) zeolites represent a superior class of catalysts. Hierarchical USY, ZSM-5, and beta zeolites have been prepared, characterized, and catalytically evaluated, with the aim of combining the highest catalytic performance with the most sustainable synthetic protocol. These zeolites are prepared by alkaline treatment in aqueous solutions of NH4 OH, NaOH, diethylamine, and NaOH complemented with tetrapropylammonium bromide. The hierarchical USY zeolite is the most attractive catalyst of the tested series, and is able to combine an overall organic-free synthesis with an up to sixfold activity enhancement and comparable selectivity over the conventional USY zeolite. This superior performance relates to a threefold greater activity than that of the commercial standard, namely, H2 SO4 /TiO2 . Correlation of the obtained benefits to the amount of solid lost during the postsynthetic modifications highlights that the highest activity gains are obtained with minor leaching. Furthermore, a highly zeolitic character, as determined by bulk XRD, is beneficial, but not crucial, in the conversion of α-pinene. The alkaline treatments not only result in a higher overall activity, but also a more functional external surface area, attaining up to four times the pinene conversions per square nanometer. The efficiency of the hierarchical USY zeolite is concomitantly demonstrated in the conversion of limonene and turpentine oil, which emphasizes its industrial potential. PMID:25736719

  2. Potential of sustainable hierarchical zeolites in the valorization of α-pinene.

    PubMed

    Nuttens, Nicolas; Verboekend, Danny; Deneyer, Aron; Van Aelst, Joost; Sels, Bert F

    2015-04-13

    In the valorization of α-pinene, which is an important biomass intermediate derived from turpentine oil, hierarchical (mesoporous) zeolites represent a superior class of catalysts. Hierarchical USY, ZSM-5, and beta zeolites have been prepared, characterized, and catalytically evaluated, with the aim of combining the highest catalytic performance with the most sustainable synthetic protocol. These zeolites are prepared by alkaline treatment in aqueous solutions of NH4 OH, NaOH, diethylamine, and NaOH complemented with tetrapropylammonium bromide. The hierarchical USY zeolite is the most attractive catalyst of the tested series, and is able to combine an overall organic-free synthesis with an up to sixfold activity enhancement and comparable selectivity over the conventional USY zeolite. This superior performance relates to a threefold greater activity than that of the commercial standard, namely, H2 SO4 /TiO2 . Correlation of the obtained benefits to the amount of solid lost during the postsynthetic modifications highlights that the highest activity gains are obtained with minor leaching. Furthermore, a highly zeolitic character, as determined by bulk XRD, is beneficial, but not crucial, in the conversion of α-pinene. The alkaline treatments not only result in a higher overall activity, but also a more functional external surface area, attaining up to four times the pinene conversions per square nanometer. The efficiency of the hierarchical USY zeolite is concomitantly demonstrated in the conversion of limonene and turpentine oil, which emphasizes its industrial potential.

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

    PubMed Central

    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

  4. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    SciTech Connect

    Sarah C. Larson; Vicki H. Grassian

    2006-12-31

    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{sub x}) and ammonia (NH{sub 3}) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO{sub 2} was observed at room temperature in the presence of NH{sub 3} as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO{sub 2} reduction with NH{sub 3} relative to nanocrystalline NaY.

  5. Utilizing copper(I) catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition for the surface modification of colloidal particles with electroactive and emissive moieties

    NASA Astrophysics Data System (ADS)

    Rungta, Parul

    The development of charge-transporting and fluorescing colloidal particles that can be directly printed into electroluminescent devices may result in a broad impact on the use of electrical energy for illumination. The objective of this work was to design and synthesize electroactive & fluorescing colloidal particles; establish their optical, electronic, and thermodynamic properties; and transition them into a device format for potential applications. The original intended application of this work was to build "better" colloidally-based organic light emitting devices (OLEDs) by creating functional particles with superior electrical and optical performance relative to commercially available technologies, but through the course of the research, the particles that were developed were found to be better suited for medical applications. Nonetheless, the global objective envisioned at the onset of this research was consistent with its final outcomes. The research tasks pursued to accomplish this global objective included: (1) The design and synthesis of electroactive moieties and their conversion into organic light emitting devices; An electron-transporting monomer was synthesized that was structurally & energetically similar to the small molecule 2-biphenyl-4-yl-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD). The monomer was copolymerized with 2-(9H-carbazol-9-yl)ethyl 2-methylacrylate (CE) and the resulting copolymer was utilized in OLEDs which employed fluorescent coumarin 6 (C6) or phosphorescent tris(2-phenylpyridine)iridium(III) [Ir(ppy)3] emitters. The copolymer devices exhibited a mean luminance of ca. 400 and 3,552 cd/m2 with the C6 and Ir(ppy)3 emitters, that were stable with thermal aging at temperatures ranging from 23°C to 130°C. Comparable poly(9-vinyl-9H-carbazole)/tBu-PBD blend devices exhibited more pronounced variations in performance with thermal aging. (2) The surface-modification of colloids with electroactive & fluorescing moieties via "click

  6. Multi-component lanthanide hybrids based on zeolite A/L and zeolite A/L-polymers for tunable luminescence.

    PubMed

    Chen, Lei; Yan, Bing

    2015-02-01

    Some multi-component hybrids based on zeolite L/A are prepared. Firstly, zeolite A/L is loaded with lanthanide complexes (Eu-DBM or Tb-AA (acetylacetone = AA, dibenzoylmethane = DBM)) into its channels. Secondly, 3-methacryloyloxypropyltrimethoxysilane (γ-MPS) is used to covalently graft onto the surface of functionalized zeolite A/L (Si-[ZA/L⊃Eu-DBM(Tb-AA)]). Thirdly, lanthanide ions (Eu(3+)/Tb(3+)) are coordinated to the functionalized zeolite A/L and ligands (phen(1,10-phenanthroline) or bipy (2,2'-bipyridyl)) are introduced by a ship-in-bottle method. The inside-outside double modifications of ZA/L with lanthanide complexes afford the final hybrids and these are characterized by means of XRD, FT-IR, UV-vis DRS, SEM and luminescence spectroscopy, some of which display white or near-white light emission. Furthermore, selected above-mentioned hybrids are incorporated into PEMA/PMMA (poly ethyl methylacryate/poly methyl methacrylate) hosts to prepare luminescent polymer films. These results provide abundant data that these hybrid materials can be expected to have potential application in various practical fields.

  7. Utilizing copper(I) catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition for the surface modification of colloidal particles with electroactive and emissive moieties

    NASA Astrophysics Data System (ADS)

    Rungta, Parul

    The development of charge-transporting and fluorescing colloidal particles that can be directly printed into electroluminescent devices may result in a broad impact on the use of electrical energy for illumination. The objective of this work was to design and synthesize electroactive & fluorescing colloidal particles; establish their optical, electronic, and thermodynamic properties; and transition them into a device format for potential applications. The original intended application of this work was to build "better" colloidally-based organic light emitting devices (OLEDs) by creating functional particles with superior electrical and optical performance relative to commercially available technologies, but through the course of the research, the particles that were developed were found to be better suited for medical applications. Nonetheless, the global objective envisioned at the onset of this research was consistent with its final outcomes. The research tasks pursued to accomplish this global objective included: (1) The design and synthesis of electroactive moieties and their conversion into organic light emitting devices; An electron-transporting monomer was synthesized that was structurally & energetically similar to the small molecule 2-biphenyl-4-yl-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD). The monomer was copolymerized with 2-(9H-carbazol-9-yl)ethyl 2-methylacrylate (CE) and the resulting copolymer was utilized in OLEDs which employed fluorescent coumarin 6 (C6) or phosphorescent tris(2-phenylpyridine)iridium(III) [Ir(ppy)3] emitters. The copolymer devices exhibited a mean luminance of ca. 400 and 3,552 cd/m2 with the C6 and Ir(ppy)3 emitters, that were stable with thermal aging at temperatures ranging from 23°C to 130°C. Comparable poly(9-vinyl-9H-carbazole)/tBu-PBD blend devices exhibited more pronounced variations in performance with thermal aging. (2) The surface-modification of colloids with electroactive & fluorescing moieties via "click

  8. Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

    SciTech Connect

    Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige; Sakurai, Takeshi

    2014-07-18

    Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The single turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.

  9. Unconventional, highly selective CO2 adsorption in zeolite SSZ-13.

    PubMed

    Hudson, Matthew R; Queen, Wendy L; Mason, Jarad A; Fickel, Dustin W; Lobo, Raul F; Brown, Craig M

    2012-02-01

    Low-pressure adsorption of carbon dioxide and nitrogen was studied in both acidic and copper-exchanged forms of SSZ-13, a zeolite containing an 8-ring window. Under ideal conditions for industrial separations of CO(2) from N(2), the ideal adsorbed solution theory selectivity is >70 in each compound. For low gas coverage, the isosteric heat of adsorption for CO(2) was found to be 33.1 and 34.0 kJ/mol for Cu- and H-SSZ-13, respectively. From in situ neutron powder diffraction measurements, we ascribe the CO(2) over N(2) selectivity to differences in binding sites for the two gases, where the primary CO(2) binding site is located in the center of the 8-membered-ring pore window. This CO(2) binding mode, which has important implications for use of zeolites in separations, has not been observed before and is rationalized and discussed relative to the high selectivity for CO(2) over N(2) in SSZ-13 and other zeolites containing 8-ring windows. PMID:22235866

  10. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na{sub 2}O added as NAOH instead of Na{sub 2}CO{sub 3} to avoid severe foaming due to CO{sub 2} evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  11. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na[sub 2]O added as NAOH instead of Na[sub 2]CO[sub 3] to avoid severe foaming due to CO[sub 2] evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  12. Zeolite synthesis: an energetic perspective.

    PubMed

    Zwijnenburg, Martijn A; Bromley, Stefan T

    2010-11-21

    Taking |D(H(2)O)(x)|[AlSiO(4)] based materials (where D is Li, Na, K, Rb or Cs) as an archetypal aluminosilicate system, we use accurate density functional theory calculations to demonstrate how the substitution of silicon cations in silica, with pairs of aluminium and (alkali metal) cations, changes the energetic ordering of different competing structure-types. For large alkali metal cations we further show that the formation of porous aluminosilicate structures, the so-called zeolites, is energetically favored. These findings unequivocally demonstrate that zeolites can be energetic preferred reaction products, rather than being kinetically determined, and that the size of the (hydrated) cations in the pore, be it inorganic or organic, is critical for directing zeolite synthesis.

  13. Zeolite synthesis: an energetic perspective.

    PubMed

    Zwijnenburg, Martijn A; Bromley, Stefan T

    2010-11-21

    Taking |D(H(2)O)(x)|[AlSiO(4)] based materials (where D is Li, Na, K, Rb or Cs) as an archetypal aluminosilicate system, we use accurate density functional theory calculations to demonstrate how the substitution of silicon cations in silica, with pairs of aluminium and (alkali metal) cations, changes the energetic ordering of different competing structure-types. For large alkali metal cations we further show that the formation of porous aluminosilicate structures, the so-called zeolites, is energetically favored. These findings unequivocally demonstrate that zeolites can be energetic preferred reaction products, rather than being kinetically determined, and that the size of the (hydrated) cations in the pore, be it inorganic or organic, is critical for directing zeolite synthesis. PMID:20938518

  14. Studies of zeolite-based artificial photosynthetic systems

    NASA Astrophysics Data System (ADS)

    Zhang, Haoyu

    used as a model system. A MV2+-loaded zeolite was treated with disilazane reagents under ambient conditions and the grafting of siloxy functionality on the zeolite was confirmed by infrared, NMR spectroscopy and elemental analysis. Surface modification of MV2+-loaded zeolites encapsulated the guest molecules in the zeolite cages and release of MV2+ by ion-exchange with sodium ions was studied. The total amount of MV2+ released was dependent on the concentration of Na+ in solution, and was similar for the derivatized and underivatized samples. In the absence of surface modification, equilibration occurred within 20 minutes, whereas with surface modification, the equilibration time was extended to 7 days. These kinetics are reflected in the effective diffusion coefficients (D) of MV2+, with D = 1.2 x 10-15 cm 2 s-1 for derivatized zeolite Y and D = 0.2 -1.1 x 10-7 cm2 s-1 for the underivatized sample. (Abstract shortened by UMI.)

  15. Enhanced selectivity of zeolites by controlled carbon deposition

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Kartin, Mutlu

    2006-05-09

    A method for carbonizing a zeolite comprises depositing a carbon coating on the zeolite pores by flowing an inert carrier gas stream containing isoprene through a regenerated zeolite at elevated temperature. The carbonized zeolite is useful for the separation of light hydrocarbon mixtures due to size exclusion and the differential adsorption properties of the carbonized zeolite.

  16. Synthesis and testing of nanosized zeolite Y

    NASA Astrophysics Data System (ADS)

    Karami, Davood

    This work focuses on the synthesis and testing of nanosized zeolite Y. The synthesis formulations of faujasite-type structure of zeolite Y prepared in nanosized form are described. The synthetic zeolite Y is the most widely employed for the preparation of fluid catalytic cracking (FCC) catalysts. The synthesis of zeolite Y is very complicated process. The mean particle size of zeolite Y is 1800 nm. The major challenge of this work involved reducing this average particle size to less than 500 nm. The preliminary experiments were conducted to obtain the pure zeolite Y using the soluble silicates as a silica source. This was achieved by applying the experimental design approach to study the effects of many parameters. The ageing time turned out to be the most significant variable affecting product purity. Based on the preliminary results, a detailed investigation was carried out to determine the effects of silica-alumina precursor preparations on zeolite Y synthesis. Aluminosilicate precursors were prepared by gelling and precipitation of soluble silicate. The as-prepared precursors were used for the hydrothermal synthesis of zeolite Y. The procedure of the precipitation of soluble silicate yielded pure zeolite Y at the conventional synthesis conditions. The extent of purity of zeolite Y depends on the surface areas of aluminosilicate precursors. A novel approach to zeolite Y synthesis was employed for the preparation of the pure nanosized zeolite Y. This was achieved by applying the method of impregnation of precipitated silica. This novel method of impregnation for zeolite Y preparation allows eliminating the vigorous agitation step required for the preparation of a homogeneous silica solution, thereby simplifying the synthesis of zeolite Y in one single vessel. In case of the synthesis of nanosized zeolite Y, the effect of varying the organic templates on the formation of nanosized particles of zeolite Y was investigated, while all other reaction parameters were

  17. Modification of the charge transport properties of the copper phthalocyanine/poly(vinyl alcohol) interface using cationic or anionic surfactant for field-effect transistor performance enhancement

    NASA Astrophysics Data System (ADS)

    Jastrombek, Diana; Nawaz, Ali; Koehler, Marlus; Meruvia, Michelle S.; Hümmelgen, Ivo A.

    2015-08-01

    We report on the performance enhancement of organic field-effect transistors prepared using cross-linked poly(vinyl alcohol) as gate dielectric and copper phthalocyanine as channel semiconductor through gate dielectric surface treatment. The gate dielectric surface was treated using either a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), or an anionic surfactant, sodium dodecyl sulfate (SDS). We determined the charge-carrier field-effect mobility ( μ FET) in these transistors as a function of the effective channel thickness in the channel bottleneck, near to the transistor source. When compared to the untreated devices, in the devices treated with CTAB or SDS, the channel formation occurs at lower gate voltage and the carrier mobility in the thinnest channel region, corresponding to the immediate vicinity of the insulator/semiconductor interface, is significantly higher. The surfactant treatment leads to a tenfold increase in μ FET and significant enhancement in capacitance, on/off current ratio and transconductance of the transistor.

  18. Hydrogen Selective Exfoliated Zeolite Membranes

    SciTech Connect

    Tsapatsis, Michael; Daoutidis, Prodromos; Elyassi, Bahman; Lima, Fernando; Iyer, Aparna; Agrawal, Kumar; Sabnis, Sanket

    2015-04-06

    The objective of this project was to develop and evaluate an innovative membrane technology at process conditions that would be representative of Integrated Gasification Combined Cycle (IGCC) advanced power generation with pre-combustion capture of carbon dioxide (CO2). This research focused on hydrogen (H2)-selective zeolite membranes that could be utilized to separate conditioned syngas into H2-rich and CO2-rich components. Both experiments and process design and optimization calculations were performed to evaluate the concept of ultra-thin membranes made from zeolites nanosheets. In this work, efforts in the laboratory were made to tackle two fundamental challenges in application of zeolite membranes in harsh industrial environments, namely, membrane thickness and membrane stability. Conventional zeolite membranes have thicknesses in the micron range, limiting their performance. In this research, we developed a method for fabrication of ultimately thin zeolite membranes based on zeolite nanosheets. A range of layered zeolites (MWW, RWR, NSI structure types) suitable for hydrogen separation was successfully exfoliated to their constituent nanosheets. Further, membranes were made from one of these zeolites, MWW, to demonstrate the potential of this group of materials. Moreover, long-term steam stability of these zeolites (up to 6 months) was investigated in high concentrations of steam (35 mol% and 95 mole%), high pressure (10 barg), and high temperatures (350 °C and 600 °C) relevant to conditions of water-gas-shift and steam methane reforming reactions. It was found that certain nanosheets are stable, and that stability depends on the concentration of structural defects. Additionally, models that represent a water-gas-shift (WGS) membrane reactor equipped with the zeolite membrane were developed for systems studies. These studies had the aim of analyzing the effect of the membrane reactor integration into IGCC plants

  19. UTILITY OF ZEOLITES IN HAZARDOUS METAL REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic pollutants have been removed from water at room temperature by using synthetic zeolites. Zeolite Faujasite Y has been used to remove inorganic pollutants including arseni...

  20. The influence of using Jordanian natural zeolite on the adsorption, physical, and mechanical properties of geopolymers products.

    PubMed

    Yousef, Rushdi Ibrahim; El-Eswed, Bassam; Alshaaer, Mazen; Khalili, Fawwaz; Khoury, Hani

    2009-06-15

    Geopolymers consist of an amorphous, three-dimensional structure resulting from the polymerization of aluminosilicate monomers that result from dissolution of kaolin in an alkaline solution at temperatures around 80 degrees C. One potential use of geopolymers is as Portland cement replacement. It will be of great importance to provide a geopolymer with suitable mechanical properties for the purpose of water storage and high adsorption capacity towards pollutants. The aim of this work is to investigate the effect of using Jordanian zeolitic tuff as filler on the mechanical performance and on the adsorption capacity of the geopolymers products. Jordanian zeolitic tuff is inexpensive and is known to have high adsorption capacity. The results confirmed that this natural zeolitic tuff can be used as a filler of stable geopolymers with high mechanical properties and high adsorption capacity towards methylene blue and Cu(II) ions. The XRD measurements showed that the phillipsite peaks (major mineral constituent of Jordanian zeolite) were disappeared upon geopolymerization. The zeolite-based geopolymers revealed high compressive strength compared to reference geopolymers that employ sand as filler. Adsorption experiments showed that among different geopolymers prepared, the zeolite-based geopolymers have the highest adsorption capacity towards methylene blue and copper(II) ions.

  1. Mesoporous MFI zeolites by microwave induced assembly between sulfonic acid functionalized MFI zeolite nanoparticles and alkyltrimethylammonium cationic surfactants.

    PubMed

    Jin, Hailian; Ansari, Mohd Bismillah; Park, Sang-Eon

    2011-07-14

    Mesoporous MFI zeolites (ZSM-5, TS-1, S-1) having intracrystalline mesoporosity within zeolite crystals were synthesized by microwave induced assembly through the ionic interaction between the sulfonic acid functionalized MFI zeolite nanoparticles and alkyltrimethylammonium cationic surfactants.

  2. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    SciTech Connect

    Kajikawa, Takao; Kataoka, Kunishige; Sakurai, Takeshi

    2012-05-25

    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  3. Kinetics of Sr/Ba and Sr/Ca ion exchange in synthetic zeolite A

    SciTech Connect

    Gaus, H.; Lutze, W.

    1981-01-08

    The isotopic exchange kinetics of Sr, Ba, and Ca have been measured in zeolites with different compositions and found to be describable as self-diffusion. The self-diffusion coefficients are strongly dependent on the composition. Also the Sr/Ba and Sr/Ca ion exchanges are measured in both directions and described as interdiffusion. While for Sr/Ba tolerable agreement is reached, for Sr/Ca a modification is necessary. The interdiffusion coefficient is multiplied by a factor which takes into account the activity, i.e., the selectivity of the zeolite. As a continuation of an earlier paper the zeolite is described as a mixture of microcells and free water. The above-mentioned factor must be calculated for a nonequilibrium state with respect to the water content in order to get agreement with the measurements.

  4. [What a physician should know about zeolites].

    PubMed

    Boranić, M

    2000-01-01

    Zeolites are natural and synthetic hydrated crystalline aluminosilicates endowed with absorptive and ion exchange properties. They have found numerous and multifarous applications--in industry as catalysts and absorbents, in water sanitation for the removal of ammonia and heavy metals, in agriculture as fertilizers, and in animal husbandry as the absorbents of excreted material and as food additives. Medical applications have included the use in filtration systems for anesthesia or dialysis and as the contrast materials in NMR imaging. Recently, zeolite powders for external use have found application as deodorants, antimycotic agents and wound dressings. Peroral use of encapsulated zeolite powders enriched with vitamins, oligoelements or other ingredients has been claimed to exert beneficial medical effects. Ingestion of zeolites may be considered analogous to the clay eating (geophagia), considered in traditional medicine as a remedy for various illnesses. Being amphoteric, zeolites are partly soluble in acid or alkaline media, but within the physiological pH range the solubility is generally low. Minimal amounts of free aluminium or silicium from the ingested zeolites are resorbed from the gut. The bulk of ingested zeolite probably remains undissolved in the gut. In view of the ion exchange properties, zeolites may be expected to change the ionic content, pH and buffering capacity of the gastrointestinal secretions and to affect the transport through the intestinal epithelium. In addition, zeolites could affect the bacterial flora and the resorption of bacterial products, vitamins and oligoelements. The contact of zeolite particles with gastrointestinal mucosa may elicit the secretion of cytokines with local and systemic actions. Reactive silicium ions might react with biomolecules of the intestinal epithelium, and if resorbed, do so in other cells. Mutagenic and carcinogenic effects of zeolite particles have been described, resembling such effects of asbestos

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

    PubMed Central

    van der Bij, Hendrik E.

    2015-01-01

    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. PMID:26051875

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

    PubMed

    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.

  7. Synthesis of ‘unfeasible’ zeolites

    NASA Astrophysics Data System (ADS)

    Mazur, Michal; Wheatley, Paul S.; Navarro, Marta; Roth, Wieslaw J.; Položij, Miroslav; Mayoral, Alvaro; Eliášová, Pavla; Nachtigall, Petr; Čejka, Jiří; Morris, Russell E.

    2016-01-01

    Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum—why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such ‘unfeasible’ zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.

  8. Increased thermal conductivity monolithic zeolite structures

    DOEpatents

    Klett, James; Klett, Lynn; Kaufman, Jonathan

    2008-11-25

    A monolith comprises a zeolite, a thermally conductive carbon, and a binder. The zeolite is included in the form of beads, pellets, powders and mixtures thereof. The thermally conductive carbon can be carbon nano-fibers, diamond or graphite which provide thermal conductivities in excess of about 100 W/mK to more than 1,000 W/mK. A method of preparing a zeolite monolith includes the steps of mixing a zeolite dispersion in an aqueous colloidal silica binder with a dispersion of carbon nano-fibers in water followed by dehydration and curing of the binder is given.

  9. Amine-functionalized, silver-exchanged zeolite NaY: Preparation, characterization and antibacterial activity

    NASA Astrophysics Data System (ADS)

    Hanim, Siti Aishah Mohd; Malek, Nik Ahmad Nizam Nik; Ibrahim, Zaharah

    2016-01-01

    Amine-functionalized, silver-exchanged zeolite NaY (ZSA) were prepared with three different concentrations of 3-aminopropyltriethoxysilane (APTES) (0.01, 0.20 and 0.40 M) and four different concentrations of silver ions (25%, 50%, 100% and 200% from zeolite cation exchange capacity (CEC)). The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), surface area analysis, thermogravimetric analysis (TGA) and zeta potential (ZP) analysis. The FTIR results indicated that the zeolite was functionalized by APTES and that the intensity of the peaks corresponding to APTES increased as the concentration of APTES used was increased. The antibacterial activities of the silver-exchanged zeolite NaY (ZS) and ZSA were studied against Escherichia coli ATCC11229 and Staphylococcus aureus ATCC6538 using the disc diffusion technique (DDT) and minimum inhibitory concentration (MIC). The antibacterial activity of ZSA increased with the increase in APTES on ZS, and E. coli was more susceptible towards the sample compared to S. aureus. The FESEM micrographs of the bacteria after contact with the ZSA suggested different mechanisms of bacterial death for these two bacteria due to exposure to the studied sample. The functionalization of ZS with APTES improved the antibacterial activity of the silver-zeolite, depending on the concentration of silver ions and APTES used during modification.

  10. Zeolites Remove Sulfur From Fuels

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

    Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

  11. Factors affecting adsorption characteristics of Zn2+ on two natural zeolites.

    PubMed

    Oren, Ali Hakan; Kaya, Abidin

    2006-04-17

    Mining-related and industrial wastes are primary sources of heavy metal contamination in soils and groundwater. The limitation of such waste in drinking water needs to meet government requirements in order to safeguard human health and environment. Zinc, one of the most preponderant pollutants, is difficult to remove from wastewater rather than other heavy metals (i.e. lead, copper and cadmium). This paper investigates Zn2+ adsorption characteristics of two natural zeolites found in the regions of Gordes and Bigadic, in western Turkey. The results show that the Zn2+ adsorption behavior of both zeolites is highly dependent on the pH. Adsorption dependence on lower pH values (pH<4) is explained by the dissolution of crystal structure and the competition of the zinc ions with the H+. Between pH 4 and 6, the basic mechanism is the ion exchange process. The results also showed that decrease in grain size does not increase the adsorption capacity of zeolite from Gordes, yet it increases that of zeolite from Bigadic about 23%. The results also reveal that an increase in the initial concentration of Zn2+ in the system causes an increase in the adsorption capacity to a degree, then it becomes more constant at higher concentrations. With this, the removal efficiency of Gordes zeolite is two times higher than that of Bigadic zeolite. Results show that an increase in slurry concentration results in a lower uptake of Zn2+. In the final part of the paper, we compared the experimental data with the Langmuir and Freundlich isotherms. The results show that there is a good fit between the experimental data and empirical isotherms.

  12. Factors affecting adsorption characteristics of Zn2+ on two natural zeolites.

    PubMed

    Oren, Ali Hakan; Kaya, Abidin

    2006-04-17

    Mining-related and industrial wastes are primary sources of heavy metal contamination in soils and groundwater. The limitation of such waste in drinking water needs to meet government requirements in order to safeguard human health and environment. Zinc, one of the most preponderant pollutants, is difficult to remove from wastewater rather than other heavy metals (i.e. lead, copper and cadmium). This paper investigates Zn2+ adsorption characteristics of two natural zeolites found in the regions of Gordes and Bigadic, in western Turkey. The results show that the Zn2+ adsorption behavior of both zeolites is highly dependent on the pH. Adsorption dependence on lower pH values (pH<4) is explained by the dissolution of crystal structure and the competition of the zinc ions with the H+. Between pH 4 and 6, the basic mechanism is the ion exchange process. The results also showed that decrease in grain size does not increase the adsorption capacity of zeolite from Gordes, yet it increases that of zeolite from Bigadic about 23%. The results also reveal that an increase in the initial concentration of Zn2+ in the system causes an increase in the adsorption capacity to a degree, then it becomes more constant at higher concentrations. With this, the removal efficiency of Gordes zeolite is two times higher than that of Bigadic zeolite. Results show that an increase in slurry concentration results in a lower uptake of Zn2+. In the final part of the paper, we compared the experimental data with the Langmuir and Freundlich isotherms. The results show that there is a good fit between the experimental data and empirical isotherms. PMID:16266781

  13. Zeolite-like liquid crystals

    PubMed Central

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-01-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension. PMID:26486751

  14. Copper transport.

    PubMed

    Linder, M C; Wooten, L; Cerveza, P; Cotton, S; Shulze, R; Lomeli, N

    1998-05-01

    In adult humans, the net absorption of dietary copper is approximately 1 mg/d. Dietary copper joins some 4-5 mg of endogenous copper flowing into the gastrointestinal tract through various digestive juices. Most of this copper returns to the circulation and to the tissues (including liver) that formed them. Much lower amounts of copper flow into and out of other major parts of the body (including heart, skeletal muscle, and brain). Newly absorbed copper is transported to body tissues in two phases, borne primarily by plasma protein carriers (albumin, transcuprein, and ceruloplasmin). In the first phase, copper goes from the intestine to the liver and kidney; in the second phase, copper usually goes from the liver (and perhaps also the kidney) to other organs. Ceruloplasmin plays a role in this second phase. Alternatively, liver copper can also exit via the bile, and in a form that is less easily reabsorbed. Copper is also present in and transported by other body fluids, including those bathing the brain and central nervous system and surrounding the fetus in the amniotic sac. Ceruloplasmin is present in these fluids and may also be involved in copper transport there. The concentrations of copper and ceruloplasmin in milk vary with lactational stage. Parallel changes occur in ceruloplasmin messenger RNA expression in the mammary gland (as determined in pigs). Copper in milk ceruloplasmin appears to be particularly available for absorption, at least in rats. PMID:9587137

  15. Copper transport.

    PubMed

    Linder, M C; Wooten, L; Cerveza, P; Cotton, S; Shulze, R; Lomeli, N

    1998-05-01

    In adult humans, the net absorption of dietary copper is approximately 1 mg/d. Dietary copper joins some 4-5 mg of endogenous copper flowing into the gastrointestinal tract through various digestive juices. Most of this copper returns to the circulation and to the tissues (including liver) that formed them. Much lower amounts of copper flow into and out of other major parts of the body (including heart, skeletal muscle, and brain). Newly absorbed copper is transported to body tissues in two phases, borne primarily by plasma protein carriers (albumin, transcuprein, and ceruloplasmin). In the first phase, copper goes from the intestine to the liver and kidney; in the second phase, copper usually goes from the liver (and perhaps also the kidney) to other organs. Ceruloplasmin plays a role in this second phase. Alternatively, liver copper can also exit via the bile, and in a form that is less easily reabsorbed. Copper is also present in and transported by other body fluids, including those bathing the brain and central nervous system and surrounding the fetus in the amniotic sac. Ceruloplasmin is present in these fluids and may also be involved in copper transport there. The concentrations of copper and ceruloplasmin in milk vary with lactational stage. Parallel changes occur in ceruloplasmin messenger RNA expression in the mammary gland (as determined in pigs). Copper in milk ceruloplasmin appears to be particularly available for absorption, at least in rats.

  16. Nanocrystalline Zeolites: Synthesis, Mechanism, and Applications

    NASA Astrophysics Data System (ADS)

    Severance, Michael Andrew

    Nanocrystalline zeolite particles are becoming an important material in many technical applications (e.g. zeolite membranes). Synthetic methods that minimize the zeolite crystal diameter, while providing a narrow particle size distribution, are of primary importance in these technical applications. However, there are several limitations to currently existing synthetic routes aimed at producing nanozeolites and zeolite membrane devices. For example, zeolite growth in these contexts typically requires days to weeks at high temperature to crystallize. Despite excellent performance of zeolite membranes in several separation applications, the long synthesis times required undermine any practical application of these technologies. This work focuses on chemical manipulation of zeolite nucleation processes in sol gel systems in effort to address such limitations. The primary findings indicate that careful control of the nucleation stage of a clear zeolite synthesis (optically transparent sol gel) allow the formation of zeolite Y nanocrystals less than 50 nm in diameter with a polydispersity index less than 0.2. Furthermore, chemical perturbations made during the nucleation stage of zeolite Y hydrogel synthesis is shown to accelerate crystal growth by a factor of 3-4, depending on the specific sol gel chemistry. These findings are applied to the nanocrystal seeding and rapid hydrothermal growth of zeolite Y membranes on inexpensive polymeric supports. A novel synthetic method is developed to this end. Also, the chemical and physical properties of monodisperse nanocrystalline zeolite Y synthesized herein are explored by electrochemical impedance spectroscopy. It is found that the particle interface plays an important role in the ionic conductivity of nanocrystalline zeolites in contrast to their larger zeolite counterparts in analogy to other ceramic and metal oxide ion conductors. Finally, the possibility to produce novel organic and inorganic composite systems through

  17. Treating Coalbed Natural Gas Produced Water for Beneficial Use By MFI Zeolite Membranes

    SciTech Connect

    Robert Lee; Liangxiong Li

    2008-03-31

    membranes and optimize operating conditions to enhance water flux and ion rejection, and (3) to perform long-term RO operation on tubular membranes to study membrane stability and to collect experimental data necessary for reliable evaluations of technical and economic feasibilities. Our completed research has resulted in deep understanding of the ion and organic separation mechanism by zeolite membranes. A two-step hydrothermal crystallization process resulted in a highly efficient membrane with good reproducibility. The zeolite membranes synthesized therein has an overall surface area of {approx}0.3 m{sup 2}. Multichannel vessels were designed and machined for holding the tubular zeolite membrane for water purification. A zeolite membrane RO demonstration with zeolite membranes fabricated on commercial alpha-alumina support was established in the laboratory. Good test results were obtained for both actual produced water samples and simulated samples. An overall 96.9% ion rejection and 2.23 kg/m{sup 2}.h water flux was achieved in the demonstration. In addition, a post-synthesis modification method using Al{sup 3+}-oligomers was developed for repairing the undesirable nano-scale intercrystalline pores. Considerable enhancement in ion rejection was achieved. This new method of zeolite membrane modification is particularly useful for enhancing the efficiency of ion separation from aqueous solutions because the modification does not need high temperature operation and may be carried out online during the RO operation. A long-term separation test for actual CBM produced water has indicated that the zeolite membranes show excellent ion separation and extraordinary stability at high pressure and produced water environment.

  18. UTILITY OF ZEOLITES IN ARSENIC REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange and adsorption properties. So far the cation exchanger properties of zeolites have been extensively studied and utilized. The anion exchanger properties of zeolites are less studied. Zeolite Faujasite Y has been used to remove arseni...

  19. Novel Approach for Clustering Zeolite Crystal Structures.

    PubMed

    Lach-Hab, M; Yang, S; Vaisman, I I; Blaisten-Barojas, E

    2010-04-12

    Informatics approaches play an increasingly important role in the design of new materials. In this work we apply unsupervised statistical learning for identifying four framework-type attractors of zeolite crystals in which several of the zeolite framework types are grouped together. Zeolites belonging to these super-classes manifest important topological, chemical and physical similarities. The zeolites form clusters located around four core framework types: LTA, FAU, MFI and the combination of EDI, HEU, LTL and LAU. Clustering is performed in a 9-dimensional space of attributes that reflect topological, chemical and physical properties for each individual zeolite crystalline structure. The implemented machine learning approach relies on hierarchical top-down clustering approach and the expectation maximization method. The model is trained and tested on ten partially independent data sets from the FIZ/NIST Inorganic Crystal Structure Database.

  20. Synthesis, characterization and catalytic activity of indium substituted nanocrystalline Mobil Five (MFI) zeolite

    SciTech Connect

    Shah, Kishor Kr.; Nandi, Mithun; Talukdar, Anup K.

    2015-06-15

    Highlights: • In situ modification of the MFI zeolite by incorporation of indium. • The samples were characterized by XRD, FTIR, TGA, UV–vis (DRS), SAA, EDX and SEM. • The incorporation of indium was confirmed by XRD, FT-IR, UV–vis (DRS), EDX and TGA. • Hydroxylation of phenol reaction was studied on the synthesized catalysts. - Abstract: A series of indium doped Mobil Five (MFI) zeolite were synthesized hydrothermally with silicon to aluminium and indium molar ratio of 100 and with aluminium to indium molar ratios of 1:1, 2:1 and 3:1. The MFI zeolite phase was identified by XRD and FT-IR analysis. In XRD analysis the prominent peaks were observed at 2θ values of around 6.5° and 23° with a few additional shoulder peaks in case of all the indium incorporated samples suggesting formation of pure phase of the MFI zeolite. All the samples under the present investigation were found to exhibit high crystallinity (∼92%). The crystallite sizes of the samples were found to vary from about 49 to 55 nm. IR results confirmed the formation of MFI zeolite in all cases showing distinct absorbance bands near 1080, 790, 540, 450 and 990 cm{sup −1}. TG analysis of In-MFI zeolites showed mass losses in three different steps which are attributed to the loss due to adsorbed water molecules and the two types TPA{sup +} cations. Further, the UV–vis (DRS) studies reflected the position of the indium metal in the zeolite framework. Surface area analysis of the synthesized samples was carried out to characterize the synthesized samples The analysis showed that the specific surface area ranged from ∼357 to ∼361 m{sup 2} g{sup −1} and the pore volume of the synthesized samples ranged from 0.177 to 0.182 cm{sup 3} g{sup −1}. The scanning electron microscopy studies showed the structure of the samples to be rectangular and twinned rectangular shaped. The EDX analysis was carried out for confirmation of Si, Al and In in zeolite frame work. The catalytic activities of

  1. Physicochemical properties and different sequence of metal loading (CuFe) over nanoporous of SUZ-4 zeolite.

    PubMed

    Pornrattanapimolchai, Choompoonut; Worathanakul, Patcharin

    2013-04-01

    Different sequence of Cu and Fe loading over nanoporous SUZ-4 zeolite were prepared by incipient wetness impregnation method. K/SUZ-4 zeolite was prepared with SiO2:Al2O3 molar ratio of 21.2 under hydrothermal process at 150 degrees C, 250 rpm for 1 day using tetraethylammonium hydroxide (TEAOH) as a template. Copper(II) and Iron(III) were loaded in K/SUZ-4 with 2.3 and 5.5 wt.% of Copper(II) and 1.0 and 5.0 wt.% of Iron(III). The physico-chemical characterization of CuFe/SUZ-4 were investigated using X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), BET-N2 adsorption, Scanning electron microscopy (SEM) and chemical element analysis. The results show the several types of sequential loading of Cu and Fe metals did not change the structure and pore size of nanoporous SUZ-4 zeolite. The obtained CuFe/SUZ-4 zeolites has a narrow pore size distribution with approximately 0.06 microm diameter with 0.66 microm length of needle crystal shape. PMID:23763208

  2. Energy and materials flows in the copper industry

    SciTech Connect

    Gaines, L.L.

    1980-12-01

    The copper industry comprises both the primary copper industry, which produces 99.9%-pure copper from copper ore, and the secondary copper industry, which salvages and recycles copper-containing scrap metal to extract pure copper or copper alloys. The United States uses about 2 million tons of copper annually, 60% of it for electrical applications. Demand is expected to increase less than 4% annually for the next 20 years. The primary copper industry is concentrated in the Southwest; Arizona produced 66% of the 1979 total ore output. Primary production uses about 170 x 10/sup 12/ Btu total energy annually (about 100 x 10/sup 6/ Btu/ton pure copper produced from ore). Mining and milling use about 60% of the total consumption, because low-grade ore (0.6% copper) is now being mined. Most copper is extracted by smelting sulfide ores, with concomitant production of sulfur dioxide. Clean air regulations will require smelters to reduce sulfur emissions, necessitating smelting process modifications that could also save 20 x 10/sup 12/ Btu (10 x 10/sup 6/ Btu/ton of copper) in smelting energy. Energy use in secondary copper production averages 20 x 10/sup 6/ Btu/ton of copper. If all copper products were recycled, instead of the 30% now salvaged, the energy conservation potential would be about one-half the total energy consumption of the primary copper industry.

  3. Zeolites on Mars: Prospects for Remote Sensing

    NASA Technical Reports Server (NTRS)

    Gaffney, E. S.; Singer, R. B.; Kunkle, T. D.

    1985-01-01

    The Martian surface composition measured by Viking can be represented by several combinations of minerals incorporating major fractions of zeolites known to occur in altered mafic rocks and polar soils on Earth. The abundant occurrence of zeolites on Mars is consistent with what is known about both the physical and chemical environment of that planet. The laboratory reflectance spectra (0.65 to 2.55 microns) of a number of relatively pure zeolite minerals and some naturally occurring zeolite-clay soils were measured. All of the spectra measured are dominated by strong absorption near 1.4 and 1.9 microns and a steep reflectance drop longward of about 2.2 microns, all of which are due to abundant H2O. Weaker water overtone bands are also apparent, and in most cases there is spectral evidence for minor Fe(3+). In these features the zeolite spectra are similar to spectra of smectite clays which have abundant interlayer water. The most diagnostic difference between clay and zeolite spectra is the total absence in the zeolites of the weak structural OH absorption.

  4. Synthesis, characterization and energetics of zeolites

    NASA Astrophysics Data System (ADS)

    Sun, Pingping

    Zeolites are microporous aluminosilicates, and Al or Si can be substituted by other elements, such as Ge, Ga, or P. Zeolites have been studied for more than two hundred years, because of their wide application and importance in mineralogy and technology. With high acidity and special pore system, zeolite beta (IZA code BEA) receives much attention. In the dissertation, the formation and dehydration enthalpy of cation exchanged zeolite beta, Li/Na/K/Rb/Cs/Mg/Ca/Sr/Ba -BEA 14 (14 is the Si/Al ratio), Mg/Ca - BEA 4 (4 is the Si/Al ratio), were studied by high-temperature oxide melt solution calorimetry. From an energetic point of view, zeolites beta are less stable than other zeolites of similar Si/Al ratio and cation content. Their enthalpies of formation and dehydration become more endothermic with increasing average ionic potential of the cations in the channels. The unfavorable enthalpy of low silica Mg-BEA 4 and Ca-BEA 4 suggests a possible energy barrier in their direct synthesis. The formation and partial molar dehydration enthalpy of Li-BEA 3 and Na-BEA 3.67 are also investigated by high temperature calorimetry. The partial molar dehydration enthalpies are a linear function of water content. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents. Ga substitution is of great interest due to the special catalytic character of Ga zeolites and the directing agent effect of Ga atoms. The energetics of gallosilicate zeolites Ga-NaSOD, Ga-NaFAU, Ga-NaNAT, Ga-KNAT, Ga-KLTL and Ga-KTUN-1 were studied. The lattice parameters and adsorbed water content increase after Ga substitution of Al. Compared to analogous aluminosilicate zeolites, the gallosilicate zeolites have a similar dehydration enthalpy per mole of tetrahedra, but a less endothermic dehydration enthalpy per mole of water. The gallosilicate zeolites also have less exothermic formation enthalpies from oxide components. The energetics of Ga

  5. Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

    SciTech Connect

    Dutta, Prabir K.

    2001-09-30

    Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

  6. Tetraethylenepentamine embedded zeolite A for carbon dioxide adsorption.

    PubMed

    Kim, Young-Ki; Mo, Yong-Hwan; Lee, Jun; You, Hyo-Sang; Yi, Chang-Keun; Park, Young Cheol; Park, Sang-Eon

    2013-04-01

    Tetraethylenepentamine (TEPA) embedded zeolite A crystals were synthesized by using TEPA and the preformed zeolite A precursor under the microwave irradiation. The presence of TEPA in zeolite A crystal was confirmed by TG analysis and FTIR, Raman spectra. The CO2 adsorptive behavior of TEPA embedded zeolite A samples was investigated by CO2 isotherms measured at 25 degrees C comparing with zeolite A. The optimum CO2 sorption capacity was found in the case of 7.5% TEPA embedded zeolite A, which showed 3.75 mmol g(-1) where as the zeolite A showed less CO2 adsorption capacity of 2.88 mmol g(-1). The adsorption capacity of TEPA embedded Zeolite A was sustained up to 90% during 4 cycles of temperature swing adsorption (TSA) from 40 degrees C to 140 degrees C, indicating that the TEPA embedded Zeolite A was found to be useful as one of the application to solid amine adsorbent for CO2.

  7. Dispersion strengthened copper

    DOEpatents

    Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

    1990-01-01

    A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

  8. Dispersion strengthened copper

    DOEpatents

    Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

    1989-01-01

    A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

  9. Copper Metallochaperones

    PubMed Central

    Robinson, Nigel J.; Winge, Dennis R.

    2014-01-01

    The current state of knowledge on how copper metallochaperones support the maturation of cuproproteins is reviewed. Copper is needed within mitochondria to supply the CuA and intramembrane CuB sites of cytochrome oxidase, within the trans-Golgi network to supply secreted cuproproteins and within the cytosol to supply superoxide dismutase 1 (Sod1). Subpopulations of copper-zinc superoxide dismutase also localize to mitochondria, the secretory system, the nucleus and, in plants, the chloroplast, which also requires copper for plastocyanin. Prokaryotic cuproproteins are found in the cell membrane and in the periplasm of gram-negative bacteria. Cu(I) and Cu(II) form tight complexes with organic molecules and drive redox chemistry, which unrestrained would be destructive. Copper metallochaperones assist copper in reaching vital destinations without inflicting damage or becoming trapped in adventitious binding sites. Copper ions are specifically released from copper metallochaperones upon contact with their cognate cuproproteins and metal transfer is thought to proceed by ligand substitution. PMID:20205585

  10. Thermodynamic modeling of natural zeolite stability

    SciTech Connect

    Chipera, S.J.; Bish, D.L.

    1997-06-01

    Zeolites occur in a variety of geologic environments and are used in numerous agricultural, commercial, and environmental applications. It is desirable to understand their stability both to predict future stability and to evaluate the geochemical conditions resulting in their formation. The use of estimated thermodynamic data for measured zeolite compositions allows thermodynamic modeling of stability relationships among zeolites in different geologic environments (diagenetic, saline and alkaline lakes, acid rock hydrothermal, basic rock, deep sea sediments). This modeling shows that the relative cation abundances in both the aqueous and solid phases, the aqueous silica activity, and temperature are important factors in determining the stable zeolite species. Siliceous zeolites (e.g., clinoptilolite, mordenite, erionite) present in saline and alkaline lakes or diagenetic deposits formed at elevated silica activities. Aluminous zeolites (e.g., natrolite, mesolite/scolecite, thomsonite) formed in basic rocks in association with reduced silica activities. Likewise, phillipsite formation is favored by reduced aqueous silica activities. The presence of erionite, chabazite, and phillipsite are indicative of environments with elevated potassium concentrations. Elevated temperature, calcic water conditions, and reduced silica activity help to enhance the laumontite and wairakite stability fields. Analcime stability increases with increased temperature and aqueous Na concentration, and/or with decreased silica activity.

  11. Three Mile Island zeolite vitirification demonstration program

    SciTech Connect

    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.

  12. Probing zeolites by vibrational spectroscopies.

    PubMed

    Bordiga, Silvia; Lamberti, Carlo; Bonino, Francesca; Travert, Arnaud; Thibault-Starzyk, Frédéric

    2015-10-21

    This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Brønsted and Lewis acidity and surface basicity are treated in detail. The role of probe molecules and the relevance of tuning both the proton affinity and the steric hindrance of the probe to fully understand and map the complex site population present inside microporous materials are critically discussed. A detailed description of the methods needed to precisely determine the IR absorption coefficients is given, making IR a quantitative technique. The thermodynamic parameters of the adsorption process that can be extracted from a variable-temperature IR study are described. Finally, cutting-edge space- and time-resolved experiments are reviewed. All aspects are discussed by reporting relevant examples. When available, the theoretical literature related to the reviewed experimental results is reported to support the interpretation of the vibrational spectra on an atomic level.

  13. The zeolite deposits of Greece

    USGS Publications Warehouse

    Stamatakis, M.G.; Hall, A.; Hein, J.R.

    1996-01-01

    Zeolites are present in altered pyroclastic rocks at many localities in Greece, and large deposits of potential economic interest are present in three areas: (1) the Evros region of the province of Thrace in the north-eastern part of the Greek mainland; (2) the islands of Kimolos and Poliegos in the western Aegean; and (3) the island of Samos in the eastern Aegean Sea. The deposits in Thrace are of Eocene-Oligocene age and are rich in heulandite and/or clinoptilolite. Those of Kimolos and Poliegos are mainly Quaternary and are rich in mordenite. Those of Samos are Miocene, and are rich in clinoptilolite and/or analcime. The deposits in Thrace are believed to have formed in an open hydrological system by the action of meteoric water, and those of the western Aegean islands in a similar way but under conditions of high heat flow, whereas the deposits in Samos were formed in a saline-alkaline lake.

  14. Salt-occluded zeolite waste forms: Crystal structures and transformability

    SciTech Connect

    Richardson, J.W. Jr.

    1996-12-31

    Neutron diffraction studies of salt-occluded zeolite and zeolite/glass composite samples, simulating nuclear waste forms loaded with fission products, have revealed complex structures, with cations assuming the dual roles of charge compensation and occlusion (cluster formation). These clusters roughly fill the 6--8 {angstrom} diameter pores of the zeolites. Samples are prepared by equilibrating zeolite-A with complex molten Li, K, Cs, Sr, Ba, Y chloride salts, with compositions representative of anticipated waste systems. Samples prepared using zeolite 4A (which contains exclusively sodium cations) as starting material are observed to transform to sodalite, a denser aluminosilicate framework structure, while those prepared using zeolite 5A (sodium and calcium ions) more readily retain the zeolite-A structure. Because the sodalite framework pores are much smaller than those of zeolite-A, clusters are smaller and more rigorously confined, with a correspondingly lower capacity for waste containment. Details of the sodalite structures resulting from transformation of zeolite-A depend upon the precise composition of the original mixture. The enhanced resistance of salt-occluded zeolites prepared from zeolite 5A to sodalite transformation is thought to be related to differences in the complex chloride clusters present in these zeolite mixtures. Data relating processing conditions to resulting zeolite composition and structure can be used in the selection of processing parameters which lead to optimal waste forms.

  15. Luminescent host–guest materials of electrostatically adsorbed Eu{sup 3+}(tta){sub 3}-tpyIL on zeolite L crystals

    SciTech Connect

    Li, Peng; Wang, Dongyue; Liang, Dong; Zhang, Li; Zhang, Shuming; Wang, Yige

    2014-07-01

    Graphical abstract: Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes. - Highlights: • Luminescent ionic europium(III) complex was synthesized. • Outer surface of zeolite L was modified by electrostatic adsorption of the ionic complex. • Luminescent host–guest material with tunable emission color was obtained. - Abstract: The surface modification of zeolite L crystals with lanthanide complexes was achieved by electrostatic adsorption of ionic europium(III) complexes that are prepared by the reaction of tris(2-thenoyltrifluoroacetonate) europium(III) dehydrate with an organic salt containing terpyridine moieties on the negative charge-bearing surfaces of zeolite L crystals. Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes.

  16. Zeolite-based SCR catalysts and their use in diesel engine emission treatment

    DOEpatents

    Narula, Chaitanya K; Yang, Xiaofan

    2015-03-24

    A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

  17. Zeolite-based SCR catalysts and their use in diesel engine emission treatment

    DOEpatents

    Narula, Chaitanya K.; Yang, Xiaofan

    2016-08-02

    A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

  18. The adsorption and mass-transfer process of cationic red X-GRL dye on natural zeolite.

    PubMed

    Tian, Jingjing; Guan, Junfang; Gao, Huimin; Wen, Yafei; Ren, Zijie

    2016-01-01

    The adsorption behavior of natural zeolite was studied in order to determine the adsorption capacity and mass-transfer process of cationic red X-GRL (C(18)H(21)BrN(6)) onto the adsorbent. The adsorption tests to determine both the uptake capacity and the mass-transfer process at equilibrium were performed under batch conditions, which showed rapid uptake in general for the initial 5 min, corresponding to 92% total removal. The equilibrium adsorption capacity value (q(e,cal)) in pseudo-second-order kinetics was 13.51 mg/g at 293 K and the whole adsorption process was governed by physical adsorption with an endothermic, endothermic spontaneous nature. Adsorption tests indicated that the zeolite has great potential as an alternative low-cost material in the treatment of X-GRL drainage. However, the mass-transfer process to determine the rate-controlling steps showed that both film diffusion and pore diffusion were important in controlling the adsorption rate. The adsorption process was governed by film diffusion while pore diffusion was poor because the X-GRL molecules could not penetrate into the zeolite easily. The X-GRL molecules were only adsorbed on the external surface of the zeolite. Hence, to improve the adsorption capacity of natural zeolite further, modification to expand its micropores is necessary.

  19. The adsorption and mass-transfer process of cationic red X-GRL dye on natural zeolite.

    PubMed

    Tian, Jingjing; Guan, Junfang; Gao, Huimin; Wen, Yafei; Ren, Zijie

    2016-01-01

    The adsorption behavior of natural zeolite was studied in order to determine the adsorption capacity and mass-transfer process of cationic red X-GRL (C(18)H(21)BrN(6)) onto the adsorbent. The adsorption tests to determine both the uptake capacity and the mass-transfer process at equilibrium were performed under batch conditions, which showed rapid uptake in general for the initial 5 min, corresponding to 92% total removal. The equilibrium adsorption capacity value (q(e,cal)) in pseudo-second-order kinetics was 13.51 mg/g at 293 K and the whole adsorption process was governed by physical adsorption with an endothermic, endothermic spontaneous nature. Adsorption tests indicated that the zeolite has great potential as an alternative low-cost material in the treatment of X-GRL drainage. However, the mass-transfer process to determine the rate-controlling steps showed that both film diffusion and pore diffusion were important in controlling the adsorption rate. The adsorption process was governed by film diffusion while pore diffusion was poor because the X-GRL molecules could not penetrate into the zeolite easily. The X-GRL molecules were only adsorbed on the external surface of the zeolite. Hence, to improve the adsorption capacity of natural zeolite further, modification to expand its micropores is necessary. PMID:27148713

  20. Monitoring early zeolite formation via in situ electrochemical impedance spectroscopy.

    PubMed

    Brabants, G; Lieben, S; Breynaert, E; Reichel, E K; Taulelle, F; Martens, J A; Jakoby, B; Kirschhock, C E A

    2016-04-01

    Hitherto zeolite formation has not been fully understood. Although electrochemical impedance spectroscopy has proven to be a versatile tool for characterizing ionic solutions, it was never used for monitoring zeolite growth. We show here that EIS can quantitatively monitor zeolite formation, especially during crucial early steps where other methods fall short. PMID:27020096

  1. Monitoring early zeolite formation via in situ electrochemical impedance spectroscopy.

    PubMed

    Brabants, G; Lieben, S; Breynaert, E; Reichel, E K; Taulelle, F; Martens, J A; Jakoby, B; Kirschhock, C E A

    2016-04-01

    Hitherto zeolite formation has not been fully understood. Although electrochemical impedance spectroscopy has proven to be a versatile tool for characterizing ionic solutions, it was never used for monitoring zeolite growth. We show here that EIS can quantitatively monitor zeolite formation, especially during crucial early steps where other methods fall short.

  2. Molecular simulations and experimental studies of zeolites

    NASA Astrophysics Data System (ADS)

    Moloy, Eric C.

    Zeolites are microporous aluminosilicate tetrahedral framework materials that have symmetric cages and channels with open-diameters between 0.2 and 2.0 nm. Zeolites are used extensively in the petrochemical industries for both their microporosity and their catalytic properties. The role of water is paramount to the formation, structure, and stability of these materials. Zeolites frequently have extra-framework cations, and as a result, are important ion-exchange materials. Zeolites also play important roles as molecular sieves and catalysts. For all that is known about zeolites, much remains a mystery. How, for example, can the well established metastability of these structures be explained? What is the role of water with respect to the formation, stabilization, and dynamical properties? This dissertation addresses these questions mainly from a modeling perspective, but also with some experimental work as well. The first discussion addresses a special class of zeolites: pure-silica zeolites. Experimental enthalpy of formation data are combined with molecular modeling to address zeolitic metastability. Molecular modeling is used to calculate internal surface areas, and a linear relationship between formation enthalpy and internal surface areas is clearly established, producing an internal surface energy of approximately 93 mJ/m2. Nitrate bearing sodalite and cancrinite have formed under the caustic chemical conditions of some nuclear waste processing centers in the United States. These phases have fouled expensive process equipment, and are the primary constituents of the resilient heels in the bottom of storage tanks. Molecular modeling, including molecular mechanics, molecular dynamics, and density functional theory, is used to simulate these materials with respect to structure and dynamical properties. Some new, very interesting results are extracted from the simulation of anhydrous Na6[Si6Al 6O24] sodalite---most importantly, the identification of two distinct

  3. The structure of actinide ions exchanged into native and modified zeolites and clays

    SciTech Connect

    Wasserman, S. R.; Soderholm, L.; Giaquinta, D. M.

    2000-02-16

    X-ray absorption spectroscopy (XAS) has been used to investigate the structure and valence of thorium (Th{sup 4+}) and uranyl (UO{sub 2}{sup 2+}) cations exchanged into two classes of microporous aluminosilicate minerals: zeolites and smectite clays. XAS is also employed to examine the fate of the exchanged cations after modification of the mineral surface using self-assembled organic films and/or exposure to hydrothermal conditions. These treatments serve as models for the forces that ultimately determine the chemical fate of the actinide cations in the environment. The speciation of the cations depends on the pore size of the aluminosilicate, which is fixed for the zeolites and variable for the smectites.

  4. Low-temperature synthesis of zeolite from perlite waste — Part II: characteristics of the products

    NASA Astrophysics Data System (ADS)

    Król, Magdalena; Morawska, Justyna; Mozgawa, Włodzimierz; Pichór, Waldemar

    2014-12-01

    The paper investigates the properties of sodium zeolites synthesized using the hydrothermal method under autogenous pressure at low temperature with NaOH solutions of varying concentrations. During this modification, zeolites X, Na-P1 and hydroxysodalite were synthesized. The synthesis parameters, and thus, phase composition of resulting samples, significantly affected the specific surface area (SSA) and cation exchange capacity (CEC). SSA increased from 2.9 m2/g to a maximum of 501.2 m2/g, while CEC rose from 16 meq/100 g to a maximum of 500 meq/100 g. The best properties for use as a sorbent were obtained for perlite waste modified with 4.0 M NaOH at 70 °C or 80 °C.

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

    PubMed

    Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

    2015-01-01

    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.

  6. Towards a sustainable manufacture of hierarchical zeolites.

    PubMed

    Verboekend, Danny; Pérez-Ramírez, Javier

    2014-03-01

    Hierarchical zeolites have been established as a superior type of aluminosilicate catalysts compared to their conventional (purely microporous) counterparts. An impressive array of bottom-up and top-down approaches has been developed during the last decade to design and subsequently exploit these exciting materials catalytically. However, the sustainability of the developed synthetic methods has rarely been addressed. This paper highlights important criteria to ensure the ecological and economic viability of the manufacture of hierarchical zeolites. Moreover, by using base leaching as a promising case study, we verify a variety of approaches to increase reactor productivity, recycle waste streams, prevent the combustion of organic compounds, and minimize separation efforts. By reducing their synthetic footprint, hierarchical zeolites are positioned as an integral part of sustainable chemistry.

  7. Hydrogen Purification Using Natural Zeolite Membranes

    NASA Technical Reports Server (NTRS)

    DelValle, William

    2003-01-01

    The School of Science at Universidad del Turabo (UT) have a long-lasting investigation plan to study the hydrogen cleaning and purification technologies. We proposed a research project for the synthesis, phase analysis and porosity characterization of zeolite based ceramic perm-selective membranes for hydrogen cleaning to support NASA's commitment to achieving a broad-based research capability focusing on aerospace-related issues. The present study will focus on technology transfer by utilizing inorganic membranes for production of ultra-clean hydrogen for application in combustion. We tested three different natural zeolite membranes (different particle size at different temperatures and time of exposure). Our results show that the membranes exposured at 900 C for 1Hr has the most higher permeation capacity, indicated that our zeolite membranes has the capacity to permeate hydrogen.

  8. Growth of zeolite crystals in the microgravity environment of space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Sand, L. B.; Collette, D.; Dieselman, K.; Crowley, J.; Feitelberg, A.

    1986-01-01

    Zeolites are hydrated, crystalline aluminosilicates with alkali and alkaling earth metals substituted into cation vacancies. Typically zeolite crystals are 3 to 8 microns. Larger cyrstals are desirable. Large zeolite crystals were produced (100 to 200 microns); however, they have taken restrictively long times to grow. It was proposed if the rate of nucleation or in some other way the number of nuclei can be lowered, fewer, larger crystals will be formed. The microgravity environment of space may provide an ideal condition to achieve rapid growth of large zeolite crystals. The objective of the project is to establish if large zeolite crystals can be formed rapidly in space.

  9. Simultaneous determination of arsenic, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, selenium, and zinc in fertilizers by microwave acid digestion and inductively coupled plasma-optical emission spectrometry detection: single-laboratory validation of a modification and extension of AOAC 2006.03.

    PubMed

    Webb, Sharon; Bartos, James; Boles, Rhonda; Hasty, Elaine; Thuotte, Ethel; Thiex, Nancy J

    2014-01-01

    A single-laboratory validation study was conducted for the simultaneous determination of arsenic, cadmium, calcium, cobalt, copper, chromium, iron, lead, magnesium, manganese, molybdenum, nickel, selenium, and zinc in all major types of commercial fertilizer products by microwave digestion and inductively coupled plasma-optical emission spectroscopy analysis. This validation study proposes an extension and modification of AOAC 2006.03. The extension is the inclusion of calcium, copper, iron, magnesium, manganese, and zinc, and the modification is incorporation of hydrochloric acid in the digestion system. This dual acid digestion utilizes both hydrochloric and nitric acids in a 3 to 9 mL volume ratio/100 mL. In addition to 15 of the 30 original validation materials used in the 2006.03 collaborative study, National Institute of Standards and Technology Standard Reference Material 695 and Magruder 2009-06 were incorporated as accuracy materials. The main benefits of this proposed method are a significant increase in laboratory efficiency when compared to the use of both AOAC Methods 965.09 and 2006.03 to achieve the same objective and an enhanced recovery of several metals.

  10. The effects of surface modification on the speciation of metal ions intercalated into aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Giaquinta, D.M.; Yuchs, S.E.; Soderholm, L.

    1996-12-31

    Microporous aluminosilicates, including clay minerals and zeolites, are ion-exchange materials. In their most common forms, they have the ability to incorporate cationic species within their matrices. Because of this property, microporous aluminosilicates have been proposed as storage media for hazardous waste. In this paper the authors use X-ray absorption spectroscopy (XAS) to examine the structure of cations held within smectite clay minerals and to determine how modification of the surface of the clay using an organic monolayer affects the coordination of the stored cation. The effects of hydrothermal and thermal processing on the coordination of the ions contained within these systems are also investigated. The presence of the monolayer changes the surface of the clay from hydrophilic to hydrophobic. It inhibits the interlayer ions from exchanging freely into environmental water and reduces the leach rate of cations out of the clay by approximately a factor of 20. Significant changes are observed when these coated samples are treated under hydrothermal and thermal conditions. Reductions of uranium (VI), in the form of uranyl, and cupric ions occur. In addition, the uranium aggregates, forming small particles that appear similar to UO{sub 2}. Comparable conglomeration occurs with lead cations and with the reduced copper species.

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

    PubMed

    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.

  12. Synthesis of zeolite as ordered multicrystal arrays.

    PubMed

    Lee, Jin Seok; Lee, Yun-Jo; Tae, Eunju Lee; Park, Yong Soo; Yoon, Kyung Byung

    2003-08-01

    Zeolites are crystalline nanoporous aluminosilicates widely used in industry. In order for zeolites to find applications as innovative materials, they need to be organized into large two- and three-dimensional (2D and 3D) arrays. We report that uniformly aligned polyurethane films can serve as templates for the synthesis of uniformly aligned 2D and possibly 3D arrays of silicalite-1 crystals, in which the orientations of the crystals are controlled by the nature of the polymers. We propose that the supramolecularly organized organic-inorganic composites that consist of the hydrolyzed organic products and the seed crystals are responsible for this phenomenon.

  13. Fly ash zeolite catalyst support for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Campen, Adam

    This dissertation research aimed at evaluating a fly ash zeolite (FAZ) catalyst support for use in heterogeneous catalytic processes. Gas phase Fischer-Tropsch Synthesis (FTS) over a fixed-bed of the prepared catalyst/FAZ support was identified as an appropriate process for evaluation, by comparison with commercial catalyst supports (silica, alumina, and 13X). Fly ash, obtained from the Wabash River Generating Station, was first characterized using XRD, SEM/EDS, particle size, and nitrogen sorption techniques. Then, a parametric study of a two-step alkali fusion/hydrothermal treatment process for converting fly ash to zeolite frameworks was performed by varying the alkali fusion agent, agent:flyash ratio, fusion temperature, fused ash/water solution, aging time, and crystallization time. The optimal conditions for each were determined to be NaOH, 1.4 g NaOH: 1 g fly ash, 550 °C, 200 g/L, 12 hours, and 48 hours. This robust process was applied to the fly ash to obtain a faujasitic zeolite structure with increased crystallinity (40 %) and surface area (434 m2/g). Following the modification of fly ash to FAZ, ion exchange of H+ for Na+ and cobalt incipient wetness impregnation were used to prepare a FTS catalyst. FTS was performed on the catalysts at 250--300 °C, 300 psi, and with a syngas ratio H2:CO = 2. The HFAZ catalyst support loaded with 11 wt% cobalt resulted in a 75 % carbon selectivity for C5 -- C18 hydrocarbons, while methane and carbon dioxide were limited to 13 and 1 %, respectively. Catalyst characterization was performed by XRD, N2 sorption, TPR, and oxygen pulse titration to provide insight to the behavior of each catalyst. Overall, the HFAZ compared well with silica and 13X supports, and far exceeded the performance of the alumina support under the tested conditions. The successful completion of this research could add value to an underutilized waste product of coal combustion, in the form of catalyst supports in heterogeneous catalytic processes.

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

    PubMed

    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. PMID:27483802

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

    PubMed

    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.

  16. Home Modification

    MedlinePlus

    ... it is important to consider certain safety modifications. Adaptations such as those in the following list can ... The importance of a Consumer Perspective in Home Adaptation of Alzheimer’s Households” (Chapter 6 pp 91-112) ...

  17. Multicomponent liquid ion exchange with chabazite zeolites

    SciTech Connect

    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.

  18. MERCURY SEPARATION FROM POLLUTANT WATER USING ZEOLITES

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water that causes arsenical dermatitis and skin cancer. In the present work, the potential use of a variety of synthetic zeolites for removal of arsenic from water has been examined at room temperature. Experiments have...

  19. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  20. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  1. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    ERIC Educational Resources Information Center

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  2. Chemical interactions in multimetal/zeolite catalysts

    SciTech Connect

    Sachtler, W.M.H.

    1992-02-07

    Mechanistic explanations have been found for the migration of atoms and ions through the zeolite channels leading to specific distribution of ions and the metal clusters. In this report, we summarize the state of understanding attained on a number of topics in the area of mono- and multimetal/zeolite systems, to which our recent research has made significant contributions. The following topics are discussed: (1) Formation of isolated metal atoms in sodalite cages; (2) differences of metal/zeolite systems prepared by ion reduction in channels or via isolated atoms; (3) rejuvenation of Pd/NaY and Pd/HY catalysts by oxidative redispersion of the metal; (4) formation of mono- or bimetal particles in zeolites by programmed reductive decomposition of volatile metal complexes; (5) cation-cation interaction as a cause of enhanced reducibility; (6) formation of palladium carbonyl clusters in supercages; (7) enhanced catalytic activity of metal particle-proton complexes for hydrocarbon conversion reactions; (8) stereoselectivity of catalytic reactions due to geometric constraints of particles in cages.

  3. Ubiquitin modifications

    PubMed Central

    Swatek, Kirby N; Komander, David

    2016-01-01

    Protein ubiquitination is a dynamic multifaceted post-translational modification involved in nearly all aspects of eukaryotic biology. Once attached to a substrate, the 76-amino acid protein ubiquitin is subjected to further modifications, creating a multitude of distinct signals with distinct cellular outcomes, referred to as the 'ubiquitin code'. Ubiquitin can be ubiquitinated on seven lysine (Lys) residues or on the N-terminus, leading to polyubiquitin chains that can encompass complex topologies. Alternatively or in addition, ubiquitin Lys residues can be modified by ubiquitin-like molecules (such as SUMO or NEDD8). Finally, ubiquitin can also be acetylated on Lys, or phosphorylated on Ser, Thr or Tyr residues, and each modification has the potential to dramatically alter the signaling outcome. While the number of distinctly modified ubiquitin species in cells is mind-boggling, much progress has been made to characterize the roles of distinct ubiquitin modifications, and many enzymes and receptors have been identified that create, recognize or remove these ubiquitin modifications. We here provide an overview of the various ubiquitin modifications present in cells, and highlight recent progress on ubiquitin chain biology. We then discuss the recent findings in the field of ubiquitin acetylation and phosphorylation, with a focus on Ser65-phosphorylation and its role in mitophagy and Parkin activation. PMID:27012465

  4. Copper cyanide

    Integrated Risk Information System (IRIS)

    Copper cyanide ; CASRN 544 - 92 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  5. Conversion of Ethanol to Hydrocarbons on Hierarchical HZSM-5 Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Zhang, He; Sun, Junming; Wang, Yong

    2014-02-22

    This study reports synthesis, characterization, and catalytic activity of the nano-size hierarchical HZSM-5 zeolite with high mesoporosity produced via a solvent evaporation procedure. Further, this study compares hierarchical zeolites with conventional HZSM-5 zeolite with similar Si/Al ratios for the ethanol-to-hydrocarbon conversion process. The catalytic performance of the hierarchical and conventional zeolites was evaluated using a fixed-bed reactor at 360 °C, 300 psig, and a weight hourly space velocity of 7.9 h-1. For the low Si/Al ratio zeolite (~40), the catalytic life-time for the hierarchical HZSM-5 was approximately 2 times greater than the conventional HZSM-5 despite its coking amount deposited 1.6 times higher than conventional HZSM-5. For the high Si/Al ratio zeolite (~140), the catalytic life-time for the hierarchical zeolite was approximately 5 times greater than the conventional zeolite and the amount of coking deposited was 2.1 times higher. Correlation was observed between catalyst life time, porosity, and the crystal size of the zeolite. The nano-size hierarchical HZSM-5 zeolites containing mesoporosity demonstrated improved catalyst life-time compared to the conventional catalyst due to faster removal of products, shorter diffusion path length, and the migration of the coke deposits to the external surface from the pore structure.

  6. Energetics of sodium-calcium exchanged zeolite A.

    PubMed

    Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

    2015-05-01

    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.

  7. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    PubMed Central

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-01-01

    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. PMID:26616161

  8. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins.

    PubMed

    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

    2015-01-01

    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. PMID:26616161

  9. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    NASA Astrophysics Data System (ADS)

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-11-01

    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.

  10. MCM-41 impregnated with A zeolite precursor: Synthesis, characterization and tetracycline antibiotics removal from aqueous solution

    PubMed Central

    Liu, Minmin; Hou, Li-an; Yu, Shuili; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-01-01

    In this paper, the MCM-41 has been modified by impregnation with zeolite A to prepare a kind of new adsorbent. The adsorption of TC from aqueous solutions onto modified MCM-41 has been studied. It was discovered that the adsorption capability of zeolite A modified MCM-41 (A-MCM-41) increased dramatically after modification. The modified MCM-41 was characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption, Fourier Transform Infrared (FTIR) analysis, Transmission electron microscopy (TEM) images, and 29Si and 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectra. The modified MCM-41 structure was still retained after impregnated with zeolite A but the surface area and pore diameter decreased due to pore blockage. The adsorption of TC on modified MCM-41 was discussed regarding various parameters such as pH, initial TC concentration, and the reaction time. The pH effects on TC adsorption indicated that the adsorbents had better adsorption performances in acidic and neutral conditions. The adsorption isotherms were fitted well by the Langmuir model. The adsorption kinetics was well described by both pseudo-second order equation and the intra-particle diffusion model. The adsorption behavior in a fixed-bed column system followed Thomas model. The adsorption behavior of TC was the chemical adsorption with an ion exchange process and electrostatic adsorption. PMID:24976787

  11. Mechanisms of CPB Modified Zeolite on Mercury Adsorption in Simulated Wastewater.

    PubMed

    Liu, Jiang; Huang, Hui; Huang, Rong; Zhang, Jinzhong; Hao, Shuoshuo; Shen, Yuanyuan; Chen, Hong

    2016-06-01

    A systematic study was carried out to analyze the effects of mercury(II) adsorption by surface modified zeolite (SMZ) and adsorption mechanism. Cetylpyridinium bromide (CPB) was used to prepare SMZ. The characterization methods by means of powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscope (SEM) showed that both the surface and internal zeolite were covered with CPB molecules, but the main binding sites were surface. Results showed that the organic carbon and cation exchange capacity of the SMZ were 7.76 times and 4.22 times higher than those of natural zeolite (NZ), respectively. Zeta potentials before and after modification were measured at -7.80 mV and -30.27 mV, respectively. Moreover, the saturation adsorptive capacity of SMZ was 16.35 times higher than NZ in mercury-containing wastewater. The possible mechanisms of mercury elimination were surface adsorption, hydrophobic interaction, ion exchange, electricity neutralization. The adsorption process was affected little by competitive ions.

  12. UTILITY OF ZEOLITES IN REMOVAL OF INORGANIC AND ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic and organic pollutants have been removed from water at room temperature using various zeolites. Synthetic zeolite Faujasite Y has been used to remove inorganic pollutants...

  13. CO2 SEPARATIONS USING ZEOLITE MEMBRANES

    SciTech Connect

    Richard D. Noble; John L. Falconer

    2001-06-30

    Zeolite and other inorganic molecular sieve membranes have shown potential for separations based on molecular size and shape because of their small pore sized, typically less than 1 nm, and their narrow pore size distribution. The high thermal and chemical stability of these inorganic crystals make them ideal materials for use in high temperature applications such as catalytic membrane reactors. Most of the progress with zeolite membranes has been with MFI zeolites prepared on porous disks and tubes. The MFI zeolite is a medium pore size structure having nearly circular pores with diameters between .53 and .56 nm. Separation experiments through MFI membranes indicate that competitive adsorption separates light gas mixtures. Light gas selectivities are typically small, however, owing to small differences in adsorption strengths and their small sizes relative to the MFI pore opening. Furthermore, competitive adsorption does not work well at high temperature where zeolite membranes are stable and have potential application. Separation by differences in size has a greater potential to work at high temperature than competitive adsorption, but pores smaller than those in MFI zeolites are required. Therefore, some studies focused on the synthesis of a small, 8-membered-pore structures such as zeolite A (0.41-nm pore diameter) and SAPO-34, a chabazite (about .4-nm pore diameter with about 1.4 nm cages) analog. The small pore size of the zeolite A and SAPO-34 structures made the separation of smaller molecules by differences in size possible. Zeolite MFI and SAPO-34 membranes were prepared on the inside surface of porous alumina tubes by hydrothermal synthesis, and single gas and binary mixture permeances were measured to characterize the membrane's performance. A mathematical diffusion model was developed to determine the relative quantities of zeolite and non-zeolite pores in different membranes by modeling the permeation date of CO{sub 2}. This model expresses the total

  14. In situ DRIFTS-MS studies on the oxidation of adsorbed NH3 by NOx over a Cu-SSZ-13 zeolite

    SciTech Connect

    Zhu, Haiyang; Kwak, Ja Hun; Peden, Charles HF; Szanyi, Janos

    2013-04-30

    DRIFT spectroscopy combined with mass spectrometry was used to investigate the oxidation of adsorbed ammonia by NO2, NO+O2 and NO2+O2 on a copper ion exchanged SSZ 13 (Cu-SSZ-13) zeolite. Compared with both NO2 and NO, the adsorption of ammonia is much stronger on the Cu-SSZ-13 zeolite. Two adsorbed ammonia species were found over the Cu-SSZ-13 zeolite studied here; notably ammonia on Brönsted acid sites (proton) and ammonia on Lewis acid sites (copper ions). These adsorbed ammonia species present different activity profiles and selectivity to N2 during NH3 oxidation. The results obtained suggest that ammonia adsorbed onto copper ions in Cu-SSZ-13 are more active at low temperatures than proton-adsorbed NH3, and give rise to a higher selectivity to N2. The formation of N2O is associated primarily with the reaction of NOx with proton-adsorbed NH3 via the formation and subsequent thermal decomposition of NH4NO3. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. Portions of this work were performed in the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for the US DOE by Battelle.

  15. Preparation of Robust, Thin Zeolite Membrane Sheet for Molecular Separation

    SciTech Connect

    Liu, Wei; Zhang, Jian; Canfield, Nathan L.; Saraf, Laxmikant V.

    2011-10-19

    This paper reports a feasibility study on the preparation of zeolite membrane films on a thin, porous metal support sheet (50-{micro}m thick). Zeolite sodium A (NaA) and silicalite zeolite frameworks are chosen to represent synthesis of respective hydrophilic-type and hydrophobic-type zeolite membranes on this new support. It is found that a dense, continuous inter-grown zeolite crystal layer at a thickness less than 2 {micro}m can be directly deposited on such a support by using direct and secondary growth techniques. The resulting membrane shows excellent adhesion on the metal sheet. Molecular-sieving functions of the prepared membranes are characterized with ethanol/water separation, CO2 separation, and air dehumidification. The results show great potential to make flexible metal-foil-like zeolite membranes for a range of energy conversion and environmental applications.

  16. Atomic sites and stability of Cs+ captured within zeolitic nanocavities.

    PubMed

    Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H; Sasaki, Yukichi

    2013-01-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as (137)Cs(+) from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs(+) ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs(+) ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

  17. Atomic sites and stability of Cs+ captured within zeolitic nanocavities

    NASA Astrophysics Data System (ADS)

    Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

    2013-08-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

  18. Zeolite catalysis in conversion of cellulosics. Annual report

    SciTech Connect

    Tsao, G.T.

    1994-02-01

    The authors have studied the kinetics of oxylose/xylulose isomerization in significant detail over a variety of zeolites and obtained the pseudo-first order reaction rate constants. The authors have found that HY zeolite is still the best material and zeolites are more selective than homogeneous acid catalysts where decomposition of the sugar compounds is much faster. They have completed, as described in the Year 2 Work Plan, the study of cellobiose hydrolysis with an ion exchange resin. The kinetics of the solid-catalyzed reaction is qualitatively similar to that for catalysis by homogeneous acids. The planned program of NMR studies has revealed the dynamics of sugar molecules within the zeolite cavities. Two chemisorbed and a physisorbed state have been identified in HY zeolite. A new state, accounting for as much as a half of the sugar, has been found in ZSM-5 zeolite.

  19. Prediction of Zeolite Framework Types by a Machine Learning Approach

    NASA Astrophysics Data System (ADS)

    Yang, Shujiang; Lach-Hab, Mohammed; Vaisman, Iosif; Blaisten-Barojas, Estela

    2009-03-01

    Zeolites are microporous crystalline materials with highly regular framework structures consisting of molecular-sized pores and channels. Characteristic framework types of zeolites are traditionally determined by the combined information of coordination sequences and vertex symbols. Here we present a machine learning model for classifying zeolite crystals according to their framework types. An eighteen-dimensional feature vector is defined including topological descriptors and physical/chemical properties of zeolite crystals [Microporous and Mesoporous Materials 117, 339 (2009)]. Trained with crystallographic data of known zeolites, the new model can predict the framework types of unknown zeolite crystals with up to 98 % accuracy. Compared with conventional methods, the machine learning model is more robust handling crystal disorder and/or crystal defects in a more effective manner. This model can be adapted for classifying and clustering other crystalline species.

  20. Zeolite and swine inoculum effect on poultry manure biomethanation

    NASA Astrophysics Data System (ADS)

    Kougias, P. G.; Fotidis, I. A.; Zaganas, I. D.; Kotsopoulos, T. A.; Martzopoulos, G. G.

    2013-03-01

    Poultry manure is an ammonia-rich substrate that inhibits methanogenesis, causing severe problems to the anaerobic digestion process. In this study, the effect of different natural zeolite concentrations on the mesophilic anaerobic digestion of poultry waste inoculated with well-digested swine manure was investigated. A significant increase in methane production was observed in treatments where zeolite was added, compared to the treatment without zeolite.Methane production in the treatment with 10 g dm-3 of natural zeolite was found to be 109.75% higher compared to the treatment without zeolite addition. The results appear to be influenced by the addition of zeolite, which reduces ammonia toxicity in anaerobic digestion and by the ammonia-tolerant swine inoculum.

  1. Inclusion of polyaniline filaments in zeolite molecular sieves

    SciTech Connect

    Enzel, P.; Bein, T. )

    1989-08-24

    Polyaniline has been synthesized in the channels of mordenite (one-dimensional) and zeolite Y (three-dimensional). Aniline was diffused from hexane solution into dehydrated zeolite pores containing different concentrations of framework hydroxyl groups. Addition of (NH{sub 4}){sub 2}S{sub 2}O{sub 8} to an aqueous suspension of the loaded zeolites afforded intrazeolite polyaniline chains, as demonstrated by FTIR, electronic absorption data, and recovery of the included polymer. Stoichiometric, kinetic, XPS, and microscopic data and the absence of bulk conductivity of the polymer/zeolite powders lead to the conclusion that the polymer is formed inside the host channel system. While the polyaniline chains in mordenite channels appear to be more highly oxidized than in Y zeolite, both systems show spectroscopic features typical of emeraldine base and emeraldine salt polymers. The polyaniline/zeolite hybrids represent a new class of materials containing synthetic conductors encapsulated in crystalline inorganic hosts with channel systems of molecular dimensions.

  2. [Lifestyle modifications].

    PubMed

    Kawano, Yuhei

    2015-11-01

    Lifestyle modifications are important in the prevention and treatment of hypertension. The Japanese Society of Hypertension Guidelines for the Management of Hypertension (JSH2014) recommend salt reduction (< 6 g/day), increased intake of vegetables/fruit and fish (fish oil), reduced intake of cholesterol and saturated fatty acids, weight loss (body mass index < 25kg/m2), exercise (≥ 30 min/day), reduction of alcohol intake (≤ 20-30 mL/day in men, ≤ 10-20 mL/day in women as ethanol), and quitting smoking. These lifestyle modifications are capable of reducing blood pressure and ameliorating other cardiovascular risk factors. However, the reduction in blood pressure is mild to moderate and the adherence to lifestyle modifications has been still suboptimal. PMID:26619658

  3. Bioinspired conical copper wire with gradient wettability for continuous and efficient fog collection.

    PubMed

    Ju, Jie; Xiao, Kai; Yao, Xi; Bai, Hao; Jiang, Lei

    2013-11-01

    Inspired by the efficient fog collection on cactus spines, conical copper wires with gradient wettability are fabricated through gradient electrochemical corrosion and subsequent gradient chemical modification. These dual-gradient copper wires' fog-collection ability is demonstrated to be higher than that of conical copper wires with pure hydrophobic surfaces or pure hydrophilic surfaces, and the underlying mechanism is also analyzed.

  4. Asymmetric printing of molecules and zeolites on self assembled monolayers.

    PubMed

    Kehr, Nermin Seda; Schäfer, Andreas; Ravoo, Bart Jan; De Cola, Luisa

    2010-04-01

    Microcontact printing (mCP) is used to immobilize dyes and peptides asymmetrically, by a "peptide coupling" reaction, on monolayers of zeolite L crystals in the contact area between the stamp and the surface of the monolayer. Chemically patterned surfaces of monolayers of zeolite L crystals are obtained by using patterned stamps with different ink solutions. Additional printing of functionalized nano-objects on SAMs of zeolite L crystals is demonstrated.

  5. Large zeolites - Why and how to grow in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.

    1991-01-01

    The growth of zeolite crystals which are considered to be the most valuable catalytic and adsorbent materials of the chemical processing industry are discussed. It is proposed to use triethanolamine as a nucleation control agent to control the time release of Al in a zeolite A solution and to increase the average and maximum crystal size by 25-50 times. Large zeolites could be utilized to make membranes for reactors/separators which will substantially increase their efficiency.

  6. Fluoride-assisted synthesis of bimodal microporous SSZ-13 zeolite.

    PubMed

    Zhu, Xiaochun; Kosinov, Nikolay; Hofmann, Jan P; Mezari, Brahim; Qian, Qingyun; Rohling, Roderigh; Weckhuysen, Bert M; Ruiz-Martínez, Javier; Hensen, Emiel J M

    2016-02-21

    The presence of small amount of fluoride in alkaline hydrothermal synthesis of SSZ-13 zeolite yields bimodal microporous particles with substantially improved performance in the methanol-to-olefins (MTO) reaction. Hydrocarbon uptake measurements and fluorescence microspectroscopy of spent catalysts demonstrate enhanced diffusion through micropores at the grain boundaries of nanocrystals running through the zeolite particles. Fluoride-assisted SSZ-13 synthesis is a cheap and scalable approach to optimize the performance of MTO zeolite catalysts. PMID:26810114

  7. Dispersion strengthened copper

    DOEpatents

    Sheinberg, H.; Meek, T.T.; Blake, R.D.

    1990-01-09

    A composition of matter is described which is comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide. A method for making this composition of matter is also described. This invention relates to the art of powder metallurgy and, more particularly, it relates to dispersion strengthened metals.

  8. Peculiarities of the dielectric response of natural zeolite composites prepared by using zeolite and silicon powders

    NASA Astrophysics Data System (ADS)

    Ozturk Koc, S.; Orbukh, V. I.; Eyvazova, G. M.; Lebedeva, N. N.; Salamov, B. G.

    2016-03-01

    We present the real and imaginary part of the dielectric permittivity of natural zeolite composites prepared by using zeolite and silicon powders. The dielectric response (DR) dependences on the frequency (3-300 GHz) of electric field and different Si concentrations (5-33%) are non-monotonic and a maximum peak is observed. This peak position is practically independent on the frequency and its maximum is observed in zeolite composites which included 9% of the Si-powder. Also the maximum peak is decreased by about an order of magnitude when frequency increases from 500 Hz to 5 kHz. Addition of the conductive Si-particles to zeolite-powder leads to two opposite effects. Firstly, the movement of electrons in the Si-particles provides increase of DR. Secondly, cations which leaving from zeolite pores can be neutralized by the particles of Si in the intercrystalline-space. Such a peculiar mechanism for recombination of Si electrons and cations from pores leads to a reduction of DR for large silicon concentrations. Due to the fact that the contribution of free carriers in the decreasing of the DR as the frequency increases, it is consistent with the suggestion that the maximum peak decreases with increasing frequency.

  9. Large zeolites: why and how to grow in space

    NASA Astrophysics Data System (ADS)

    Sacco, Albert, Jr.

    1991-12-01

    Zeolite crystals are one of the Chemical Process Industry's most valuable catalytic and adsorbent materials. Large, essentially defect-free zeolite crystals could be used to better understand zeolite catalysis mechanisms, and could help in designing better zeolite adsorption systems. In addition, if zeolites could be made large enough, they could be used to make zeolite membranes; these could be used as reactors/separators, resulting in highly improved efficiency. Space provides a unique environment to grow large zeolites by allowing them to continue to grow suspended in their nutrient field. In order to better utilize this microgravity environment, it is necessary to control the nucleation event. Triethanolamine (TEA) can be used to control the time release of aluminum in a zeolite A solution. In a 1 g environment, the use of TEA resulted in a 25 - 50X increase in average and maximum crystal size. It is proposed that if fluid motion can be controlled and the rate of nutrient transport increased, substantially larger zeolite crystals can be formed in microgravity, using such nucleation control agents.

  10. Zeolite Crystal Growth in Microgravity and on Earth

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP), a NASA-sponsored Research Partnership Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Shown here are zeolite crystals (top) grown in a ground control experiment and grown in microgravity on the USML-2 mission (bottom). Zeolite experiments have also been conducted aboard the International Space Station.

  11. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, George A.

    1986-01-01

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  12. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, G.A.

    1985-03-05

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  13. Dry method for recycling iodine-loaded silver zeolite

    DOEpatents

    Thomas, Thomas R.; Staples, Bruce A.; Murphy, Llewellyn P.

    1978-05-09

    Fission product iodine is removed from a waste gas stream and stored by passing the gas stream through a bed of silver-exchanged zeolite until the zeolite is loaded with iodine, passing dry hydrogen gas through the bed to remove the iodine and regenerate the bed, and passing the hydrogen stream containing the hydrogen iodide thus formed through a lead-exchanged zeolite which adsorbs the radioactive iodine from the gas stream and permanently storing the lead-exchanged zeolite loaded with radioactive iodine.

  14. Ion exchange properties of Japanese natural zeolites in seawater.

    PubMed

    Wajima, Takaaki

    2013-01-01

    Ion exchange properties of five different Japanese natural zeolites in seawater were examined. Sodium ions could be reduced by all zeolites, although anions, Cl(-) and SO(4)(2-), in seawater showed barely changes. Natural zeolite desalination treatment mainly depends on the ion exchange between Na(+), K(+) and Mg(2+) in seawater and Ca(2+) in natural zeolite. This study found that mordenite is superior to clinoptilolite for use in Na(+) reduction. Mordenite with high cation exchange capacity containing Ca(2+) resulted in the highest Na(+) reduction from seawater.

  15. Low-temperature synthesis of zeolite from perlite waste — Part I: review of methods and phase compositions of resulting products

    NASA Astrophysics Data System (ADS)

    Król, Magdalena; Morawska, Justyna; Mozgawa, Włodzimierz; Pichór, Waldemar

    2014-09-01

    In this paper a review of the recent studies on the synthesis of zeolites from expanded perlite under hydrothermal conditions is presented. Attention is paid to possible outcomes of synthesis from low cost glass material, such as perlite. The study also investigates the phase composition of zeolitic materials obtained by modification of by-product derived from an expanded perlite production process. The synthesis was made using the hydrothermal method with sodium hydroxide under autogenous pressure at a temperature below 100 °C for 1 to 72 h. It was possible to obtain a zeolitic material at a temperature as low as 60 °C using 4.0 M NaOH. The X-ray diffraction pattern showed the biggest peak intensity of zeolite X with 4.0 M NaOH at the temperature of 70 °C. During synthesis at higher temperature zeolite Na-P1 (with 3.0 M NaOH at 90 °C) and hydroxysodalite (with 5.0 M NaOH at 90 °C) were obtained.

  16. Pf/Zeolite Catalyst for Tritium Stripping

    SciTech Connect

    Hsu, R.H.

    2001-03-26

    This report described promising hydrogen (protium and tritium) stripping results obtained with a Pd/zeolite catalyst at ambient temperature. Preliminary results show 90-99+ percent tritium stripping efficiency may be obtained, with even better performance expected as bed configuration and operating conditions are optimized. These results suggest that portable units with single beds of the Pd/zeolite catalyst may be utilized as ''catalytic absorbers'' to clean up both tritium gas and tritiated water. A cart-mounted prototype stripper utilizing this catalyst has been constructed for testing. This portable stripper has potential applications in maintenance-type jobs such as tritium line breaks. This catalyst can also potentially be utilized in an emergency stripper for the Replacement Tritium Facility.

  17. Delaminated zeolites: Combining the benefits of zeolites and mesoporous materials for catalytic uses

    SciTech Connect

    Corma, A.; Fornes, V.; Martinez-Triguero, J.; Pergher, S.B.

    1999-08-15

    The delamination of the layered precursor of the MCM-22 zeolite (MWW structure) affords monolayers of a crystalline aluminosilicate with more than 700 m{sup 2}/g of a well defined external surface formed by cups of 0.7 x 0.7 nm. In this layered structure the circular 10-member-ring microporous system is preserved. The resultant material presents the strong acidity and stability characteristic of the zeolites but, at the same time, offers the high accessibility to large molecules characteristic of the amorphous aluminosilicates. The cracking behavior during the process of small and large molecules has been compared with that of the zeolite MCM-22 and pillared laminar precursor MCM-36.

  18. Copper urine test (image)

    MedlinePlus

    The copper urine test is performed by collecting urine at specific times for a 24-hour period. The urine is tested for the amount of copper present. The copper urine test is used to determine the presence of Wilson ...

  19. Characterization of active sites in zeolite catalysts

    SciTech Connect

    Eckert, J.; Bug, A.; Nicol, J.M.

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Atomic-level details of the interaction of adsorbed molecules with active sites in catalysts are urgently needed to facilitate development of more effective and/or environmentally benign catalysts. To this end the authors have carried out neutron scattering studies combined with theoretical calculations of the dynamics of small molecules inside the cavities of zeolite catalysts. The authors have developed the use of H{sub 2} as a probe of adsorption sites by observing the hindered rotations of the adsorbed H{sub 2} molecule, and they were able to show that an area near the four-rings is the most likely adsorption site for H{sub 2} in zeolite A while adsorption of H{sub 2} near cations located on six-ring sites decreases in strength as Ni {approximately} Co > Ca > Zn {approximately} Na. Vibrational and rotational motions of ethylene and cyclopropane adsorption complexes were used as a measure for zeolite-adsorbate interactions. Preliminary studies of the binding of water, ammonia, and methylamines were carried out in a number of related guest-host materials.

  20. Effect of NaX zeolite-modified graphite felts on hexavalent chromium removal in biocathode microbial fuel cells.

    PubMed

    Wu, Xiayuan; Tong, Fei; Yong, Xiaoyu; Zhou, Jun; Zhang, Lixiong; Jia, Honghua; Wei, Ping

    2016-05-01

    Two kinds of NaX zeolite-modified graphite felts were used as biocathode electrodes in hexavalent chromium (Cr(VI))-reducing microbial fuel cells (MFCs). The one was fabricated through direct modification, and the other one processed by HNO3 pretreatment of graphite felt before modification. The results showed that two NaX zeolite-modified graphite felts are excellent bio-electrode materials for MFCs, and that a large NaX loading mass, obtained by HNO3 pretreatment (the HNO3-NaX electrode), leads to a superior performance. The HNO3-NaX electrode significantly improved the electricity generation and Cr(VI) removal of the MFC. The maximum Cr(VI) removal rate increased to 10.39±0.28 mg/L h, which was 8.2 times higher than that of the unmodified control. The improvement was ascribed to the strong affinity that NaX zeolite particles, present in large number on the graphite felt, have for microorganisms and Cr(VI) ions. PMID:26852205

  1. Effect of NaX zeolite-modified graphite felts on hexavalent chromium removal in biocathode microbial fuel cells.

    PubMed

    Wu, Xiayuan; Tong, Fei; Yong, Xiaoyu; Zhou, Jun; Zhang, Lixiong; Jia, Honghua; Wei, Ping

    2016-05-01

    Two kinds of NaX zeolite-modified graphite felts were used as biocathode electrodes in hexavalent chromium (Cr(VI))-reducing microbial fuel cells (MFCs). The one was fabricated through direct modification, and the other one processed by HNO3 pretreatment of graphite felt before modification. The results showed that two NaX zeolite-modified graphite felts are excellent bio-electrode materials for MFCs, and that a large NaX loading mass, obtained by HNO3 pretreatment (the HNO3-NaX electrode), leads to a superior performance. The HNO3-NaX electrode significantly improved the electricity generation and Cr(VI) removal of the MFC. The maximum Cr(VI) removal rate increased to 10.39±0.28 mg/L h, which was 8.2 times higher than that of the unmodified control. The improvement was ascribed to the strong affinity that NaX zeolite particles, present in large number on the graphite felt, have for microorganisms and Cr(VI) ions.

  2. Zeolite thin films: from computer chips to space stations.

    PubMed

    Lew, Christopher M; Cai, Rui; Yan, Yushan

    2010-02-16

    Zeolites are a class of crystalline oxides that have uniform and molecular-sized pores (3-12 A in diameter). Although natural zeolites were first discovered in 1756, significant commercial development did not begin until the 1950s when synthetic zeolites with high purity and controlled chemical composition became available. Since then, major commercial applications of zeolites have been limited to catalysis, adsorption, and ion exchange, all using zeolites in powder form. Although researchers have widely investigated zeolite thin films within the last 15 years, most of these studies were motivated by the potential application of these materials as separation membranes and membrane reactors. In the last decade, we have recognized and demonstrated that zeolite thin films can have new, diverse, and economically significant applications that others had not previously considered. In this Account, we highlight our work on the development of zeolite thin films as low-dielectric constant (low-k) insulators for future generation computer chips, environmentally benign corrosion-resistant coatings for aerospace alloys, and hydrophilic and microbiocidal coatings for gravity-independent water separation in space stations. Although these three applications might not seem directly related, they all rely on the ability to fine-tune important macroscopic properties of zeolites by changing their ratio of silicon to aluminum. For example, pure-silica zeolites (PSZs, Si/Al = infinity) are hydrophobic, acid stable, and have no ion exchange capacity, while low-silica zeolites (LSZs, Si/Al < 2) are hydrophilic, acid soluble, and have a high ion exchange capacity. These new thin films also take advantage of some unique properties of zeolites that have not been exploited before, such as a higher elastic modulus, hardness, and heat conductivity than those of amorphous porous silicas, and microbiocidal capabilities derived from their ion exchange capacities. Finally, we briefly discuss our

  3. Zeolite thin films: from computer chips to space stations.

    PubMed

    Lew, Christopher M; Cai, Rui; Yan, Yushan

    2010-02-16

    Zeolites are a class of crystalline oxides that have uniform and molecular-sized pores (3-12 A in diameter). Although natural zeolites were first discovered in 1756, significant commercial development did not begin until the 1950s when synthetic zeolites with high purity and controlled chemical composition became available. Since then, major commercial applications of zeolites have been limited to catalysis, adsorption, and ion exchange, all using zeolites in powder form. Although researchers have widely investigated zeolite thin films within the last 15 years, most of these studies were motivated by the potential application of these materials as separation membranes and membrane reactors. In the last decade, we have recognized and demonstrated that zeolite thin films can have new, diverse, and economically significant applications that others had not previously considered. In this Account, we highlight our work on the development of zeolite thin films as low-dielectric constant (low-k) insulators for future generation computer chips, environmentally benign corrosion-resistant coatings for aerospace alloys, and hydrophilic and microbiocidal coatings for gravity-independent water separation in space stations. Although these three applications might not seem directly related, they all rely on the ability to fine-tune important macroscopic properties of zeolites by changing their ratio of silicon to aluminum. For example, pure-silica zeolites (PSZs, Si/Al = infinity) are hydrophobic, acid stable, and have no ion exchange capacity, while low-silica zeolites (LSZs, Si/Al < 2) are hydrophilic, acid soluble, and have a high ion exchange capacity. These new thin films also take advantage of some unique properties of zeolites that have not been exploited before, such as a higher elastic modulus, hardness, and heat conductivity than those of amorphous porous silicas, and microbiocidal capabilities derived from their ion exchange capacities. Finally, we briefly discuss our

  4. Mechanism of Mineral Phase Reconstruction for Improving the Beneficiation of Copper and Iron from Copper Slag

    NASA Astrophysics Data System (ADS)

    Guo, Zhengqi; Zhu, Deqing; Pan, Jan; Zhang, Feng

    2016-08-01

    To maximize the recovery of iron and copper from copper slag, the modification process by adding a compound additive (a mixture of hematite, pyrite and manganous oxide) and optimizing the cooling of the slag was studied. The phase reconstruction mechanism of the slag modification process was revealed by thermodynamic calculations, x-ray diffraction, optical microscopy and scanning electron microscopy. The results show that the synergy between the burnt lime and the compound additive promotes the generation of target minerals, such as magnetite and copper matte. In addition, the multifunctional compound additive is able to improve the fluidity of the molten slag, which facilitates the coalescence and growth of fine particles of the target minerals. As a result, the percentage of iron distributed in the form of magnetite increased from 32.9% to 65.1%, and that of the copper exiting in the form of metallic copper and copper sulfide simultaneously increased from 80.0% to 90.3%. Meanwhile, the grains of the target minerals in the modified slag grew markedly to a mean size of over 50 μm after slow cooling. Ultimately, the beneficiation efficiency of copper and iron was improved because of the ease with which the target minerals could be liberated.

  5. Mechanism of Mineral Phase Reconstruction for Improving the Beneficiation of Copper and Iron from Copper Slag

    NASA Astrophysics Data System (ADS)

    Guo, Zhengqi; Zhu, Deqing; Pan, Jan; Zhang, Feng

    2016-09-01

    To maximize the recovery of iron and copper from copper slag, the modification process by adding a compound additive (a mixture of hematite, pyrite and manganous oxide) and optimizing the cooling of the slag was studied. The phase reconstruction mechanism of the slag modification process was revealed by thermodynamic calculations, x-ray diffraction, optical microscopy and scanning electron microscopy. The results show that the synergy between the burnt lime and the compound additive promotes the generation of target minerals, such as magnetite and copper matte. In addition, the multifunctional compound additive is able to improve the fluidity of the molten slag, which facilitates the coalescence and growth of fine particles of the target minerals. As a result, the percentage of iron distributed in the form of magnetite increased from 32.9% to 65.1%, and that of the copper exiting in the form of metallic copper and copper sulfide simultaneously increased from 80.0% to 90.3%. Meanwhile, the grains of the target minerals in the modified slag grew markedly to a mean size of over 50 μm after slow cooling. Ultimately, the beneficiation efficiency of copper and iron was improved because of the ease with which the target minerals could be liberated.

  6. Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads for magnetic affinity separation of histidine-tagged proteins.

    PubMed

    Vereshchagina, T A; Fedorchak, M A; Sharonova, O M; Fomenko, E V; Shishkina, N N; Zhizhaev, A M; Kudryavtsev, A N; Frank, L A; Anshits, A G

    2016-01-28

    Magnetic Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads (Ni-ferrosphere beads - NFB) of a core-shell structure were synthesized starting from coal fly ash ferrospheres having diameters in the range of 0.063-0.050 mm. The strategy of NFB fabrication is an oriented chemical modification of the outer surface preserving the magnetic core of parent beads with the formation of micro-mesoporous coverings. Two routes of ferrosphere modification were realized, such as (i) hydrothermal treatment in an alkaline medium resulting in a NaP zeolite layer and (ii) synthesis of micro-mesoporous silica on the glass surface using conventional methods. Immobilization of Ni(2+) ions in the siliceous porous shell of the magnetic beads was carried out via (i) the ion exchange of Na(+) for Ni(2+) in the zeolite layer or (ii) deposition of NiO clusters in the zeolite and silica pores. The final NFB were tested for affinity in magnetic separation of the histidine-tagged green fluorescent protein (GFP) directly from a cell lysate. Results pointed to the high affinity of the magnetic beads towards the protein in the presence of 10 mM EDTA. The sorption capacity of the ferrosphere-based Ni-beads with respect to GFP was in the range 1.5-5.7 mg cm(-3). PMID:26688000

  7. Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads for magnetic affinity separation of histidine-tagged proteins.

    PubMed

    Vereshchagina, T A; Fedorchak, M A; Sharonova, O M; Fomenko, E V; Shishkina, N N; Zhizhaev, A M; Kudryavtsev, A N; Frank, L A; Anshits, A G

    2016-01-28

    Magnetic Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads (Ni-ferrosphere beads - NFB) of a core-shell structure were synthesized starting from coal fly ash ferrospheres having diameters in the range of 0.063-0.050 mm. The strategy of NFB fabrication is an oriented chemical modification of the outer surface preserving the magnetic core of parent beads with the formation of micro-mesoporous coverings. Two routes of ferrosphere modification were realized, such as (i) hydrothermal treatment in an alkaline medium resulting in a NaP zeolite layer and (ii) synthesis of micro-mesoporous silica on the glass surface using conventional methods. Immobilization of Ni(2+) ions in the siliceous porous shell of the magnetic beads was carried out via (i) the ion exchange of Na(+) for Ni(2+) in the zeolite layer or (ii) deposition of NiO clusters in the zeolite and silica pores. The final NFB were tested for affinity in magnetic separation of the histidine-tagged green fluorescent protein (GFP) directly from a cell lysate. Results pointed to the high affinity of the magnetic beads towards the protein in the presence of 10 mM EDTA. The sorption capacity of the ferrosphere-based Ni-beads with respect to GFP was in the range 1.5-5.7 mg cm(-3).

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

    PubMed

    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. PMID:26652350

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

    PubMed

    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.

  10. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, H.; Blatter, F.; Sun, H.

    1999-06-22

    A process is described for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts. 19 figs.

  11. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2001-01-01

    A process for a combined selective thermal oxidation and photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly combined selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  12. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2000-01-01

    A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  13. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1999-01-01

    A process for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  14. FUNDAMENTALS AND APPLICATIONS OF PERVAPORATION THROUGH ZEOLITE MEMBRANES

    EPA Science Inventory

    Zeolite membranes are well suited for separating liquid-phase mixtures by pervaporation because of their molecular-sized pores and their hydrophilic/hydrophobic nature, and the first commercial application of zeolite membranes has been for dehydrating organics [1]. Because of ...

  15. Crewmember working on the mid deck Zeolite Crystal Growth experiment.

    NASA Technical Reports Server (NTRS)

    1992-01-01

    View showing Payload Specialist Bonnie Dunbar, in the mid deck, conducting the Zeolite Crystal Growth (ZCG) Experiment in the mid deck stowage locker work area. View shows assembly of zeolite sample in the metal autoclave cylinders prior to insertion into the furnace.

  16. Zeolites in the Pine Ridge Indian Reservation, South Dakota

    USGS Publications Warehouse

    Raymond, William H.; Bush, Alfred L.; Gude, Arthur J.

    1982-01-01

    Zeolites of possible commercial value occur in the Brule Formation of Oligocene age and the Sharps Formation (Harksen, 1961) of Miocene age which crop out in a wide area in the northern part of the Pine Ridge Indian Reservation. The thickness of the zeolite-bearing Interval and the extent of areas within the Interval which contain significant amounts of zeolites are far greater than was expected prior to this investigation. The shape of the zeolite-bearing Interval is tabular and the dimensions of Its exposure are roughly 10 ml x 200 mi x 150 ft (16 km x 160 km x 45 m) thick. Within the study area, there are tracts in which the zeolite resource potential is significant (see pl. 2). This report is intended to inform the Oglala Sioux Tribe of some of the most promising zeolite occurrences. Initial steps can then be taken by the Tribe toward possible development of the resources, should they wish to do so. The data contained herein identify areas of high zeolite potential, but are not adequate to establish economic value for the deposits. If development is recommended by the tribal government, we suggest that the tribal government contact companies involved in research and production of natural zeolites and provide them with the data in this report.

  17. Factors that Determine Zeolite Stability in Hot Liquid Water.

    PubMed

    Zhang, Lu; Chen, Kuizhi; Chen, Banghao; White, Jeffery L; Resasco, Daniel E

    2015-09-16

    The susceptibility of zeolites to hot liquid water may hamper their full utilization in aqueous phase processes, such as those involved in biomass conversion and upgrading reactions. Interactions of zeolites with water strongly depend on the presence of hydrophilic moieties including Brønsted acid sites (BAS), extraframework cations, and silanol defects, which facilitate wetting of the surface. However, it is not clear which of these moieties are responsible for the susceptibility of zeolites to liquid water. Previous studies have offered contradictory explanations because the role of each of these characteristics has not been investigated independently. In this work, a systematic comparison has been attempted by relating crystallinity losses to the variation of each of the five zeolite characteristics that may influence their stability in liquid water, including number of BAS, Si-O-Si bonds, framework type, silanol defects, and extraframework Al. In this study, we have systematically monitored the crystallinity changes of a series of HY, H-ZSM-5, and H-β zeolite samples with varying Si/Al ratio, density of BAS, zeolite structure, and density of silanol defects upon exposure to liquid water at 200 °C. The results of this comparison unambiguously indicate that the density of silanol defects plays the most crucial role in determining susceptibility of zeolites to hot liquid water. By functionalizing the silanol defects with organosilanes, the hydrophobicity of defective zeolite is increased and the tolerance to hot liquid water is significantly enhanced. PMID:26301890

  18. Zeolites in Eocene basaltic pillow lavas of the Siletz River Volcanics, Central Coast Range, Oregon.

    USGS Publications Warehouse

    Keith, T.E.C.; Staples, L.W.

    1985-01-01

    Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence. Although the zeolite assemblages are similar to those found in other major zeolite occurrences in basaltic pillow lavas, regional zoning of the zeolite assemblages is not apparent. The formation of the different assemblages is discussed.-D.F.B.

  19. Synthesis and catalytic applications of combined zeolitic/mesoporous materials

    PubMed Central

    Vernimmen, Jarian; Cool, Pegie

    2011-01-01

    Summary In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i) the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii) the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials. PMID:22259762

  20. Fly ash based zeolitic pigments for application in anticorrosive paints

    NASA Astrophysics Data System (ADS)

    Shaw, Ruchi; Tiwari, Sangeeta

    2016-04-01

    The purpose of this work is to evaluate the utilization of waste fly ash in anticorrosive paints. Zeolite NaY was synthesized from waste fly ash and subsequently modified by exchanging its nominal cation Na+ with Mg2+ and Ca2+ ions. The metal ion exchanged zeolite was then used as anticorrosive zeolitic pigments in paints. The prepared zeolite NaY was characterized using X-Ray diffraction technique and Scanning electron microscopy. The size, shape and density of the prepared fly ash based pigments were determined by various techniques. The paints were prepared by using fly ash based zeolitic pigments in epoxy resin and the percentages of pigments used in paints were 2% and 5%. These paints were applied to the mild steel panels and the anticorrosive properties of the pigments were assessed by the electrochemical spectroscopy technique (EIS).

  1. Potential and actual uses of zeolites in crop protection.

    PubMed

    De Smedt, Caroline; Someus, Edward; Spanoghe, Pieter

    2015-10-01

    In this review, it is demonstrated that zeolites have a potential to be used as crop protection agents. Similarly to kaolin, zeolites can be applied as particle films against pests and diseases. Their honeycomb framework, together with their carbon dioxide sorption capacity and their heat stress reduction capacity, makes them suitable as a leaf coating product. Furthermore, their water sorption capacity and their smaller particle sizes make them effective against fungal diseases and insect pests. Finally, these properties also ensure that zeolites can act as carriers of different active substances, which makes it possible to use zeolites for slow-release applications. Based on the literature, a general overview is provided of the different basic properties of zeolites as promising products in crop protection.

  2. A pair distribution function analysis of zeolite beta

    SciTech Connect

    Martinez-Inesta, M.M.; Peral, I.; Proffen, T.; Lobo, R.F.

    2010-07-20

    We describe the structural refinement of zeolite beta using the local structure obtained with the pair distribution function (PDF) method. A high quality synchrotron and two neutron scattering datasets were obtained on two samples of siliceous zeolite beta. The two polytypes that make up zeolite beta have the same local structure; therefore refinement of the two structures was possible using the same experimental PDF. Optimized structures of polytypes A and B were used to refine the structures using the program PDFfit. Refinements using only the synchrotron or the neutron datasets gave results inconsistent with each other but a cyclic refinement with the two datasets gave a good fit to both PDFs. The results show that the PDF method is a viable technique to analyze the local structure of disordered zeolites. However, given the complexity of most zeolite frameworks, the use of both X-ray and neutron radiation and high-resolution patterns is essential to obtain reliable refinements.

  3. Mineral resource of the month: natural and synthetic zeolites

    USGS Publications Warehouse

    Virta, R.

    2008-01-01

    Robert Virta, mineral commodity specialist for the U.S. Geological Survey, prepared the following information about the zeolite industry. Volcanic rocks containing natural zeolites — hydrated aluminosilicate minerals that contain alkaline and alkaline-earth metals — have been mined worldwide for more than 1,000 years for use as cements and building stone. For centuries, people thought natural zeolites occurred only in small amounts inside cavities of volcanic rock. But in the 1950s and early 1960s, large zeolite deposits were discovered in volcanic tuffs in the western United States and in marine tuffs in Italy and Japan. And since then, similar deposits have been found around the world, from Hungary to Cuba to New Zealand. The discovery of these larger deposits made commercial mining of natural zeolite possible.

  4. Widening Synthesis Bottlenecks: Realization of Ultrafast and Continuous-Flow Synthesis of High-Silica Zeolite SSZ-13 for NOx Removal.

    PubMed

    Liu, Zhendong; Wakihara, Toru; Oshima, Kazunori; Nishioka, Daisuke; Hotta, Yuusuke; Elangovan, Shanmugam P; Yanaba, Yutaka; Yoshikawa, Takeshi; Chaikittisilp, Watcharop; Matsuo, Takeshi; Takewaki, Takahiko; Okubo, Tatsuya

    2015-05-01

    Characteristics of zeolite formation, such as being kinetically slow and thermodynamically metastable, are the main bottlenecks that obstruct a fast zeolite synthesis. We present an ultrafast route, the first of its kind, to synthesize high-silica zeolite SSZ-13 in 10 min, instead of the several days usually required. Fast heating in a tubular reactor helps avoid thermal lag, and the synergistic effect of addition of a SSZ-13 seed, choice of the proper aluminum source, and employment of high temperature prompted the crystallization. Thanks to the ultra-short period of synthesis, we established a continuous-flow preparation of SSZ-13. The fast-synthesized SSZ-13, after copper-ion exchange, exhibits outstanding performance in the ammonia selective catalytic reduction (NH3 -SCR) of nitrogen oxides (NOx ), showing it to be a superior catalyst for NOx removal. Our results indicate that the formation of high-silica zeolites can be extremely fast if bottlenecks are effectively widened. PMID:25801140

  5. Influence of NaA Zeolite Crystal Expansion/Contraction on Zeolite Membrane Separations

    SciTech Connect

    Sorenson, Stephanie G; Payzant, E Andrew; Gibbons, Will T; Soydas, Belma; Kita, Hidetoshi; Noble, Richard D; Falconer, John L.

    2011-01-01

    In-situ powder XRD measurements showed that the NaA zeolite unit cell contracts and expands upon adsorption, and these changes in zeolite crystal size correlate with permeation changes through NaA zeolite membranes. These membranes had high pervaporation selectivities, even though gas permeation was mainly through defects, as indicated by Knudsen selectivities for gases. At 300 K and a thermodynamic activity of 0.03, water contracted the NaA crystals by 0.22 vol%, and this contraction increased the helium flux through two NaA membranes by approximately 80%. Crystal contraction also increased the fluxes of i-butane during vapor permeation and i-propanol (IPA) during pervaporation (~ 0.03 wt% water). At activities above 0.07, water expanded NaA crystals and correspondingly decreased the membrane fluxes of helium, i-butane, and IPA. Similarly, methanol contracted NaA crystals by 0.05 vol% at an activity of 0.02, and this contraction slightly increased the helium and i-butane fluxes through a NaA membrane. Above an activity of 0.06, methanol expanded the crystals, and the fluxes of helium and i-butane through a NaA membrane decreased. The adsorbate-induced changes explain some pervaporation behavior reported by others, and they indicate that crystal expansion and contraction may increase or decrease zeolite NaA membrane selectivity by changing the defect sizes.

  6. Radiation-induced silver agglomeration in molecular sieves: A comparison between A and X zeolites

    NASA Astrophysics Data System (ADS)

    Sadło, Jarosław; Waşowicz, Tomasz; Michalik, Jacek

    1995-06-01

    The stabilization conditions of silver atoms and clusters in hydrated and dehydrated AgNa-A and AgNa-X zeolites γ-irradiated at 77 K have been studied by ESR. It was found that silver agglomeration mechanisms in hydrated A and X zeolites are very similar and are controlled by the migration of silver atoms into the α-cages. In dehydrated zeolites agglomeration leads to completely different silver clusters in A and X zeolites. Small cationic clusters are stabilized in A zeolites and metallic clusters in X zeolites. Various factors affecting the agglomeration process in A and X zeolites are discussed.

  7. Investigation on the effect of zeolite precursor on the formation process of MCM-41 containing zeolite Y building units

    NASA Astrophysics Data System (ADS)

    Li, Peng; Xiong, Guang; Liu, Liping; Wang, Longlong

    2013-04-01

    The formation process of MCM-41 containing zeolite Y building units has been investigated by UV Raman spectroscopy, 29Si and 27Al MAS NMR spectroscopy, X-ray diffraction (XRD), N2 adsorption and electron microscopy (SEM and TEM). It is found that the precursor containing zeolite Y secondary building units promotes the formation of a metastable mesopore structure just after mixing the zeolite precursors with CTAB. In contrast, the low-polymerized aluminosilicates and well-crystallized zeolite crystals cannot be assembled with CTAB at this stage. The result supports that the zeolite secondary building units should promote to the formation of the mesopore wall. This has been ascribed to its high anionic charge density as well as the appropriate multidentate coordination. Lowering down the pH value to 9.3 facilitates the further polymerization of the aluminosilicate species to build up a stable mesoporous phase.

  8. [Copper and copper alloys. Technology updates].

    PubMed

    Loconsolo, V; Crespi, M

    2012-01-01

    The correlations between copper and copper alloys and human health have been the subject of some recent and extensive scientific researches. The voluntary risks evaluation, which anticipated the EU REACH Directive application, has shown that copper is a "safe" product for human health and for environment. In addition, it could be of great help thanks to its antibacterial properties. Copper tube can contribute in a relevant way to the prevention of water systems pollution by Legionella. Also the spreading of nosocomial infections is significantly contrasted by the use of copper and copper alloys for the production of articles intended for being frequently touched by people. The Environmental Protection Agency of the United States has in fact "registered" as antibacterial over 350 of copper alloys. PMID:23213799

  9. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-01-01

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  10. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-12-31

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  11. Characteristics of Lead Sorption by Zeolite Minerals

    NASA Astrophysics Data System (ADS)

    Al-Sewailem, M. S.

    Lead adsorption behavior was investigated using four Zeolite minerals (clinoptilolite, analcime, phillipsite and chabazite). The used Pb2+ concentrations were 0, 0.1, 0.5, 1.0, 2.0, 3.0 and 5 µmol mL-1. Results indicated that Pb2+ sorption followed the Langmuir adsorption isotherm, but over limited concentration ranges for clinoptilolite and analcime. The bindg energy (Kd) reached, 2.400 and 0.875 g L-1 for phillipsite and chabazite, respectively. The maximum adsorption capacity for such minerals reached 208.33 and 204.08 mg g-1 with correlation coefficient (R2) reached, 0.997 and 0.995, respectively. Meanwhile, two stages for Pb2+adsorption were observed with clinoptilolite and analcime in the low and high concentrations of the applied Pb2+. Data also was applicable to the Freundlich adsorption isotherm over the used entire Pb2+ concentration ranges. The binding energy (n) reached, 1.014, 1.005, 1.001 and 1.001 g L-1 for clinoptilolite, analcime, phillipsite and chabazite, respectively. However, the b values (maximum adsorption capacity) reached 202.582, 201.651, 207.062 and 206.871 mg g-1 with correlation coefficient (R2) nearly one for all studying minerals, respectively. Desorption data indicated that most of the sorbed Pb2+ was extractedin the 1st extraction following the adsorption experiment. The ability of the used zeolite minerals to retain Pb2+ was high and there were differences between the studied minerals in sorption of Pb2+. In conclusion, data eliminated that, zeolite minerals especially, philipsite and chabazite, could be successfully used as packing material in subsurface reactive barriers intercepting ground water plumes and for fixed bed reactors designed to remove Pb2+ from industrial wastewater.

  12. Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach.

    PubMed

    Fathima, Nishtar Nishad; Aravindhan, Rathinam; Rao, Jonnalagadda Raghava; Nair, Balachandran Unni

    2008-01-01

    Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.

  13. Structural analysis of hierarchically organized zeolites

    NASA Astrophysics Data System (ADS)

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

    2015-10-01

    Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact.

  14. Growth of large zeolite crystals in space

    SciTech Connect

    Sacco, A. Jr.; Dixon, A.; Thompson, R.; Scott, G.; Ditr, J.

    1988-01-01

    Synthesis studies performed using close analogs of triethanolamine (TEA) have shown that all three hydroxyl groups and the amine group in this molecule are necessary to provide nucleation suppression. Studies using C-13 nuclear magnetic resonance (NMR) revealed that the hydroxyl ions and the amine group are involved in the formation of an aluminum complex. It was also shown that silicate species do not interact this way with TEA in an alkaline solution. These results suggest that successful aluminum complexation leads to nucleation in zeolite-A crystallization.

  15. Hydrogen storage in Chabazite zeolite frameworks.

    PubMed

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

    2005-09-01

    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.

  16. Structural analysis of hierarchically organized zeolites

    PubMed Central

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

    2015-01-01

    Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact. PMID:26482337

  17. Imperfect wetting of hydrogen in zeolite

    SciTech Connect

    Sullivan, N.S.; Rall, M.

    1995-11-01

    We have considered the theoretical dependencies of the amount of supercooling of liquid hydrogen as a function of pore size for constrained geometries in order to compare the different mechanisms for supercooling that can be observed: notably the inhibition of nucleation in small geometries and the use of surfaces for which there is imperfect wetting. Analysis of the dependence of the observed supercooling reported elsewhere for molecular hydrogen and hydrogen deuteride on the pore size in zeolites supports the view that imperfect wetting occurs for small pores that have rough surfaces and dimension less than approximately 10{angstrom}.

  18. Hydrogen storage in Chabazite zeolite frameworks.

    PubMed

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

    2005-09-01

    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. PMID:16240032

  19. Growth of large zeolite crystals in space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Dixon, A.; Thompson, R.; Scott, G.; Ditr, J.

    1988-01-01

    Synthesis studies performed using close analogs of triethanolamine (TEA) have shown that all three hydroxyl groups and the amine group in this molecule are necessary to provide nucleation suppression. Studies using C-13 nuclear magnetic resonance (NMR) revealed that the hydroxyl ions and the amine group are involved in the formation of an aluminum complex. It was also shown that silicate species fo not interact this way with TEA in an alkaline solution. These results suggest that successful aluminum complexation leads to nucleation in zeolite-A crystallization.

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

    PubMed

    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.

  1. Microcalorimetric study of silica- and zeolite-supported platinum catalysts

    SciTech Connect

    Sharma, S.B.; Dumesic, J.A. ); Miller, J.T. )

    1994-07-01

    Microcalorimetric measurements of the differential heats of hydrogen and carbon monoxide adsorption versus adsorbate coverate were made at 403 K for platinum supported on silica, magnesia/alumina, L-zeolite, Y-zeolite, and ZSM-5. The differential heats at zero coverage for hydrogen and carbon monoxide adsorption were 90 and 140 kJ/mol, respectively, for platinum supported on silica and nonacidic zeolites. The differential heats were large by approximately 20 kJ/mol for hydrogen and carbon monoxide adsorption on platinum particles supported on basis supports such as potassium/silica, magnesia/alumina, and zeolites containing basic cations (K[sup +], Ba[sup 2+]) exchanged in excess of the zeolite framework aluminum content. The microcalorimetric results suggest that the high paraffin aromatization activity and selectivity observed for L-zeolite-supported platinum catalysts do not appear to be caused solely by changes in the adsorptive properties of the cluster-size platinum particles located within the zeolite. 35 refs., 10 figs., 2 tabs.

  2. Zeolite Crystal Growth (ZCG) Flight on USML-2

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, Nurcan; Warzywoda, Juliusz; Guray, Ipek; Marceau, Michelle; Sacco, Teran L.; Whalen, Leah M.

    1997-01-01

    The extensive use of zeolites and their impact on the world's economy has resulted in many efforts to characterize their structure, and improve the knowledge base for nucleation and growth of these crystals. The zeolite crystal growth (ZCG) experiment on USML-2 aimed to enhance the understanding of nucleation and growth of zeolite crystals, while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16 day - USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. The external surfaces of zeolite A, X, and Silicalite crystals grown in microgravity were smoother (lower surface roughness) than their terrestrial controls. Catalytic studies with zeolite Beta indicate that crystals grown in space exhibit a lower number of Lewis acid sites located in micropores. This suggests fewer structural defects for crystals grown in microgravity. Transmission electron micrographs (TEM) of zeolite Beta crystals also show that crystals grown in microgravity were free of line defects while terrestrial/controls had substantial defects.

  3. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    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.

  4. Study of fungicidal and antibacterial effect of the Cu(II)-complexes of thiophene oligomers synthesized in ZSM-5 zeolite channels.

    PubMed

    Cík, G; Bujdáková, H; Sersen, F

    2001-07-01

    The influence of the Cu(II)-complexes of thiophene oligomers synthesized by oxidative polymerization of thiophene with Cu2+ ions in ZSM-5 zeolite channels on fungicidal and antimicrobial properties was studied. It has been found that the heterogeneous system culture medium-modified zeolite increases sporulation of the tested fungus (Aspergillus niger) and concurrently kills yeast (Candida albicans). These effects are attributed to a slow release of Cu2+ ions and thiophene oligomers into the culture medium. As for the tested bacteria (G+ Staphylococcus aureus, G- Escherichia coli), the percentage of the killed cells increases due to light activation of the system. The light effect is assigned to photogeneration of the reactive oxygen species (ROS), mainly *OH radicals, which were registered in the water solution by EPR spectroscopy. It has been confirmed that the thiophene oligomers present in the Cu-ZSM-5 microstructure slow down the release of copper into the medium. PMID:11459134

  5. One-Pot Template-Free Synthesis of Cu-MOR Zeolite toward Efficient Catalyst Support for Aerobic Oxidation of 5-Hydroxymethylfurfural under Ambient Pressure.

    PubMed

    Zhang, Wei; Xie, Jingyan; Hou, Wei; Liu, Yangqing; Zhou, Yu; Wang, Jun

    2016-09-01

    Supported catalysts are widely studied, and exploring new promising supports is significant to access more applications. In this work, novel copper-containing MOR-type zeolites Cu-MOR were synthesized in a one-pot template-free route and served as efficient supports for vanadium oxide. In the heterogeneous oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with molecular oxygen (O2) under ambient pressure, the obtained catalyst demonstrated high yield (91.5%) and good reusability. Even under the ambient air pressure, it gave a DFF yield of 72.1%. Structure-activity relationship analysis indicated that the strong interaction between the framework Cu species and the guest V sites accounted for the remarkable performance. This work reveals that the Cu-MOR zeolite uniquely acts as the robust support toward well-performed non-noble metal heterogeneous catalyst for biomass conversion. PMID:27523255

  6. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  7. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  8. Gallium Zeolites for Light Paraffin Aromatization

    SciTech Connect

    Price, G.L.; Dooley, K.M.

    1999-02-10

    The primary original goal of this project was to investigate the active state of gallium-containing MFI catalysts for light paraffin aromatization, in particular the state of gallium in the active material. Our original hypothesis was that the most active and selective materials were those which contained gallium zeolitic cations, and that previously reported conditions for the activation of gallium-containing catalysts served to create these active centers. We believed that in high silica materials such as MFI, ion-exchange is most effectively accomplished with metals in their 1+ oxidation state, both because of the sparsity of the anionic ion-exchange sites associated with the zeolite, and because the large hydration shells associated with aqueous 3+ cations hinder transport. Metals such as Ga which commonly exist in higher oxidation states need to be reduced to promote ion-exchange and this is the reason that reduction of gallium-containing catalysts for light paraffin aromatization often yields a dramatic enhancement in catalytic activity. We have effectively combined reduction with ion-exchange and we term this combined process ''reductive solid-state ion-exchange''. Our hypothesis has largely been proven true, and a number of the papers we have published directly address this hypothesis.

  9. Quantitatively Probing the Al Distribution in Zeolites

    SciTech Connect

    Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas; Pin, Sonia; Mei, Donghai; Schenter, Gregory K.; Govind, Niranjan; Camaioni, Donald M.; Hu, Jian Z.; Lercher, Johannes A.

    2014-06-11

    The degree of substitution of Si4+ by Al3+ in the oxygen-terminated tetrahedra (Al T-sites) of zeolites determines the concentration of ion-exchange and Brønsted acid sites. As the location of the tetrahedra and the associated subtle variations in bond angles influence the acid strength, quantitative information about Al T-sites in the framework is critical to rationalize catalytic properties and to design new catalysts. A quantitative analysis is reported that uses a combination of extended X-ray absorption fine structure (EXAFS) analysis and 27Al MAS NMR spectroscopy supported by DFT-based molecular dynamics simulations. To discriminate individual Al atoms, sets of ab initio EXAFS spectra for various T-sites are generated from DFT-based molecular dynamics simulations allowing quantitative treatment of the EXAFS single- and multiple-photoelectron scattering processes out to 3-4 atom shells surrounding the Al absorption center. It is observed that identical zeolite types show dramatically different Al-distributions. A preference of Al for T-sites that are part of one or more 4-member rings in the framework over those T-sites that are part of only 5- and 6-member rings in the HBEA150 sample has been determined from a combination of these methods. This work was supported by the U. S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.

  10. [Copper transport and metabolism].

    PubMed

    Kurasaki, Masaaki; Saito, Takeshi

    2016-07-01

    In this review, copper metabolism and transport in mammalian tissues are introduced and discussed. Firstly, the copper required amounts and LD50 levels are shown to explain the difficult balances of copper in the cells between necessity and toxicity. Furthermore, on the basis of literatures published, relationship between copper-binding metallothioneins and mechanisms for the absorption and excretion of copper or hereditary copper metabolic disorders metabolism abnormality symptom are explained. Finally it has been indicated that apoptosis induced by heavy metals, especially copper was initiated by production of reactive oxygen species and oxidative stress in the cells. To understand precise mechanism for copper homeostasis in mammalian cells, further investigation will be needed to clarify the copper behaviors in normal and abnormal situations. PMID:27455798

  11. Multinuclear MAS NMR investigation of zeolites reacted with chlorofluorocarbons

    NASA Astrophysics Data System (ADS)

    Hannus, I.; Kónya, Z.; Lentz, P.; Nagy, J. B.; Kiricsi, I.

    1999-05-01

    Multinuclear ( 23Na, 27Al, 29Si, 13C) MAS NMR techniques were used for investigation of surface reaction of Y-type zeolites with CFCs (CCl 4, CCl 3F, CCl 2F 2, CClF 3, CF 4) and HCFC (CHClF 2). The hydrogen containing derivative reacts slowly. Those possessing more than 2 F atoms can be regarded as stable unreactive materials. CCl 4, CCl 3F, CCl 2F 2 react strongly with the zeolites. The reaction of HCFC with zeolites has a different mechanism to the other CFCs tested. On the basis of multinuclear NMR results a mechanism is given for the decomposition of HCFC.

  12. Accelerated crystallization of zeolites via hydroxyl free radicals.

    PubMed

    Feng, Guodong; Cheng, Peng; Yan, Wenfu; Boronat, Mercedes; Li, Xu; Su, Ji-Hu; Wang, Jianyu; Li, Yi; Corma, Avelino; Xu, Ruren; Yu, Jihong

    2016-03-11

    In the hydrothermal crystallization of zeolites from basic media, hydroxide ions (OH(-)) catalyze the depolymerization of the aluminosilicate gel by breaking the Si,Al-O-Si,Al bonds and catalyze the polymerization of the aluminosilicate anions around the hydrated cation species by remaking the Si,Al-O-Si,Al bonds. We report that hydroxyl free radicals (•OH) are involved in the zeolite crystallization under hydrothermal conditions. The crystallization processes of zeolites-such as Na-A, Na-X, NaZ-21, and silicalite-1-can be accelerated with hydroxyl free radicals generated by ultraviolet irradiation or Fenton's reagent.

  13. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, M.A.; Pereira, C.

    1997-03-18

    A method is described for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000 K to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  14. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, Michele A.; Pereira, Candido

    1997-01-01

    A method for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000.degree. K. to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  15. Zeolite crystal growth in space - What has been learned

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Thompson, R. W.; Dixon, A. G.

    1993-01-01

    Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

  16. Hierarchical zeolites from class F coal fly ash

    NASA Astrophysics Data System (ADS)

    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

  17. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  18. Synthesis of NaY zeolite on preformed kaolinite spheres. Evolution of zeolite content and textural properties with the reaction time

    SciTech Connect

    Basaldella, E.I.; Bonetto, R.; Tara, J.C. )

    1993-04-01

    The synthesis of NaY zeolite was carried out on fired kaolinite microspheres. Changes in porosity, chemical composition, and crystallinity of the solid show zeolite growth on both internal and external microsphere surfaces. It was also observed that, as a consequence of the alkaline treatment, the SiO[sub 2]/Al[sub 2]O[sub 3] ratio in the solid diminishes prior to the appearance of the zeolite, but increases when the zeolite begins to crystallize.

  19. Mimicking high-silica zeolites: highly stable germanium- and tin-rich zeolite-type chalcogenides.

    PubMed

    Lin, Qipu; Bu, Xianhui; Mao, Chengyu; Zhao, Xiang; Sasan, Koroush; Feng, Pingyun

    2015-05-20

    High-silica zeolites, as exemplified by ZSM-5, with excellent chemical and thermal stability, have generated a revolution in industrial catalysis. In contrast, prior to this work, high-silica-zeolite-like chalcogenides based on germanium/tin remained unknown, even after decades of research. Here six crystalline high-germanium or high-tin zeolite-type sulfides and selenides with four different topologies are reported. Their unprecedented framework compositions give these materials much improved thermal and chemical stability with high surface area (Langmuir surface area of 782 m(2)/g(-1)) comparable to or better than zeolites. Among them, highly stable CPM-120-ZnGeS allows for ion exchange with diverse metal or complex cations, resulting in fine-tuning in porosity, fast ion conductivity, and photoelectric response. Being among the most porous crystalline chalcogenides, CPM-120-ZnGeS (exchanged with Cs(+) ions) also shows reversible adsorption with high capacity and affinity for CO2 (98 and 73 cm(3) g(-1) at 273 and 298 K, respectively, isosteric heat of adsorption = 40.05 kJ mol(-1)). Moreover, CPM-120-ZnGeS could also function as a robust photocatalyst for water reduction to generate H2. The overall activity of H2 production from water, in the presence of Na2S-Na2SO3 as a hole scavenger, was 200 μmol h(-1)/(0.10 g). Such catalytic activity remained undiminished under illumination by UV light for as long as measured (200 h), demonstrating excellent resistance to photocorrosion even under intense UV radiation.

  20. Atomic force microscopy of novel zeolitic materials prepared by top-down synthesis and ADOR mechanism.

    PubMed

    Smith, Rachel L; Eliášová, Pavla; Mazur, Michal; Attfield, Martin P; Čejka, Jiří; Anderson, Michael W

    2014-08-11

    Top-down synthesis of 2D materials from a parent 3D zeolite with subsequent post-synthetic modification is an interesting method for synthesis of new materials. Assembly, disassembly, organisation, reassembly (ADOR) processes towards novel materials based on the zeolite UTL are now established. Herein, we present the first study of these materials by atomic force microscopy (AFM). AFM was used to monitor the ADOR process through observation of the changes in crystal surface and step height of the products. UTL surfaces were generally complex and contained grain boundaries and low-angle intergrowths, in addition to regular terraces. Hydrolysis of UTL to IPC-1P did not have adverse effects on the surfaces as compared to UTL. The layers remained intact after intercalation and calcination forming novel materials IPC-2 and IPC-4. Measured step heights gave good correlation with the X-ray diffraction determined d200 -spacing in these materials. However, swelling gave rise to significant changes to the surface topography, with significantly less regular terrace shapes. The pillared material yielded the roughest surface with ill-defined surface features. The results support a mechanism for the majority of these materials in which the UTL layers remain intact during the ADOR process as opposed to dissolving and recrystallising during each step. PMID:25042288

  1. Hydrophobic high surface area zeolites derived from fly ash for oil spill remediation.

    PubMed

    Sakthivel, Tamilselvan; Reid, David L; Goldstein, Ian; Hench, Larry; Seal, Sudipta

    2013-06-01

    Fly ash, a coal combustion byproduct with a predominantly aluminosilicate composition, is modified to develop an inexpensive sorbent for oil spill remediation. The as-produced fly ash is a hydrophilic material with poor sorption capacity. A simple two-step chemical modification process is designed to improve the oil sorption capacity. First, the fly ash was transformed to a zeolitic material via an alkali treatment, which increased the specific surface area up to 404 m(2) g(-1). Then, the material was surface functionalized to form a hydrophobic material with high contact angle up to 147° that floats on the surface of an oil-water mixture. The reported oil sorption capacities of X-type zeolite sorbent with different surface functionalization (propyl-, octyl-, octadecyl-trimethoxysilane and esterification) were estimated to 1.10, 1.02, 0.86, and 1.15 g g(-1), respectively. Oil sorption was about five times higher than the as-received fly ash (0.19 g g(-1)) and also had high buoyancy critical for economic cleanup of oil over water.

  2. Magnesia-alumina-aluminum phosphate-zeolite catalyst

    SciTech Connect

    Reynolds, E.H.; Stanulonis, J.J.; Swift, H.E.

    1980-09-16

    A catalyst for cracking gasoline feedstock with superior selectivity to gasoline production and greater metals tolerance comprises a magnesia-alumina-aluminum phosphate matrix composited with a zeolite having cracking activity.

  3. [Zeolite-containing tripoli powder in experimental hepatology].

    PubMed

    Kolotilova, M L; Ivanov, L N

    2005-01-01

    Biological activity of zeolite-containing tripoli powder was studied in rats. Biochemical, enzymatic and lipid peroxidation indices were assessed. The results of the study confirm enterosorption and detoxication activity of the powder.

  4. Characterization of a zeolite membrane for catalytic membrane reactor application

    SciTech Connect

    Giroir-Fendler, A.; Peureux, J.; Mozzanega, H.; Dalmon, J.A.

    1996-12-31

    This paper describes the morphological and transport properties of a composite zeolite (silicalite) - alumina membrane. Some advantages obtained in combining the membrane with a conventional fixed-bed catalyst are also reported.

  5. 12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH LOOKING WEST TO FOUNTAIN. STAIRWAY RUNS DOWN TO FILTRATION BAYS. - F. E. Weymouth Filtration Plant, 700 North Moreno Avenue, La Verne, Los Angeles County, CA

  6. Zeolite - A Natural Filter Material for Lead Polluted Water

    NASA Astrophysics Data System (ADS)

    Neamţu, Corina Ioana; Pică, Elena Maria; Rusu, Tiberiu

    2014-11-01

    Reducing the concentration of lead ions in a wastewater using zeolite has proven to be a successful water treatement method, all over the world. Putting the two media (solid and liquid) in contact in static conditions had good results regarding the concentration of the filtered solution, the pH and the electric conductivity, depending on the values of certain parameters such as the amount of the zeolite, volume of the solution or interaction time. The present study highlights the zeolite ability to retain the lead ions from a solution, in dynamic interaction conditions between the two environments, in a short interaction time. The results confirmed the effectiveness of ion exchange water treatment method in the conditions set, emphasizing once again the properties of the filter material - the zeolite

  7. CO2 capture using zeolite 13X prepared from bentonite

    NASA Astrophysics Data System (ADS)

    Chen, Chao; Park, Dong-Wha; Ahn, Wha-Seung

    2014-02-01

    Zeolite 13X was prepared using bentonite as the raw material by alkaline fusion followed by a hydrothermal treatment without adding any extra silica or alumina sources. The prepared zeolite 13X was characterized by X-ray powder diffraction, N2-adsorption-desorption measurements, and scanning electron microscopy. The CO2 capture performance of the prepared zeolite 13X was examined under both static and flow conditions. The prepared zeolite 13X showed a high BET surface area of 688 m2/g with a high micropore volume (0.30 cm3/g), and exhibited high CO2 capture capacity (211 mg/g) and selectivity to N2 (CO2/N2 = 37) at 25 °C and 1 bar. In addition, the material showed fast adsorption kinetics, and stable CO2 adsorption-desorption recycling performance at both 25 and 200 °C.

  8. Uniformly microsized luminescent materials obtained through a solid state reaction of WO{sub 3} with Ln{sup 3+}-exchanged zeolite L at 700 °C

    SciTech Connect

    Wang, Yige; Fang, Yi; Zhang, Wenjun; Zhang, Li; Chen, Yuhuan; Yu, Xiaoyan

    2013-06-01

    Graphical abstract: We have reported the modification of Ln3+/ZL microcrystals by the tungstate-oxygen species via a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. Highlights: ► Luminescent materials were obtained from zeolite L crystals. ► The materials show characteristic luminescence of Eu{sup 3+} and Tb{sup 3+} ions. ► The framework of zeolite L crystals has been kept during the annealing process. ► Energy transfer from tungstate-oxygen species to lanthanide was confirmed. - Abstract: In this work, we report the uniformly microsized luminescent materials prepared by a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. The obtained materials were investigated by SEM, XRD and photoluminescence spectroscopy. The influence of tungstate-oxygen species on the morphology and luminescence of the materials were discussed in detail. Energy transfer from the tungstate-oxygen species to Eu{sup 3+} and Tb{sup 3+} ions have been demonstrated by the photoluminescence spectra, implying the loading of tungstate-oxygen species into the nanochannels of the crystals and the close proximity of which to Eu{sup 3+} ions.

  9. Design of composite photocatalyst of TiO2 and Y-zeolite for degradation of 2-propanol in the gas phase under UV and visible light irradiation.

    PubMed

    Kamegawa, Takashi; Ishiguro, Yasushi; Kido, Ryota; Yamashita, Hiromi

    2014-10-13

    Hydrophobic Y-zeolite (SiO2/Al2O3 = 810) and TiO2 composite photocatalysts were designed by using two different types of TiO2 precursors, i.e., titanium ammonium oxalate and ammonium hexafluorotitanate. The porous structure, surface property and state of TiO2 were investigated by various characterization techniques. By using an ammonium hexafluorotitanate as a precursor, hydrophobic modification of the Y-zeolite surface and realizing visible light sensitivity was successfully achieved at the same time after calcination at 773 K in the air. The prepared sample still maintained the porous structure of Y-zeolite and a large surface area. Highly crystalline anatase TiO2 was also formed on the Y-zeolite surface by the role of fluorine in the precursor. The usages of ammonium hexafluorotitanate were effective for the improvement of the photocatalytic performance of the composite in the degradation of 2-propanol in the gas phase under UV and visible light (λ > 420 nm) irradiation.

  10. Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2.

    PubMed

    Shankar, M V; Anandan, S; Venkatachalam, N; Arabindoo, B; Murugesan, V

    2006-05-01

    Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.

  11. Commander Bowersox Tends to Zeolite Crystal Samples Aboard Space Station

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Expedition Six Commander Ken Bowersox spins Zeolite Crystal Growth sample tubes to eliminate bubbles that could affect crystal formation in preparation of a 15 day experiment aboard the International Space Station (ISS). Zeolites are hard as rock, yet are able to absorb liquids and gases like a sponge. By using the ISS microgravity environment to grow better, larger crystals, NASA and its commercial partners hope to improve petroleum manufacturing and other processes.

  12. In-situ x-ray absorption study of copper films in ground watersolutions

    SciTech Connect

    Kvashnina, K.O.; Butorin, S.M.; Modin, A.; Soroka, I.; Marcellini, M.; Nordgren, J.; Guo, J.-H.; Werme, L.

    2007-10-29

    This study illustrates how the damage from copper corrosion can be reduced by modifying the chemistry of the copper surface environment. The surface modification of oxidized copper films induced by chemical reaction with Cl{sup -} and HCO{sub 3}{sup -} in aqueous solutions was monitored by in situ X-ray absorption spectroscopy. The results show that corrosion of copper can be significantly reduced by adding even a small amount of sodium bicarbonate. The studied copper films corroded quickly in chloride solutions, whereas the same solution containing 1.1 mM HCO{sub 3}{sup -} prevented or slowed down the corrosion processes.

  13. Nanocellulose-Zeolite Composite Films for Odor Elimination.

    PubMed

    Keshavarzi, Neda; Mashayekhy Rad, Farshid; Mace, Amber; Ansari, Farhan; Akhtar, Farid; Nilsson, Ulrika; Berglund, Lars; Bergström, Lennart

    2015-07-01

    Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 μm thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit. PMID:26061093

  14. Role of ammonium fluoride in crystallization process of beta zeolite

    NASA Astrophysics Data System (ADS)

    Jon, Hery; Oumi, Yasunori; Itabashi, Keiji; Sano, Tsuneji

    2007-09-01

    The addition of Na + cations to the starting gel prepared using NH 4F significantly prolonged the crystallization time of beta zeolite. However, in the case of pure silica beta zeolite an addition of more NH 4F reduced the crystallization time by one-half. From 29Si MAS NMR measurements, the signal attributed to pentacoordinated silicon was found to be more pronounced for pure silica beta zeolite in the presence of Na + cations even in the solid phase with low crystallinity, as compared to that in the absence of Na + cations. Considering the results of theoretical calculation, because of more energetically stable state of Na +[SiO 4/2F] - species, it could be presumed that Na +[SiO 4/2F] - species might exist in pure silica beta zeolite. Furthermore, as confirmed by 19F MAS NMR measurements tetraethylammonium fluoride (TEAF) species were enclathrated intact in solid phase during the initial crystallization stage. This suggests that TEAF species are required for the formation of beta zeolite framework, in other words, as "SDA" which conditions the formation of kinetically favored phase, i.e., beta zeolite. Moreover, since part of TEA + cations is replaced by sodium cations, forming Na +[SiO 4/2F] - species, the amount of TEA +[SiO 4/2F] - species involved in either nucleation or crystal growth decreases and thus the crystallization time becomes longer.

  15. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene.

  16. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene. PMID:27486717

  17. Solvent Evaporation Assisted Preparation of Oriented Nanocrystalline Mesoporous MFI Zeolites

    SciTech Connect

    Zhu, Kake; Sun, Junming; Liu, Jun; Wang, Li Q.; Wan, Haiying; Hu, Jian Z.; Wang, Yong; Peden, Charles HF; Nie, Zimin

    2011-07-01

    A solvent evaporation route to produce hierarchically porous zeolites with an oriented MFI nanocrystalline structure has been developed, and the method is scalable and productive. In this method, hexadecyltrimethoxysilane is added to an ethanol solution containing zeolitic precursors. A hard gel is formed during the evaporation process. Subsequent hydrothermal treatments produce the hierarchically porous zeolite. High resolution transmission electron microscopy (HRTEM) studies suggest that misoriented zeolite nuclei are produced in the very early stages of the hydrothermal treatment, but further reactions lead to single crystal-like aggregates composed of intergrowth nanocrystals with a mean interparticle pore diameter of 12 nm. All Al atoms exist in tetrahedral sites, as confirmed by 27Al magic angle spinning nuclear magnetic resonance (MAS NMR). Variable temperature hyperpolarized (HP) 129Xe NMR spectroscopy suggest a fast molecular diffusion process from the interconnection between micro- and mesopores. Catalytic conversion of acetone to the isobutene reactions show comparable (with respect to conventional zeolites) selectivity to isobutene. However, hierarchically porous zeolites display enhanced activity and durability because of the more accessible acidic sites in the hierarchically porous structures.

  18. Inhibition of palm oil oxidation by zeolite nanocrystals.

    PubMed

    Tan, Kok-Hou; Awala, Hussein; Mukti, Rino R; Wong, Ka-Lun; Rigaud, Baptiste; Ling, Tau Chuan; Aleksandrov, Hristiyan A; Koleva, Iskra Z; Vayssilov, Georgi N; Mintova, Svetlana; Ng, Eng-Poh

    2015-05-13

    The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.

  19. Nanocellulose-Zeolite Composite Films for Odor Elimination.

    PubMed

    Keshavarzi, Neda; Mashayekhy Rad, Farshid; Mace, Amber; Ansari, Farhan; Akhtar, Farid; Nilsson, Ulrika; Berglund, Lars; Bergström, Lennart

    2015-07-01

    Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 μm thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit.

  20. Removal of ammonium from municipal landfill leachate using natural zeolites.

    PubMed

    Ye, Zhihong; Wang, Jiawen; Sun, Lingyu; Zhang, Daobin; Zhang, Hui

    2015-01-01

    Ammonium ion-exchange performance of the natural zeolite was investigated in both batch and column studies. The effects of zeolite dosage, contact time, stirring speed and pH on ammonium removal were investigated in batch experiments. The result showed that ammonium removal efficiency increased with an increase in zeolite dosage from 25 to 150 g/L, and an increase in stirring speed from 200 to 250 r/min. But further increase in zeolite dosage and stirring speed would result in an unpronounced increase of ammonium removal. The optimal pH for the removal of ammonium was found as 7.1. In the column studies, the effect of flow rate was investigated, and the total ammonium removal percentage during 180 min operation time decreased with the flow rate though the ion-exchange capacity varied to a very small extent with the flow rate ranging from 4 to 9 mL/min. The spent zeolite was regenerated by sodium chloride solution and the ammonia removal capacity of zeolite changed little or even increased after three regeneration cycles.

  1. Synthesis and characterization of nanocrystalline and mesoporous zeolites

    NASA Astrophysics Data System (ADS)

    Petushkov, Anton

    2011-12-01

    Mesoporous aggregates of nanocrystalline zeolites with MFI and BEA frameworks have been synthesized using a one-pot and single structure directing agent. The effect of different reaction conditions, such as temperature, time, pH and water content, on the particle size, surface area and mesopore volume has been studied. Nanocrystalline and mesoporous ZSM-5, beta and Y zeolites were modified with different transition metals and the resulting single- and double metal containing catalyst materials were characterized. Nanocrystalline Silicalite-1 zeolite samples with varying particle size were functionalized with different organosilane groups and the cytotoxic activity of the zeolite nanocrystals was studied as a function of particle size, concentration, organic functional group type, as well as the type of cell line. Framework stability of nanocrystalline NaY zeolite was tested under different pH conditions. The synthesized zeolites used in this work were characterized using a variety of physico-chemical methods, including powder X-ray diffraction, Solid State NMR, nitrogen sorption, electron microscopy, Inductively Coupled Plasma -- Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy.

  2. Nanosized zeolites as a perspective material for conductometric biosensors creation

    NASA Astrophysics Data System (ADS)

    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.

  3. Characterization of Chemical Properties, Unit Cell Parameters and Particle Size Distribution of Three Zeolite Reference Materials: RM 8850 - Zeolite Y, RM 8851 - Zeolite A and RM 8852 - Ammonium ZSM-5 Zeolite

    SciTech Connect

    Turner,S.; Sieber, J.; Vetter, T.; Zeisler, R.; Marlow, A.; Moreno-Ramirez, M.; Davis, M.; Kennedy, G.; Borghard, W.; et al

    2008-01-01

    Zeolites have important industrial applications including use as catalysts, molecular sieves and ion exchange materials. In this study, three zeolite materials have been characterized by the National Institute of Standards and Technology (NIST) as reference materials (RMs): zeolite Y (RM 8850), zeolite A (RM 8851) and ZSM-5 zeolite (RM 8852). They have been characterized by a variety of chemical and physical measurement methods: X-ray fluorescence (XRF), gravimetry, instrumental neutron activation analysis (INAA), nuclear magnetic resonance (NMR), calorimetry, synchrotron X-ray diffraction, neutron diffraction, laser light extinction, laser light scattering, electric sensing zone, X-ray sedimentation, scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and optical microscopy. The chemical homogeneity of the materials has been characterized. Reference values are given for the major components (major elements, loss on ignition [LOI] and loss on fusion [LOF]), trace elements and Si/Al and Na/Al ratios. Information values are given for enthalpies of formation, unit cell parameters, particle size distributions, refractive indices and variation of mass with variation in relative humidity (RH). Comparisons are made to literature unit cell parameters. The RMs are expected to provide a basis for intercomparison studies of these zeolite materials.

  4. Moderate-temperature zeolitic alteration in a cooling pyroclastic deposit

    USGS Publications Warehouse

    Levy, S.S.; O'Neil, J.R.

    1989-01-01

    The locally zeolitized Topopah Spring Member of the Paintbrush Tuff (13 Myr.), Yucca Mountain, Nevada, U.S.A., is part of a thick sequence of zeolitized pyroclastic units. Most of the zeolitized units are nonwelded tuffs that were altered during low-temperature diagenesis, but the distribution and textural setting of zeolite (heulandite-clinoptilolite) and smectite in the densely welded Topopah Spring tuff suggest that these hydrous minerals formed while the tuff was still cooling after pyroclastic emplacement and welding. The hydrous minerals are concentrated within a transition zone between devitrified tuff in the central part of the unit and underlying vitrophyre. Movement of liquid and convected heat along fractures from the devitrified tuff to the ritrophyre caused local devitrification and hydrous mineral crystallization. Oxygen isotope geothermometry of cogenetic quartz confirms the nondiagenetic moderate temperature origin of the hydrous minerals at temperatures of ??? 40-100??C, assuming a meteoric water source. The Topopah Spring tuff is under consideration for emplacement of a high-level nuclear waste repository. The natural rock alteration of the cooling pyroclastic deposit may be a good natural analog for repository-induced hydrothermal alteration. As a result of repository thermal loading, temperatures in the Topopah Spring vitrophyre may rise sufficiently to duplicate the inferred temperatures of natural zeolitic alteration. Heated water moving downward from the repository into the vitrophyre may contribute to new zeolitic alteration. ?? 1989.

  5. Removal of ammonium from municipal landfill leachate using natural zeolites.

    PubMed

    Ye, Zhihong; Wang, Jiawen; Sun, Lingyu; Zhang, Daobin; Zhang, Hui

    2015-01-01

    Ammonium ion-exchange performance of the natural zeolite was investigated in both batch and column studies. The effects of zeolite dosage, contact time, stirring speed and pH on ammonium removal were investigated in batch experiments. The result showed that ammonium removal efficiency increased with an increase in zeolite dosage from 25 to 150 g/L, and an increase in stirring speed from 200 to 250 r/min. But further increase in zeolite dosage and stirring speed would result in an unpronounced increase of ammonium removal. The optimal pH for the removal of ammonium was found as 7.1. In the column studies, the effect of flow rate was investigated, and the total ammonium removal percentage during 180 min operation time decreased with the flow rate though the ion-exchange capacity varied to a very small extent with the flow rate ranging from 4 to 9 mL/min. The spent zeolite was regenerated by sodium chloride solution and the ammonia removal capacity of zeolite changed little or even increased after three regeneration cycles. PMID:26510611

  6. Enthalpy of formation for natural paulingite zeolite

    NASA Astrophysics Data System (ADS)

    Ogorodova, L. P.; Mel'Chakova, L. V.; Kiseleva, I. A.

    2008-01-01

    Natural paulingite zeolite of the composition (K4.48Na0.56Ca2.95Ba0.87Mg0.06)[Al11.04Fe{0.04/3+}Si30.49O84] · 35.25H2O (Vinariská Hora, Czechia) was studied calorimetrically on a high-temperature Tian-Calvet microcalorimeter. Enthalpies of formation from oxides (-1969 ± 128 kJ/mol) and elements (-52393 ± 132 kJ/mol) were determined for this mineral by melt dissolution calorimetry. The obtained experimental results and the literature data were used to calculate the Gibbs free energy of formation from elements.

  7. Photocatalyzed oxidation of hydrocarbons in zeolite cages

    SciTech Connect

    Frei, H.; Blatter, F.; Sun, H.

    1996-06-01

    Oxidation of hydrocarbons by molecular oxygen is a key process in chemical industry. But reactions that use O{sub 2} as the primary oxidant often produce large amounts of unwanted byproducts. One major reason that selectivities are low is that the desired products (such as alcohols or carbonyls) are more easily oxidized by O{sub 2} than the parent hydrocarbon. The authors recently discovered a simple method that gives partial oxidation of small alkenes, alkanes, and alkyl-substituted benzenes by O{sub 2} at unprecedented selectivity, even at high conversion of the hydrocarbon. The approach is based on visible light-induced chemistry of hydrocarbon-O{sub 2} collisional pairs in the cages of large-pore zeolites. Reactions are conducted at ambient temperature in the absence of solvent or photosensitizer. Here the authors describe the most interesting reactions established thus far and define issues that pertain to scale-up of the method.

  8. Preparation and gas permeabilities of zeolite membranes

    SciTech Connect

    Jinqu Wang; Yongfeng Wang; Shuanshi Fan

    1994-12-31

    Zeolites with less than 10 {angstrom} pore are desirable membrane materials, due to their crystallinity, resistance to high temperature, and chemical inertness. A variety of new membranous materials were synthesized composed of a continuous intergrowth of 5-50 micrometer type A, X, Y, or ZSM-5 crystals. The membranes were crystallized under hydrothermal conditions at 90 to 220{degrees}C on the external surface of a porous ceramics. The reagents used were aluminum sulphate, water glass (20.1 wt% SiO{sub 2}, 6.09 wt% Na{sub 2}O, 73.8 wt% water), sodium hydroxide, sulphuric acid, deionized water and templating agents. The molar composition was: 0.1-0.5 Na{sub 2}O:1 SiO{sub 2}:0.04-0.05 Al{sub 2}O{sub 3}:20-60H{sub 2}O.

  9. Copper-tantalum alloy

    DOEpatents

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1986-07-15

    A tantalum-copper alloy can be made by preparing a consumable electrode consisting of an elongated copper billet containing at least two spaced apart tantalum rods extending longitudinally the length of the billet. The electrode is placed in a dc arc furnace and melted under conditions which co-melt the copper and tantalum to form the alloy.

  10. On copper peroxide

    NASA Technical Reports Server (NTRS)

    Moser, L.

    1988-01-01

    The action of hydrogen superoxide on copper salts in alcoholic solutions is studied. The action of hydrogen peroxide on copper hydroxide in alcoholic suspensions, and the action of ethereal hydrogen peroxide on copper hydroxide are discussed. It is concluded that using the procedure proposed excludes almost entirely the harmful effect of hydrolysis.

  11. Demystifying Controlling Copper Corrosion

    EPA Science Inventory

    The LCR systematically misses the highest health and corrosion risk sites for copper. Additionally, there are growing concerns for WWTP copper in sludges and discharge levels. There are many corrosion control differences between copper and lead. This talk explains the sometimes c...

  12. [Copper pathology (author's transl)].

    PubMed

    Mallet, B; Romette, J; Di Costanzo, J D

    1982-01-30

    Copper is an essential dietary component, being the coenzyme of many enzymes with oxidase activity, e.g. ceruloplasmin, superoxide dismutase, monoamine oxidase, etc. The metabolism of copper is complex and imperfectly known. Active transport of copper through the intestinal epithelial cells involves metallothionein, a protein rich in sulfhydryl groups which also binds the copper in excess and probably prevents absorption in toxic amounts. In hepatocytes a metallothionein facilitates absorption by a similar mechanism and regulates copper distribution in the liver: incorporation in an apoceruloplasmin, storage and synthesis of copper-dependent enzymes. Metallothioneins and ceruloplasmin are essential to adequate copper homeostasis. Apart from genetic disorders, diseases involving copper usually result from hypercupraemia of varied origin. Wilson's disease and Menkes' disease, although clinically and pathogenetically different, are both marked by low ceruloplasmin and copper serum levels. The excessive liver retention of copper in Wilson's disease might be due to increased avidity of hepatic metallothioneins for copper and decreased biliary excretion through lysosomal dysfunction. Menkes' disease might be due to low avidity of intestinal and hepatic metallothioneins for copper. The basic biochemical defect responsible for these two hereditary conditions has not yet been fully elucidated.

  13. Pyrolysis of scrap tyres with zeolite USY.

    PubMed

    Shen, Boxiong; Wu, Chunfei; Wang, Rui; Guo, Binbin; Liang, Cai

    2006-09-21

    A zeolite catalyst of ultrastable Y-type (USY) was investigated in the research of two staged pyrolysis-catalysis of scrap tyres. Scrap tyres were pyrolysed in a fixed bed reactor and the evolved pyrolysis gases were passed through a secondary catalytic reactor. The main objective of this paper was to investigate the effect of zeolite USY on the yield of products and the composition of derived oil. The influences of several parameters such as pyrolysis temperature, catalytic temperature, catalyst/tyre ratio, heating rate, etc. on the yield of the derived oil, char and gas were investigated. It showed that the increase of catalytic temperature and catalyst/tyre ratio resulted in high yield of gas at the expense of the oil yield. For example, when the catalyst/tyre ratio increased from 0.25 to 1.0, the yield of gas increased from 30.5 to 49.9 wt.%, and the oil yield decreased nearly two-fold from 31.6 to 12.7 wt.%. The concentration of light naphtha (boiling point < 160 degrees C) was also investigated in this study. And the high catalyst/tyre ratio favored to increase the concentration of light naphtha (< 160 degrees C) in oil. In order to study the composition of derived oil, a distilled fraction (< 280 degrees C), which was 92.5 wt.% of the oil obtained from catalytic pyrolysis of scrap tyre at a pyrolysis temperature, catalytic temperature and catalyst/tyre ratio of 500, 400 degrees C and 0.5, respectively, was analyzed with gas chromatography/mass spectrometry (GC/MS). The distillate was found to contain 1.23 wt.% benzene, 9.35 wt.% toluene, 3.68 wt.% ethylbenzene, 12.64 wt.% xylenes, 1.81 wt.% limonene and 13.89 wt.% PAHs, etc., where the single ring aromatics represented a significant potential use as chemicals.

  14. Proton-loaded zeolites. 1. HX (X = Cl, Br, I) in sodium zeolite Y archetype: Packaged acids on the rod to intrazeolite semiconductors

    SciTech Connect

    Ozin, G.A.; Oezkar, S. ); Stucky, G.D. )

    1990-09-20

    This series of three papers is concerned with an in-depth investigation of proton-loaded zeolites (packaged acids), a novel class of controlled microporosity, solid-state Broensted acids. Proton-loaded zeolites are formed from the reaction between anhydrous Broensted acids and dehydrated zeolites. Initial experiments focus attention on the chemistry, spectroscopy, diffraction, and dynamics of the sorption and desorption of anhydrous hydrogen halides (HX) in zeolite Y with some important control experiments in all-silica zeolite Y (SiO{sub 2}-Y) and ALPO-5. Zeolite cation, HX anion, H/D isotope, and probe-base effects are explored to elucidate details of location, population, distribution (homogeneity), thermal/kinetic stability, acidity, and reactivity of protonation, anionation, and solvation sites in the zeolite Y lattice.

  15. Following the movement of Cu ions in a SSZ-13 zeolite during dehydration, reduction and adsorption: a combined in situ TP-XRD, XANES/DRIFTS study

    SciTech Connect

    Kwak, Ja Hun; Varga, Tamas; Peden, Charles HF; Gao, Feng; Hanson, Jonathan C.; Szanyi, Janos

    2014-05-05

    Cu-SSZ-13 has been shown to possess high activity and superior N2 formation selectivity in the selective catalytic reduction of NOx under oxygen rich conditions. Here, a combination of synchrotron-based (XRD and XANES) and vibrational (DRIFTS) spectroscopy tools have been used to follow the changes in the location and coordination environment of copper ions in a Cu-SSZ-13 zeolite during calcinations, reduction with CO, and adsorption of CO and H2O. XANES spectra collected during these procedures provides critical information not only on the variation in the oxidation state of the copper species in the zeolite structure, but also on the changes in the coordination environment around these ions as they interact with the framework, and with different adsorbates (H2O and CO). Time-resolved XRD data indicate the movement of copper ions and the consequent variation of the unit cell parameters during dehydration. DRIFT spectra provide information about the adsorbed species present in the zeolite, as well as the oxidation states of and coordination environment around the copper ions. A careful analysis of the asymmetric T-O-T vibrations of the CHA framework perturbed by copper ions in different coordination environments proved to be especially informative. The results of this study will aid the identification of the location, coordination and oxidation states of copper ions obtained during in operando catalytic studies. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. Part of this work (sample preparation) was performed in the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for the US DOE by Battelle. All of the spectroscopy work reported here was

  16. Preparation of zeolite NaA for CO2 capture from nickel laterite residue

    NASA Astrophysics Data System (ADS)

    Du, Tao; Liu, Li-ying; Xiao, Penny; Che, Shuai; Wang, He-ming

    2014-08-01

    Zeolite NaA was successfully prepared from nickel laterite residue for the first time via a fusion-hydrothermal procedure. The structure and morphology of the as-synthesized zeolite NaA were characterized with a range of experimental techniques, such as X-ray diffraction, scanning electronic microscopy, and infrared spectroscopy. It was revealed that the structures of the produced zeolites were dependent on the molar ratios of the reactants and hydrothermal reaction conditions, so the synthesis conditions were optimized to obtain pure zeolite NaA. Adsorption of nitrogen and carbon dioxide on the prepared zeolite NaA was also measured and analyzed. The results showed that zeolite NaA could be prepared with reasonable purity, it had physicochemical properties comparable with zeolite NaA made from other methods, and it had excellent gas adsorption properties, thus demonstrating that zeolite NaA could be prepared from nickel laterite residue.

  17. Removal of heavy metals from mine waters by natural zeolites

    SciTech Connect

    Ulla Wingenfelder; Carsten Hansen; Gerhard Furrer; Rainer Schulin

    2005-06-15

    The study investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes. 42 refs., 5 figs., 3 tabs.

  18. Synthesis of mesoporous zeolite single crystals with cheap porogens

    SciTech Connect

    Tao Haixiang; Li Changlin; Ren Jiawen; Wang Yanqin; Lu Guanzhong

    2011-07-15

    Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.

  19. Effect of hydrophilic defects on water transport in MFI zeolites.

    PubMed

    Humplik, Thomas; Raj, Rishi; Maroo, Shalabh C; Laoui, Tahar; Wang, Evelyn N

    2014-06-10

    The subnanometer pore structure of zeolites and other microporous materials has been proposed to act as a molecular sieve for various water separation technologies. However, due to the increased interaction between the solid and water in these nanoconfined spaces, it is unclear which type of interface, be it hydrophilic or hydrophobic, offers an advantageous medium for enhancing transport properties. In this work, we probe the role of hydrophilic defects on the transport of water inside the microporous hydrophobic MFI zeolite pore structure via combined sorption and high-pressure infiltration experiments. While the inclusion of defects was observed to increase the amount of water within the zeolite pore network by up to 7 times at the saturation pressure, the diffusivity of this infiltrated water was lowered by up to 2 orders of magnitude in comparison to that of water within the nearly defect-free hydrophobic MFI zeolite. Subsequently, the permeability of water within the more defective MFI zeolite was an order of magnitude lower than that of the nearly defect-free zeolite. The results from these experiments suggest that the intrinsic hydrophobic pore structure of MFI zeolites can facilitate faster water transport due to the decreased attraction between the water and the defect-free surface. While the strong attraction of water to the defects allows for water to infiltrate the porous network at lower pressures, the results suggest that this strong attraction decreases the mobility of the infiltrated water. The insights gained from this study can be utilized to improve the design of future membranes for water desalination and other separation techniques.

  20. A revised estimate of copper emissions from road transport in UNECE-Europe and its impact on predicted copper concentrations

    NASA Astrophysics Data System (ADS)

    Denier van der Gon, H. A. C.; Hulskotte, J. H. J.; Visschedijk, A. J. H.; Schaap, M.

    Comparisons of measured and model-predicted atmospheric copper concentrations show a severe underestimation of the observed concentrations by the models. This underestimation may be (partly) due to underestimated emissions of copper to air. Since the phase out of asbestos brake lining material, the composition of brake lining material has changed and may contain up to ˜15% copper. This makes brake wear from vehicles potentially an important source of atmospheric (particulate) copper concentrations. In this paper, we reassess the copper emissions due to exhaust emissions and brake wear from road transport. Overall, our reassessments result in an estimate of total copper emission to air in UNECE-Europe of 4.0-5.5 ktonnes yr -1, which is substantially higher than the previous estimate of 2.8 ktonnes yr -1. Copper concentrations over Europe are calculated with the LOTOS-EUROS model using the revised emission data as model input. The results show that the revised emission estimates are a major step towards gap closure of predicted versus observed copper concentrations in ambient air. Brake wear emissions may be responsible for 50-75% of the total copper emissions to air for most of Western Europe. The hypothesis that road transport is an important source of copper emissions is tested and confirmed by (1) reviewing available literature data of chemically speciated PM data from road tunnel studies and (2) the gradient observed in copper concentrations from ambient PM monitoring going from rural sites to street stations. The literature review and observational data suggest that the majority of the emitted PM10 brake wear particles is in the PM2.5-10 size range. The results of this study indicate that modification of brake lining composition is an important mitigation option to reduce copper exposure of the population in Western Europe.

  1. Bayberry-like ZnO/MFI zeolite as high performance methanol-to-aromatics catalyst.

    PubMed

    Wang, Ning; Qian, Weizhong; Shen, Kui; Su, Chang; Wei, Fei

    2016-02-01

    Unique bayberry-like MFI zeolites are synthesized through a quasi-solid-state crystallization approach. This hierarchical zeolite structure has a relatively thick shell, densely grown nanocrystals with an ordered packed channel, high mechanical stability, high surface area and a low Si/Al ratio. Its catalytic efficiency for methanol-to-aromatics is significantly higher than that of conventional MFI zeolites.

  2. Properties of Zeolite A Obtained from Powdered Laundry Detergent: An Undergraduate Experiment.

    ERIC Educational Resources Information Center

    Smoot, Alison L.; Lindquist, David A.

    1997-01-01

    Presents experiments that introduce students to the myriad properties of zeolites using the sodium form of zeolite A (Na-A) from laundry detergent. Experiments include extracting Na-A from detergent, water softening properties, desiccant properties, ion-exchange properties, and Zeolite HA as a dehydration catalyst. (JRH)

  3. Dynamic and reversible organization of zeolite L crystals induced by holographic optical tweezers.

    PubMed

    Woerdemann, Mike; Gläsener, Stefan; Hörner, Florian; Devaux, André; De Cola, Luisa; Denz, Cornelia

    2010-10-01

    Organization and patterning of zeolite L crystals with their unique properties such as their one-dimensional nano channel system is of highest topical interest with various applications in many areas of science. We demonstrate full three-dimensional optical control of single zeolite L crystals and for the first time fully reversible, dynamic organization of a multitude of individually controlled zeolite L crystals.

  4. Framework Stabilization of Si-Rich LTA Zeolite Prepared in Organic-Free Media

    SciTech Connect

    Conato, Marlon T.; Oleksiak, Matthew D.; McGrail, B. Peter; Motkuri, Radha K.; Rimer, Jeffrey D.

    2014-10-16

    Zeolite HOU-2 (LTA type) is prepared with the highest silica content (Si/Al = 2.1) reported for Na-LTA zeolites without the use of an organic structure-directing agent. The rational design of Si-rich zeolites has the potential to improve their thermal stability for applications in catalysis, gas storage, and selective separations.

  5. Micro/macroporous system: MFI-type zeolite crystals with embedded macropores.

    PubMed

    Machoke, Albert G; Beltrán, Ana M; Inayat, Alexandra; Winter, Benjamin; Weissenberger, Tobias; Kruse, Nadine; Güttel, Robert; Spiecker, Erdmann; Schwieger, Wilhelm

    2015-02-01

    Zeolite crystals with an embedded and interconnected macropore system are prepared by using mesoporous silica particles as a silica source and as a sacrificial macroporogen. These novel hierarchical zeolite crystals are expected to reduce diffusion limitations in all zeolite-catalyzed reactions, especially in the transformation of larger molecules like in the catalytic cracking of polymers and the conversion of biomass. PMID:25535114

  6. Properties of Zeolite A Obtained from Powdered Laundry Detergent: An Undergraduate Chemistry Experiment

    NASA Astrophysics Data System (ADS)

    Lindquist, David A.; Smoot, Alison L.

    1997-05-01

    Zeolites, crystalline porous aluminosilicates, are valued for their ability to absorb ions and molecules as well as function as catalysts. A number of laboratory experiments using zeolites filtered from a suspension of powdered laundry detergent are described. The various experiments illustrate the myriad uses of zeolites as desiccants, ion exchange materials, and catalysts.

  7. ZEOLITE PERFORMANCE AS AN ANION EXCHANGER FOR ARSENIC SEQUESTRATION IN WATER

    EPA Science Inventory

    Zeolites are well known for their use in ion exchange and acid catalysis reactions. The use of zeolites in anion or ligand exchange reactions is less studied. The NH4+ form of zeolite Y (NY6, Faujasite) has been tested in this work to evaluate its performance for arsenic removal...

  8. UTILITY OF SYNTHETIC ZEOLITES IN REMOVAL OF INORGANIC AND ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Zeolites are well known for their ion exchange and adsorption properties. Different inorganic and organic pollutants have been removed from water at room temperature using various zeolites. Synthetic zeolites like ZSM-5, Ferrierite, Beta and Faujasite Y have been used to remove i...

  9. The influence of framework-gallium in zeolites: Electronegativity and infrared spectroscopic study

    SciTech Connect

    Dompas, D.H.; Mortier, W.J. ); Kenter, O.C.H. ); Janssen, M.J.G.; Verduijn, J.P. )

    1991-05-01

    Based on the influence of the composition (Si/Al and Si/Ga ratio) on the framework vibrations of zeolites with different structure types (FAU, LTL, BETA, MOR, MEL, MFI, TON, and MTW), an electronegativity value for gallium substituted into zeolite frameworks is proposed (Sanderson electronegativity scale). The present electronegativity value agrees with the known physicochemical properties of gallium substituted zeolites.

  10. Synthesis of copper nanostructures on silica-based particles for antimicrobial organic coatings

    NASA Astrophysics Data System (ADS)

    Palza, Humberto; Delgado, Katherine; Curotto, Nicolás

    2015-12-01

    Sol-gel based silica nanoparticles of 100 nm were used to interact with copper ions from the dissolution of CuCl2 allowing the synthesis of paratacamite (Cu2(OH)3Cl) nanocrystals of around 20 nm. The method produced well dispersed copper nanostructures directly supported on the surface of the SiO2 particles and was generalized by using a natural zeolite microparticle as support with similar results. These hybrid Cu based nanoparticles released copper ions when immersed in water explaining their antimicrobial behavior against Escherichia coli and Staphylococcus aureus as measured by the minimum inhibitory and minimum bactericidal concentrations (MIC and MBC). Noteworthy, when these nanostructured particles were mixed with an organic coating the resulting film eliminated until a 99% of both bacteria at concentrations as low as 0.01 wt%.

  11. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

    PubMed Central

    Grundner, Sebastian; Markovits, Monica A.C.; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A.; Hensen, Emiel J.M.; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A.

    2015-01-01

    Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite. PMID:26109507

  12. Fabrication of zeolite/polymer multilayer composite membranes for carbon dioxide capture: Deposition of zeolite particles on polymer supports.

    PubMed

    Ramasubramanian, Kartik; Severance, Michael A; Dutta, Prabir K; Ho, W S Winston

    2015-08-15

    Membranes, due to their smaller footprint and potentially lower energy consumption than the amine process, offer a promising route for post-combustion CO2 capture. Zeolite Y based inorganic selective layers offer a favorable combination of CO2 permeance and CO2/N2 selectivity, membrane properties crucial to the economics. For economic viability on large scale, we propose to use flexible and scalable polymer supports for inorganic selective layers. The work described in this paper developed a detailed protocol for depositing thin zeolite Y seed layers on polymer supports, the first step in the synthesis of a polycrystalline zeolite Y membrane. We also studied the effects of support surface morphology (pore size and surface porosity) on the quality of deposition and identified favorable supports for the deposition. Two different zeolite Y particles with nominal sizes of 200 nm and 40 nm were investigated. To obtain a complete coverage of zeolite particles on the support surface with minimum defects and in a reproducible manner, a vacuum-assisted dip-coating technique was developed. Images obtained using both digital camera and optical microscope showed the presence of color patterns on the deposited surface which suggested that the coverage was complete. Electron microscopy revealed that the particle packing was dense with some drying cracks. Layer thickness with the larger zeolite Y particles was close to 1 μm while that with the smaller particles was reduced to less than 0.5 μm. In order to reduce drying cracks for layers with smaller zeolite Y particles, thickness was reduced by lowering the dispersion concentration. Transport measurement was used as an additional technique to characterize these layers.

  13. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3.

    PubMed

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-01-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3. PMID:25791958

  14. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    PubMed Central

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-01-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3. PMID:25791958

  15. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3.

    PubMed

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-03-20

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3.

  16. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    NASA Astrophysics Data System (ADS)

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-03-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3.

  17. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.

  18. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone. PMID:25078817

  19. Impact protection behavior of a mordenite zeolite system

    NASA Astrophysics Data System (ADS)

    Xu, J.; Hu, R.; Chen, X.; Hu, D.

    2016-05-01

    By combining zeolite with water, a novel nanocomposite may exhibit extraordinary capability of energy absorption and impact mitigation. The multiple size of zeolite may lead to simultaneous yet different infiltration behaviors of water molecules, and thus multi-staged energy mitigation characteristics (which may benefit the scope of application). In this study, we investigate the dynamic infiltration behavior of water into mordenite zeolite (MOR) using molecular dynamics (MD) simulations. Thanks to its hydrophobicity and multi pore-sized structure, the MOR system has a decent energy mitigation performance upon high impact speed. Parametric studies are carried out to investigate the effects of various parameters, including the impact speed, mass, and water/zeolite ratio, on energy mitigating characteristics. The MOR/water mixture may perform better at a higher impact energy with higher MOR zeolite-water ratio. Upon unloading, the defiltration of water molecules is faster and more complete at higher impact speed. Results may guide the design and application of the energy mitigation nanosystem.

  20. Risk assessment for the transportation of radioactive zeolite liners

    SciTech Connect

    Not Available

    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: /sup 90/Sr = 3000 Ci, /sup 134/Cs = 7000 Ci, /sup 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.

  1. Producing a synthetic zeolite from secondary coal fly ash.

    PubMed

    Zhou, Chunyu; Yan, Chunjie; Zhou, Qi; Wang, Hongquan; Luo, Wenjun

    2016-11-01

    Secondary coal fly ash is known as a by-product produced by the extracting alumina industry from high-alumina fly ash, which is always considered to be solid waste. Zeolitization of secondary coal fly ash offers an opportunity to create value-added products from this industrial solid waste. The influence of synthesis parameters on zeolite NaA such as alkalinity, the molar ratio of SiO2/Al2O3, crystallization time and temperature was investigated in this paper. It was found that the types of synthetic zeolites produced were to be highly dependent on the conditions of the crystallization process. Calcium ion exchange capacity and whiteness measurements revealed that the synthesized product meets the standard for being used as detergent, indicating a promising use as a builder in detergent, ion-exchangers or selective adsorbents. Yield of up to a maximum of 1.54 g/g of ash was produced for zeolite NaA from the secondary coal fly ash residue. This result presents a potential use of the secondary coal fly ash to obtain a high value-added product by a cheap and alternative zeolitization procedure. PMID:27080358

  2. Cadmium adsorption on vermiculite, zeolite and pumice: batch experimental studies.

    PubMed

    Panuccio, Maria Rosaria; Sorgonà, Agostino; Rizzo, Marcella; Cacco, Giovanni

    2009-01-01

    Batch experiments were performed to evaluate the combined effects of ionic activity, pH, and contact time on the cadmium sorption in three different minerals, vermiculite, zeolite, and pumice, commonly employed as substrata in nurseries and recently considered for their potential use in remediation methods. The extent of cadmium sorption was vermiculite>zeolite>pumice, as shown by the Langmuir and Freundlich parameters, and it was highly dependent on mineral characteristics. The percentage of cadmium sorption in zeolite and vermiculite did not depend on cadmium concentration, while in pumice this percentage was positively correlated to the initial cadmium concentration. At low cadmium concentrations (30-120 microM), the metal sorbed on zeolite was mainly present in the nonexchangeable form (70%) at levels much higher than those found for vermiculite and pumice. The primary variable responsible for determination of cadmium mobility in these minerals was confirmed to be pH. The ionic concentrations of Hoagland nutrient solution were significantly modified by both pH and mineral composition, while the presence of cadmium caused no changes. With vermiculite and zeolite, the time-course of cadmium sorption was related to mineral composition to a greater extent than to cadmium concentration. While with pumice, the percentage of cadmium sorbed after 6 weeks was lower than with the other two minerals, and it was inversely correlated to the initial cadmium concentration.

  3. Zeolite A effect on calcium homeostasis in growing goats.

    PubMed

    Schwaller, D; Wilkens, M R; Liesegang, A

    2016-04-01

    The purpose of this study was to investigate the influence of 2 different concentrations of zeolite A on calcium homeostasis. Seventeen growing goats were divided into 3 groups. Whereas the control group (5 animals) received no supplementation, 2 treatment groups were supplemented with zeolite A at either 1.2 (6 animals) or 1.6 g/kg BW (6 animals), respectively. Blood and urine samples were continually drawn and bone mineral density was measured weekly by peripheral quantitative computed tomography. After 3 wks, the animals were slaughtered and samples were taken from the rumen, duodenum, and kidneys. Plasma concentrations of phosphate ( < 0.001), magnesium ( < 0.001), and 1.25-dihydroxycholecalciferol ( < 0.01) as well as renal excretion of phosphate ( < 0.05) were significantly lower in the treatment groups compared with the control group. Although bone resorption was increased in both treatment groups ( < 0.05), no alterations in bone structure were detected. Determination of gastrointestinal absorption of calcium by Ussing chamber technique and quantification of RNA and protein expression of genes known to be involved in active calcium absorption did not reveal any stimulating effect of zeolite. Plasma calcium concentrations were not altered, probably because of the sufficient dietary calcium supply. However due to the effects of zeolite on 1,25 dihydroxycholecalciferol, bone metabolism and serum concentrations of phosphate and magenesium shown in the present study, potential negative long-termin effects on the animals should be considered whenever rations with zeolite are designed. PMID:27136016

  4. Bendable Zeolite Membranes: Synthesis and Improved Gas Separation Performance.

    PubMed

    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.

  5. Multilevel Dual Damascene copper interconnections

    NASA Astrophysics Data System (ADS)

    Lakshminarayanan, S.

    Copper has been acknowledged as the interconnect material for future generations of ICs to overcome the bottlenecks on speed and reliability present with the current Al based wiring. A new set of challenges brought to the forefront when copper replaces aluminum, have to be met and resolved to make it a viable option. Unit step processes related to copper technology have been under development for the last few years. In this work, the application of copper as the interconnect material in multilevel structures with SiO2 as the interlevel dielectric has been explored, with emphasis on integration issues and complete process realization. Interconnect definition was achieved by the Dual Damascene approach using chemical mechanical polishing of oxide and copper. The choice of materials used as adhesion promoter/diffusion barrier included Ti, Ta and CVD TiN. Two different polish chemistries (NH4OH or HNO3 based) were used to form the interconnects. The diffusion barrier was removed during polishing (in the case of TiN) or by a post CMP etch (as with Ti or Ta). Copper surface passivation was performed using boron implantation and PECVD nitride encapsulation. The interlevel dielectric way composed of a multilayer stack of PECVD SiO2 and SixNy. A baseline process sequence which ensured the mechanical and thermal compatibility of the different unit steps was first created. A comprehensive test vehicle was designed and test structures were fabricated using the process flow developed. Suitable modifications were subsequently introduced in the sequence as and when processing problems were encountered. Electrical characterization was performed on the fabricated devices, interconnects, contacts and vias. The structures were subjected to thermal stressing to assess their stability and performance. The measurement of interconnect sheet resistances revealed lower copper loss due to dishing on samples polished using HNO3 based slurry. Interconnect resistances remained stable upto 400o

  6. The use Na, Li, K cations for modification of ZSM-5 zewolite to control hydrocarbon cold-start emission

    SciTech Connect

    Golubeva V.; Rohatgi U.; Korableva, A.; Anischenko, O.; Kustov, L.; Nissenbaum, V; Viola, M.B.

    2012-08-29

    This paper addresses the problem of controlling hydrocarbon emissions from cold-start of engines by investigating the adsorbents which could adsorb the hydrocarbons at cold temperatures and hold them to 250-300 ?. The materials, that has been studied, are based on the modification of ZSM-5 (SiO{sub 2}/Al{sub 2}O{sub 3} = 35) zeolite with Li, K, Na cations. It has been shown that the introduction of Li, Na and K in an amount that is equivalent to the content of Al in zeolite results in occurrence of toluene temperature desorption peaks at high-temperatures. The toluene temperature desorption curves for 5%Li-ZSM-5 and 2.3%Na-ZSM-5 zeolites are identical and have peak toluene desorption rate between 200 to 400 ?. Upon analysis of toluene adsorption isotherms for 2.3%Na-ZSM-5 and 5%Li-ZSM-5, it was concluded that the toluene diffusion inside of the modified zeolites channels is extremely slow and the sorption capacity of 2.3%Na-ZSM-5 is higher than with 5%Li-ZSM-5. The 2.3%Na-ZSM-5 didn't change toluene temperature programmed desorption (TPD) rate of curve after the treatment in environment with 10% ?{sub 2}? at 750-800 ? for about 28 h. The 2.3%Na-ZSM-5 zeolite is very promising as adsorbent to control the cold-start hydrocarbon emissions.

  7. Silver nitrate in silver zeolite A: three-dimensional incommensurate guest ordering in a zeolite framework.

    PubMed

    Viertelhaus, M; Taylor, A E; Kloo, L; Gameson, I; Anderson, P A

    2006-05-21

    We report the results of a detailed examination of the occlusion of silver nitrate in silver zeolite A (AgA). The superlattice reported to occur in (AgNO3)9-AgA was found to melt at between 80 and 100 degrees C on heating and reappear when the sample was cooled down to 80 degrees C. Annealing in this temperature range and rigorous exclusion of water produced an enhancement of the superlattice peaks, which results from ordering of the contents of the zeolite cages. Peaks assigned to the superlattice were indexed with the tetragonal lattice parameters a = 17.440(5) and c = 12.398(4) A and proposed space group P4/nmm. The sharp peaks representing the lattice of the framework (a = 12.3711(5) A, Pm3m) remained largely unaffected by the guest in this compound, which was found to exhibit strong negative thermal expansion. The host and guest lattices are incommensurate with the tetragonal guest lattice being slightly larger than the cubic host in the c-direction and slightly smaller in the a- and b-directions. PMID:16688325

  8. Advanced NMR characterization of zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Welsh, L. B.

    1985-04-01

    The program discussed in this report is a two-year two-phase joint UOP-University of Illinois study of the application of improved high resolution solid state nuclear magnetic resonance (NMR) techniques to the characterization of zeolite catalysts. During the first phase of this program very pure, and in some cases isotopically enriched faujasites will be prepared and studied by magic angle sample spinning NMR (MASS NMR) and variable engine sample spinning NMR (VASS NMR) on 500 and 360 MHz (proton frequency) NMR spectrometers. The NMR techniques that will be emphasized are the measurement and analysis of the (17)O NMR properties, (27)Al NMR intensity quantitation, and (27)Al and (29)Si NMR relaxation rates. During the second phase of this program these NMR techniques will be used to study the effects of impurity concentration, dealumination treatments and cation exchange on the NMR properties of faujasites. The initial emphasis of this program during Phase I is on the preparation and measurement of the NMR properties of (17)O enriched Na-Y faujasties.

  9. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  10. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  11. Synthetic Zeolites and Other Microporous Oxide Molecular Sieves

    NASA Astrophysics Data System (ADS)

    Sherman, John D.

    1999-03-01

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow "tailoring" of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol.

  12. Hot isostatic pressing of glass-zeolite composites

    SciTech Connect

    Hash, M.C.; Pereira, C.; Lewis, M.A.

    1996-05-01

    Glass-zeolite waste forms are being developed for immobilizing the chloride waste salt generated from the electrometallurgical treatment of spent fuel. Glass-zeolite composites with high densities were made using hot isostatic pressing (HIP) techniques. Processing parameters were investigated to yield desirable structural ceramic properties such as mechanical, chemical, and thermal stability. Limits for these parameters were determined by differential thermal and thermogravimetric analysis. The resulting ceramic properties such as bulk density, open or apparent porosity, and leach resistance were determined. In addition, phase equilibria and particle-size distribution were observed by optical light and electron microscopy. Pre-HIP processing techniques were also studied to ensure intimate mixing of the glass and zeolite powders. Particle size distributions resulting from dry blending procedure are appropriate for needed flow and packing characteristics.

  13. Synthetic zeolites and other microporous oxide molecular sieves.

    PubMed

    Sherman, J D

    1999-03-30

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow "tailoring" of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol.

  14. Wet gringing of zeolite in stirred media mill

    NASA Astrophysics Data System (ADS)

    Mucsi, G.; Bohács, K.

    2016-04-01

    In the present study the results of systematic experimental series are presented with the specific goal of optimizing the zeolite nanoparticles' production using a wet stirred media mill. The diameter of the grinding media as well as the rotor velocity were varied in the experiments. Particle size distribution and "outer" specific surface area of the ground samples were measured by a laser particle size analyser. Additionally, BET, XRD and FT-IR analyses were performed for the characterization of the "total" specific surface area as well as the crystalline and material structure, respectively. Based on the results of the laboratory experiments it was found that wet stirred media milling provided significant reductions in the particle size of zeolite. Furthermore, the crystallinity of the samples also decreased, so not only the physical but the mineralogical characteristics of zeolite can be controlled by stirred media milling.

  15. Formulation of cracking catalyst based on zeolite and natural clays

    SciTech Connect

    Aliev, R.R.; Lupina, M.I.

    1995-11-01

    Domestically manufactured cracking catalysts are based on a synthetic amorphous aluminosilicate matrix and Y zeolite. A multistage {open_quotes}gel{close_quotes} technology is used in manufacturing the catalysts. The process includes mixing solutions of sodium silicate and acidic aluminum sulfate, forming, syneresis, and activation of the beaded gel. In the manufacture of bead catalysts, the next steps in the process are washing, drying, and calcining; in the manufacture of microbead catalysts, the next steps are dispersion and formation of a hydrogel slurry, spray-drying, and calcining. The Y zeolite is either introduced into the alumina-silica sol in the stage of forming the beads, or introduced in the dispersion stage. With the aim of developing an active and selective cracking catalyst based on Y zeolite and natural clays, with improved physicomechanical properties, the authors carried out a series of studies, obtaining results that are set forth in the present article.

  16. Ring opening of methylcyclohexane over platinum-loaded zeolites.

    PubMed

    Calemma, Vincenzo; Carati, Angela; Flego, Cristina; Giardino, Roberto; Gagliardi, Federica; Millini, Roberto; Bellussi, Giuseppe

    2008-01-01

    The activity of different platinum-loaded zeolites (Mordenite, ZSM-12, ZSM-5, ZSM-23) was investigated in the hydroconversion of methylcyclohexane (MCH), in the context of upgrading highly aromatic distillates for fuel blending. In all cases, conversion of MCH proceeds according to a pathway where the primary products are a mixture of dimethylcyclopentanes and ethylcyclopentane formed by isomerization and ring contraction of MCH. The primary products undergo consecutive ring-opening reactions with formation of n- and isoheptanes. The latter further react to form lower-molecular-weight n- and isoalkanes. The selectivity and distribution of products deriving from ring-contraction and ring-opening reactions are strongly affected by the pore size and topology of the zeolites. ZSM-5 exhibits a strong reactant shape-selectivity effect on ring-opening products. The evaluated zeolites show the following order of activity in the conversion of methylcyclohexane: Mordenite>ZSM-12>ZSM-5>ZSM-23. PMID:18702154

  17. Mechanistic proposal for the zeolite catalyzed methylation of aromatic compounds.

    PubMed

    Svelle, Stian; Bjørgen, Morten

    2010-12-01

    Alkylation and methylation reactions are important reactions in petrochemical production and form part of the reaction mechanism of many hydrocarbon transformation processes. Here, a new reaction mechanism is explored for the zeolite catalyzed methylation of arenes using quantum chemical calculations. It is proposed that the most substituted methylbenzenes, which will reside predominantly on the protonated form when adsorbed in a zeolite, can react directly with a neutral methanol molecule in the vicinity, thereby initiating the methylation reaction without having to return a proton to the zeolite surface. The calculated barriers are quite low, indicating that the suggested mechanism is plausible. This route might explain how the most substituted methylbenzenes can function as efficient reaction intermediates in the methanol to hydrocarbons reaction without themselves acting as catalyst poisons as a consequence of their high proton affinities. PMID:21049891

  18. High adherence copper plating process

    DOEpatents

    Nignardot, Henry

    1993-01-01

    A process for applying copper to a substrate of aluminum or steel by electrodeposition and for preparing an aluminum or steel substrate for electrodeposition of copper. Practice of the invention provides good adhesion of the copper layer to the substrate.

  19. Squaraines inside Zeolites: Preparation, Stability, and Photophysical Properties.

    PubMed

    Cano, María Luz; Cozens, Frances L.; Esteves, María A.; Márquez, Francisco; García, Hermenegildo

    1997-10-17

    A series of four symmetrical squaraines (ditoylyl, di-m-xylyl, dianisyl, and diresorcinyl) incorporated inside zeolites Y, mordenite, and ZSM-5 have been obtained by treating squaric acid and the corresponding arene in the presence of acid zeolites. Acid sites and high reaction temperatures (150 degrees C) were found to be crucial for the success of the preparation procedure. Surprisingly, this method failed for the preparation of the squaraine derived from N,N-dimethylaniline, which is known to be readily formed from squaric acid in homogeneous phase without a catalyst. The solid samples containing squaraines were characterized by diffuse reflectance and Raman spectroscopies and by thermogravimetry-differential scanning calorimetry. Among the hosts, mordenite was found to be the most general and convenient zeolite for the preparation of the squaraines, while in the other solids either the organic content adsorbed was comparatively smaller (ZSM-5) or some squaraines were not very stable (Y zeolite for ditolyl and dixylyl squaraines). The absorption spectra of the samples correspond to the J-aggregation state of the squaraines, except for some ZSM-5 samples, where simultaneous observation of the bands due to both monomers and aggregates occurs. Aggregation also changes with the water content of the samples. Treatment of the zeolite-bound diresorcinyl squaraine with basic aqueous solutions leads to remarkable variations in the diffuse reflectance and Raman spectra. These changes in the Raman spectrum of the diresorcinyl squaraine were found to be reversible by basic or acid washings. Laser flash photolysis using the 355- or 532-nm output of a Nd-YAG laser (<10 ns pulses; zeolite host. On the basis of the similarity of the UV-vis absorption spectra obtained in solution, these transients have been identified as the radical cation (HY) and the triplet excited

  20. Bicontinuous zeolite polymer composite membranes prepared via float casting.

    PubMed

    Kiesow, Ina; Marczewski, Dawid; Reinhardt, Lutz; Mühlmann, Marcel; Possiwan, Mario; Goedel, Werner A

    2013-03-20

    We prepared bicontinuous composite membranes comprising zeolite A particles. The particles form a monolayer which is embedded in a polymer sheet in such a way that each particle penetrates both surfaces of the polymer sheet. Preparation was done via "float casting"; a mixture of hydrophobized zeolite particles and an appropriate volume of a nonvolatile polymerizable organic liquid monomer was applied onto a water surface. The monomer was solidified via photopolymerization to form the above-mentioned membrane. In as-prepared state (without extensive drying), this membrane is permeable for water vapor (in case of zeolite 4A permeance = 8 × 10(-9) mol m(-2) s(-1) Pa(-1), permeability = 1.65 × 10(-14) mol m(-1) s(-1) Pa(-1) = 49 barrer) but impermeable for nitrogen (permeance below detection limit of 5 × 10(-12) mol m(-2) s(-1) Pa(-1), permeability below detection limit of 1 × 10(-17) mol m(-1) s(-1) Pa(-1) = 0.03 barrer). The permeance for water vapor increases with increasing pore size of the zeolite (in case of zeolite 5A, all other parameters being unchanged, permeance = 12 × 10(-9) mol m(-2) s(-1) Pa(-1), permeability = 2.4 × 10(-14) mol m(-1) s(-1) Pa(-1) = 72 barrer). These observations indicate that the water molecules are predominantly transported through the zeolite channels and at the same time block the passage of other molecules. The impermeability for nitrogen in as-prepared state indicates a low amount of defects that are not blocked by water. Furthermore, the composite nature of the membrane gives rise to a reduced brittleness; membranes can be handled manually without support structure and thus might be promising candidates for separation technology. PMID:23398555

  1. Zeolites replacing plant fossils in the Denver formation, Lakewood, Colorado.

    USGS Publications Warehouse

    Modreski, P.J.; Verbeek, E.R.; Grout, M.A.

    1984-01-01

    Well-developed crystals of heulandite and stilbite, within fossil wood, occur in sedimentary rocks in Lakewood, Jefferson County. The rocks belong to the Denver formation, a locally fossiliferous deposit of fluvial claystone, siltstone, sandstone and conglomerate, containing some volcanic mudflows (andesitic) of late Cretaceous to Palaeocene age. Altered volcanic glass released Na and Ca into the ground-water and subsequently zeolites were crystallized in the open spaces between grains and within fossil plant structures. Minor pyrite, quartz (jasper), calcite and apatite also occur as replacements of fossil wood. Similar zeolite occurrences in other areas are reviewed.-R.S.M.

  2. Synthesis process of zeolite P using a poorly crystallized kaolinite

    NASA Astrophysics Data System (ADS)

    Meftah, M.; Oueslati, W.; Ben Haj Amara, A.

    2009-11-01

    Poorly crystallized kaolinite KGa2 and metakaolinites derived from them were studied under hydrothermal conditions in an aqueous sodium hydroxide solution. Reaction was obtained in a specific reactor allowing a continuous agitation and pH and temperature controls. Metakaolinte were derived from heated kaolinite at 500∘ C and 900∘ C. Using kaolinite and metakaolinite obtained after heating at 500∘ C the main formed products w metakaolinte obtained at 900∘ C reacted with NaOH solution zeolite A (LTA) is the first synthesized product and a prolonged treatment (72 hours) leads to synthesize zeolite P. Intermediate and homogeneous phases were characterized by XRD analysis and MAS NMR spectroscopy.

  3. Method for encapsulating nanoparticles in a zeolite matrix

    DOEpatents

    Coker, Eric N.

    2007-12-11

    A method for preparing a metal nanocluster composite material. A porous zeolitic material is treated with an aqueous metal compound solution to form a metal ion-exchanged zeolitic material, heated at a temperature ramp rate of less than 2.degree. C./min to an elevated temperature, cooled, contacted with an organic monomer and heating to induce polymerization, and heating the composite material to greater than 350.degree. C. under non-oxidizing conditions to form a metal nanocluster-carbon composite material with nanocluster sizes between approximately 0.6 nm and 10 nm.

  4. Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

    NASA Astrophysics Data System (ADS)

    Phillips, Cory Bernard

    1999-11-01

    This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites

  5. Experiments with Zeolites at the Secondary School Level: Experience from The Netherlands

    NASA Astrophysics Data System (ADS)

    Coker, Eric N.; Davis, Pamela J.; Kerkstra, Aonne; van Bekkum, Herman

    1999-10-01

    This article describes a number of experiments that involve zeolites and are suitable for secondary-school chemistry laboratories. The experiments have been introduced successfully into secondary schools in The Netherlands. Zeolites are used in enormous quantities as builders (water softeners) in laundry detergents; they account for 15-30 wt % of most laundry detergents currently on the European market. In a series of experiments, students test the hardness of tap water before and after treatment with some zeolite and perform tests with a range of commercial laundry detergents containing zeolites. Zeolites are also used as catalysts in numerous industrial processes; another experiment described here highlights the use of zeolites as recyclable catalysts in an esterification reaction. A duplicate reaction is carried out in parallel, but using the conventional sulfuric acid catalyst instead of the zeolite. This experiment provides a good example of the benefit of a recyclable, heterogeneous catalyst over the conventional homogeneous one that is discarded as waste material.

  6. Improved Electroformed Structural Copper and Copper Alloys

    NASA Technical Reports Server (NTRS)

    Malone, G. A.; Hudson, W.; Babcock, B.; Edwards, R.

    1998-01-01

    Electroforming offers a superior means for fabricating internally cooled heat exchangers and structures subjected to thermal environments. Copper is deposited from many such applications because of the good thermal conductivity. It suffers from mediocre yield strength as a structural material and loses mechanical strength at intermediate temperatures. Mechanical properties similar to those of electroformed nickel are desired. Phase 1 examined innovative means to improve deposited copper structural performance. Yield strengths as high as 483 MPa (70 ksi) were obtained with useful ductility while retaining a high level of purity essential to good thermal conductivity. Phase 2 represents a program to explore new additive combinations in copper electrolytes to produce a more fine, equiaxed grain which can be thermally stabilized by other techniques such as alloying in modest degrees and dispersion strengthening. Evaluation of new technology - such as the codeposition of fullerness (diamond-like) particles were made to enhance thermal conductivity in low alloys. A test fire quality tube-bundle engine was fabricated using these copper property improvement concepts to show the superiority of the new coppers and fabrications methods over competitive technologies such as brazing and plasma deposition.

  7. Copper Delivery by Metallochaperone Proteins

    SciTech Connect

    Rosenzweig, A.C.

    2010-03-08

    Copper is an essential element in all living organisms, serving as a cofactor for many important proteins and enzymes. Metallochaperone proteins deliver copper ions to specific physiological partners by direct protein-protein interactions. The Atx1-like chaperones transfer copper to intracellular copper transporters, and the CCS chaperones shuttle copper to copper,zinc superoxide dismutase. Crystallographic studies of these two copper chaperone families have provided insights into metal binding and target recognition by metallochaperones and have led to detailed molecular models for the copper transfer mechanism.

  8. Graphene synthesis and characterization on copper

    NASA Astrophysics Data System (ADS)

    Mohsin, Ali

    Graphene, two dimensional sheet of carbon atoms has recently gained attention as some of its properties are promising for electronics applications e.g. higher mobility that translates to higher operating frequency for devices geared towards radio frequency applications. Excellent optical transmittance combined with its semi metallic behavior makes it an important material for transparent contacts in solar cells. To bring graphene to the production level, synthesis methods are needed for its growth on wafer scale. It has been shown that chemical vapor deposition (CVD) is one of the techniques that can potentially synthesize wafer scale graphene. Recently copper has gained popularity as an important substrate material for graphene growth due to its lower carbon solubility, which allows better control over number of graphene layers. Here we report optimization of graphene growth on copper foils with our home made atmospheric pressure chemical vapor deposition (APCVD) setup. Graphene growth on copper under APCVD was non self-limiting similar to other reports. It was found that apart from growth parameters surface texture plays a very important role in graphene growth. In fact, few layer and bilayer graphene were obtained on the regions where copper surface was not uniform, confirmed by Raman spectroscopy. To improve copper surface texture thin layer of copper film was evaporated by electron beam evaporation before the graphene growth process. After this modification, monolayer graphene was obtained on areas as large as 300 microm x 300 microm confirmed by Raman area maps. Graphene transfer procedure was also optimized so that graphene on metal surface could be transferred to insulating substrate.

  9. 78 FR 20137 - Probable Economic Effect of Certain Modifications to the North American Free Trade Agreement...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-04-03

    ... glassware; copper, nickel, and other base metals; machinery and parts; rail locomotives; trailers; optical... list of modifications in the attachment to the March 11, 2013, letter in the form of a correlation... modifications, and the clarifying correlation table are available on the Commission's Web site at...

  10. The growth of zeolites A, X and mordenite in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, N.; Coker, E. N.; Dixon, A. G.; Warzywoda, J.; Thompson, R. W.

    1994-01-01

    Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of

  11. Improving the osteointegration of Ti6Al4V by zeolite MFI coating

    SciTech Connect

    Li, Yong; Jiao, Yilai; Li, Xiaokang; Guo, Zheng

    2015-05-01

    Osteointegration is crucial for success in orthopedic implantation. In recent decades, there have been numerous studies aiming to modify titanium alloys, which are the most widely used materials in orthopedics. Zeolites are solid aluminosilicates whose application in the biomedical field has recently been explored. To this end, MFI zeolites have been developed as titanium alloy coatings and tested in vitro. Nevertheless, the effect of the MFI coating of biomaterials in vivo has not yet been addressed. The aim of the present work is to evaluate the effects of MFI-coated Ti6Al4V implants in vitro and in vivo. After surface modification, the surface was investigated using field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). No difference was observed regarding the proliferation of MC3T3-E1 cells on the Ti6Al4V (Ti) and MFI-coated Ti6Al4V (M−Ti) (p > 0.05). However, the attachment of MC3T3-E1 cells was found to be better in the M−Ti group. Additionally, ALP staining and activity assays and quantitative real-time RT-PCR indicated that MC3T3-E1 cells grown on the M−Ti displayed high levels of osteogenic differentiation markers. Moreover, Van-Gieson staining of histological sections demonstrated that the MFI coating on Ti6Al4V scaffolds significantly enhanced osteointegration and promoted bone regeneration after implantation in rabbit femoral condylar defects at 4 and 12 weeks. Therefore, this study provides a method for modifying Ti6Al4V to achieve improved osteointegration and osteogenesis. - Highlights: • Osteointegration is a crucial factor for orthopedic implants. • We coated MFI zeolite on Ti6Al4V substrates and investigated the effects in vitro and in vivo. • The MFI coating displayed good biocompatibility and promoted osteogenic differentiation in vitro. • The MFI coating promoted osteointegration and osteogenesis peri-implant in vivo.

  12. Improving the osteointegration of Ti6Al4V by zeolite MFI coating.

    PubMed

    Li, Yong; Jiao, Yilai; Li, Xiaokang; Guo, Zheng

    2015-05-01

    Osteointegration is crucial for success in orthopedic implantation. In recent decades, there have been numerous studies aiming to modify titanium alloys, which are the most widely used materials in orthopedics. Zeolites are solid aluminosilicates whose application in the biomedical field has recently been explored. To this end, MFI zeolites have been developed as titanium alloy coatings and tested in vitro. Nevertheless, the effect of the MFI coating of biomaterials in vivo has not yet been addressed. The aim of the present work is to evaluate the effects of MFI-coated Ti6Al4V implants in vitro and in vivo. After surface modification, the surface was investigated using field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). No difference was observed regarding the proliferation of MC3T3-E1 cells on the Ti6Al4V (Ti) and MFI-coated Ti6Al4V (M-Ti) (p > 0.05). However, the attachment of MC3T3-E1 cells was found to be better in the M-Ti group. Additionally, ALP staining and activity assays and quantitative real-time RT-PCR indicated that MC3T3-E1 cells grown on the M-Ti displayed high levels of osteogenic differentiation markers. Moreover, Van-Gieson staining of histological sections demonstrated that the MFI coating on Ti6Al4V scaffolds significantly enhanced osteointegration and promoted bone regeneration after implantation in rabbit femoral condylar defects at 4 and 12 weeks. Therefore, this study provides a method for modifying Ti6Al4V to achieve improved osteointegration and osteogenesis.

  13. Infrared spectroscopic examination of the interaction of urea with the naturally occurring zeolite clinoptilolite

    USGS Publications Warehouse

    Byler, D.M.; Gerasimowicz, W.V.; Stockette, V.M.; Eberl, D.D.

    1991-01-01

    Infrared spectroscopy has shown for the first time that the naturally occurring zeolite clinoptilolite can absorb urea, (NH2)2CO, under ambient conditions from either aqueous or ethanolic solutions. The two strongest NH stretching bands at 3441 and 3344 cm-1 in pure, solid urea shift to higher frequency (about 3504 and 3401 cm-1) after absorption. Two of the four urea bands in the 1800-1300 cm-1 range (at 1683 and 1467 cm-1) undergo marked downward shifts to about 1670 and 1445 cm-1. The other two bands show little change in frequency. The strong band at 1602 cm-1, however, diminishes in intensity to little more than an ill-defined shoulder on the 1626-cm-1 peak. When clinoptilolite is heated to 450 ??C and then treated with molten urea (ca. 140 ??C) for several minutes, and finally washed twice with ethanol to remove excess unreacted urea, further changes become apparent in the spectrum of the urea-treated clinoptilolite. The two NH stretching bands broaden without significant change in frequency. Two new bands appear in the midfrequency range at 1777 (weak) and 1719 (medium strong) cm-1. Of the four original midfrequency peaks, the one at 1602 cm-1 is now absent. Two others (1627 and 1440 cm-1) exhibit little change, while the fourth has broadened and shifted down to 1663 cm-1, where it appears as a shoulder on the band at 1627 cm-1. Both treatments clearly induce interaction between urea and the zeolite which seems to result in significant modifications in the nature of the hydrogen bonding of the substrate. ?? 1991.

  14. Mechanical durability of superhydrophobic and oleophobic copper meshes

    NASA Astrophysics Data System (ADS)

    Yin, Linting; Yang, Jin; Tang, Yongcai; Chen, Lin; Liu, Can; Tang, Hua; Li, Changsheng

    2014-10-01

    We developed a simple and inexpensive method to prepare the superhydrophobic and oleophobic copper meshes with rough structures fabrication and chemical modification. The achieved surfaces displayed liquid-repellent toward water and several organic liquids (such as hexadecane), which possessed much lower surface tension than that of water. Liquid repellency of the fabricated superhydrophobic copper mesh was demonstrated by visible experiment results and contact angle measurements. Even if the superhydrophobic copper mesh was rolled up, it still kept the superhydrophobicity. The mechanical durability was investigated by finger touch and mechanical abrasion tests. The results indicated that the copper mesh can maintain its superhydrophobicity against an abrasion length of 300 cm under a high pressure (77.2 kPa). The superhydrophobicity and oleophobicity, combined with mechanical durability, would promote the superhydrophobic surface to practical application in industry in the future.

  15. Bioaccessibility and Solubility of Copper in Copper-Treated Lumber

    EPA Science Inventory

    Micronized copper (MC)-treated lumber is a recent replacement for Chromated Copper Arsenate (CCA) and Ammonium Copper (AC)-treated lumbers; though little is known about the potential risk of copper (Cu) exposure from incidental ingestion of MC-treated wood. The bioaccessibility o...

  16. Martian zeolites as a source of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Mousis, Olivier; Simon, Jean-Marc; Bellat, Jean-Pierre; Schmidt, Frédéric; Bouley, Sylvain; Chassefière, Eric; Sautter, Violaine; Quesnel, Yoann; Picaud, Sylvain; Lectez, Sébastien

    2016-11-01

    The origin of the martian methane is still poorly understood. A plausible explanation is that methane could have been produced either by hydrothermal alteration of basaltic crust or by serpentinization of ultramafic rocks producing hydrogen and reducing crustal carbon into methane. Once formed, methane storage on Mars is commonly associated with the presence of hidden clathrate reservoirs. Here, we alternatively suggest that chabazite and clinoptilolite, which belong to the family of zeolites, may form a plausible storage reservoir of methane in the martian subsurface. Because of the existence of many volcanic terrains, zeolites are expected to be widespread on Mars and their Global Equivalent Layer may range up to more than ∼1 km, according to the most optimistic estimates. If the martian methane present in chabazite and clinoptilolite is directly sourced from an abiotic source in the subsurface, the destabilization of a localized layer of a few millimeters per year may be sufficient to explain the current observations. The sporadic release of methane from these zeolites requires that they also remained isolated from the atmosphere during its evolution. The methane release over the ages could be due to several mechanisms such as impacts, seismic activity or erosion. If the methane outgassing from excavated chabazite and/or clinoptilolite prevails on Mars, then the presence of these zeolites around Gale Crater could explain the variation of methane level observed by Mars Science Laboratory.

  17. Synthesis of mesoporous zeolite single crystals with cheap porogens

    NASA Astrophysics Data System (ADS)

    Tao, Haixiang; Li, Changlin; Ren, Jiawen; Wang, Yanqin; Lu, Guanzhong

    2011-07-01

    Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, 27Al magic angle spinning nuclear magnetic resonance ( 27Al MAS NMR), temperature-programmed desorption of ammonia (NH 3-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. 27Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites.

  18. Zeolite formation from coal fly ash and its adsorption potential

    SciTech Connect

    Duangkamol Ruen-ngam; Doungmanee Rungsuk; Ronbanchob Apiratikul; Prasert Pavasant

    2009-10-15

    The possibility in converting coal fly ash (CFA) to zeolite was evaluated. CFA samples from the local power plant in Prachinburi province, Thailand, were collected during a 3-month time span to account for the inconsistency of the CFA quality, and it was evident that the deviation of the quality of the raw material did not have significant effects on the synthesis. The zeolite product was found to be type X. The most suitable weight ratio of sodium hydroxide (NaOH) to CFA was approximately 2.25, because this gave reasonably high zeolite yield with good cation exchange capacity (CEC). The silica (Si)-to-aluminum (Al) molar ratio of 4.06 yielded the highest crystallinity level for zeolite X at 79% with a CEC of 240 meq/100 g and a surface area of 325 m{sup 2}/g. Optimal crystallization temperature and time were 90{sup o}C and 4 hr, respectively, which gave the highest CEC of approximately 305 meq/100 g. Yields obtained from all experiments were in the range of 50-72%. 29 refs., 5 tabs., 7 figs.

  19. Zeolitic imidazolate frameworks for kinetic separation of propane and propene

    DOEpatents

    Li, Jing; Li, Kunhao; Olson, David H.

    2014-08-05

    Zeolitic Imidazolate Frameworks (ZIFs) characterized by organic ligands consisting of imidazole ligands that are either essentially all 2-chloroimidazole ligands or essentially all 2-bromoimidazole ligands are disclosed. Methods for separating propane and propene with the ZIFs of the present invention, as well as other ZIFs, are also disclosed.

  20. Oxidation of bioethanol using zeolite-encapsulated gold nanoparticles.

    PubMed

    Mielby, Jerrik; Abildstrøm, Jacob Oskar; Wang, Feng; Kasama, Takeshi; Weidenthaler, Claudia; Kegnaes, Søren

    2014-11-10

    With the ongoing developments in biomass conversion, the oxidation of bioethanol to acetaldehyde may become a favorable and green alternative to the preparation from ethylene. Here, a simple and effective method to encapsulate gold nanoparticles in zeolite silicalite-1 is reported and their high activity and selectivity for the catalytic gas-phase oxidation of ethanol are demonstrated. The zeolites are modified by a recrystallization process, which creates intraparticle voids and mesopores that facilitate the formation of small and disperse nanoparticles upon simple impregnation. The individual zeolite crystals comprise a broad range of mesopores and contain up to several hundred gold nanoparticles with a diameter of 2-3 nm that are distributed inside the zeolites rather than on the outer surface. The encapsulated nanoparticles have good stability and result in 50 % conversion of ethanol with 98 % selectivity toward acetaldehyde at 200 °C, which (under the given reaction conditions) corresponds to 606 mol acetaldehyde/mol Au hour(-1) . PMID:25196739

  1. Mobil/Badger to market zeolite-based cumene technology

    SciTech Connect

    Rotman, D.

    1993-02-24

    Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) also began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing catalyst designed by Mobil to selectively catalyze the benzene/propylene reaction, avoiding unwanted propylene oligomerization. Because the olefin reactions are so fast, says Frank A. Demers, Badger's v.p./technology development and marketing, other zeolite technologies are forced to use complex reactor arrangements to stop the propylene-propylene reactions. However, he says, Mobil has designed a catalyst that wants to react benzene with propylene to make cumene.'

  2. USE OF SYNTHETIC ZEOLITES FOR ARSENATE REMOVAL FROM POLLUTANT WATER

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water that causes arsenical dermatitis and skin cancer. In the present work, the potential use of a variety of synthetic zeolites for removal of arsenic from water below the current and proposed EPA MCL has been examined...

  3. Oxidation of bioethanol using zeolite-encapsulated gold nanoparticles.

    PubMed

    Mielby, Jerrik; Abildstrøm, Jacob Oskar; Wang, Feng; Kasama, Takeshi; Weidenthaler, Claudia; Kegnaes, Søren

    2014-11-10

    With the ongoing developments in biomass conversion, the oxidation of bioethanol to acetaldehyde may become a favorable and green alternative to the preparation from ethylene. Here, a simple and effective method to encapsulate gold nanoparticles in zeolite silicalite-1 is reported and their high activity and selectivity for the catalytic gas-phase oxidation of ethanol are demonstrated. The zeolites are modified by a recrystallization process, which creates intraparticle voids and mesopores that facilitate the formation of small and disperse nanoparticles upon simple impregnation. The individual zeolite crystals comprise a broad range of mesopores and contain up to several hundred gold nanoparticles with a diameter of 2-3 nm that are distributed inside the zeolites rather than on the outer surface. The encapsulated nanoparticles have good stability and result in 50 % conversion of ethanol with 98 % selectivity toward acetaldehyde at 200 °C, which (under the given reaction conditions) corresponds to 606 mol acetaldehyde/mol Au hour(-1) .

  4. Direct Observation of Luminescent Silver Clusters Confined in Faujasite Zeolites.

    PubMed

    Altantzis, Thomas; Coutino-Gonzalez, Eduardo; Baekelant, Wouter; Martinez, Gerardo T; Abakumov, Artem M; Tendeloo, Gustaaf Van; Roeffaers, Maarten B J; Bals, Sara; Hofkens, Johan

    2016-08-23

    One of the ultimate goals in the study of metal clusters is the correlation between the atomic-scale organization and their physicochemical properties. However, direct observation of the atomic organization of such minuscule metal clusters is heavily hindered by radiation damage imposed by the different characterization techniques. We present direct evidence of the structural arrangement, at an atomic level, of luminescent silver species stabilized in faujasite (FAU) zeolites using aberration-corrected scanning transmission electron microscopy. Two different silver clusters were identified in Ag-FAU zeolites, a trinuclear silver species associated with green emission and a tetranuclear silver species related to yellow emission. By combining direct imaging with complementary information obtained from X-ray powder diffraction and Rietveld analysis, we were able to elucidate the main differences at an atomic scale between luminescent (heat-treated) and nonluminescent (cation-exchanged) Ag-FAU zeolites. It is expected that such insights will trigger the directed synthesis of functional metal nanocluster-zeolite composites with tailored luminescent properties. PMID:27391548

  5. DIFFUSION MEASUREMENTS DURING PERVAPORATION THROUGH A ZEOLITE MEMBRANE

    EPA Science Inventory


    An isotopic-transient technique was used to directly measure diffusion times of H2O, methanol, ethanol, 2-propanol, and acetone in pure and binary mixture feeds transporting through a zeolite membrane under steady-state pervaporation conditions. Diffusivities can be determ...

  6. Synthesis and Properties of Nano Zeolitic Imidazolate Frameworks

    SciTech Connect

    Nune, Satish K.; Thallapally, Praveen K.; Dohnalkova, Alice; Wang, Chong M.; Liu, Jun; Exarhos, Gregory J.

    2010-07-21

    Nano sized zeolitic imidazolate frameworks [nZIF-8] with excellent chemical and thermal stability has been synthesized at room temperature by simple mixing of 2-methylimidazole and zinc nitrate hexahydrate in methanol/ 1% high molecular weight poly(diallyldimethylammonium chloride) solution for 24 hrs

  7. Ionization and protonation of aromatic diamines by sorption in zeolites

    NASA Astrophysics Data System (ADS)

    Marquis, S.; Moissette, A.; Brémard, C.; Vezin, H.

    2003-06-01

    In situ diffuse reflectance UV visible, Raman scattering and EPR spectroscopies were used to monitor spontaneous ionization of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) by direct exposure to dehydrated M nZSM-5 zeolite (M=Na +, H +; n=0,3,6). The TMPD •+ radical cation is found to be generated in low yield in purely siliceous silicalite-1 whereas TMPD •+ is generated in high yield in aluminated Na nZSM-5 and H nZSM-5. The ejected electron is also characterized though electronic absorption spectra. The charge separation was found to be persistent over several months. The tight fit between the shape of TMPD and the pore size of straight channels of zeolites is considered to be the main factor responsible for the stabilization of the TMPD radical ion by preventing rapid electron back transfer. Within Na nZSM-5, the amounts of TMPD •+ and trapped electron were found to decrease over long time and to recombine to molecular TMPD. In contrast, in acidic H nZSM-5 zeolite the charge recombination generates diprotonated TMPDH 22+ occluded species. Furthermore, within H nZSM-5, protonation appears competitive to the ionization efficiency of zeolite.

  8. Preparation of zeolites for TEM (Transmission Electron Microscopy) using microtomy

    SciTech Connect

    Csencsits, R.; Gronsky, R.

    1987-12-01

    The application of microtomy to Transmission Electron Microscopy (TEM) specimen preparation of zeolite catalysts is explained. Using a new acrylic resin (LR White) thin sections (less than or equal to60 nm) may be cut with relative ease. Although the details described are specific to catalysts, microtomy and the use of the acrylic resin are applicable to any hard ceramic powder sample. 3 figs.

  9. High-pressure alchemy on a small-pore zeolite

    NASA Astrophysics Data System (ADS)

    Lee, Y.

    2011-12-01

    While an ever-expanding variety of zeolites with a wide range of framework topology is available, it is desirable to have a way to tailor the chemistry of the zeolitic nanopores for a given framework topology via controlling both the coordination-inclusion chemistry and framework distortion/relaxation. This is, however, subjected to the ability of a zeolitic nanopore to allow the redistribution of cations-water assembly and/or insertion of foreign molecules into the pores and channels. Small-pore zeolites such as natrolite (Na16Al16Si24O80x16H2O), however, have been known to show very limited capacity for any changes in the confinement chemistry. We have recently shown that various cation-exchanged natrolites can be prepared under modest conditions from natural sodium natrolite and exhibit cation-dependent volume expansions by up to 18.5% via converting the elliptical channels into progressively circular ones. Here, we show that pressure can be used as a unique and clean tool to further manipulate the chemistry of the natrolite nanopores. Our recent crystallographic and spectroscopic studies of pressure-insertion of foreign molecules, trivalent-cation exchange under pressure, and pressure-induced inversion of cation-water coordination and pore geometry in various cation-exchanged natrolites will be presented.

  10. Selective photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1998-01-01

    A selective photooxidation process for the conversion of hydrocarbon molecules to partially oxygenated derivatives, which comprises the steps of adsorbing a hydrocarbon and oxygen onto a dehydrated zeolite support matrix to form a hydrocarbon-oxygen contact pair, and subsequently exposing the hydrocarbon-oxygen contact pair to visible light, thereby forming a partially oxygenated derivative.

  11. Biogas cleaning and upgrading with natural zeolites from tuffs.

    PubMed

    Paolini, Valerio; Petracchini, Francesco; Guerriero, Ettore; Bencini, Alessandro; Drigo, Serena

    2016-01-01

    CO2 adsorption on synthetic zeolites has become a consolidated approach for biogas upgrading to biomethane. As an alternative to synthetic zeolites, tuff waste from building industry was investigated in this study: indeed, this material is available at a low price and contains a high fraction of natural zeolites. A selective adsorption of CO2 and H2S towards CH4 was confirmed, allowing to obtain a high-purity biomethane (CO2 <2 g m(-3), i.e. 0.1%; H2S <1.5 mg m(-3)), suitable for injection in national grids or as vehicle fuel. The loading capacity was found to be 45 g kg(-1) and 40 mg kg(-1), for CO2 and H2S, respectively. Synthetic gas mixtures and real biogas samples were used, and no significant effects due to biogas impurities (e.g. humidity, dust, moisture, etc.) were observed. Thermal and vacuum regenerations were also optimized and confirmed to be possible, without significant variations in efficiency. Hence, natural zeolites from tuffs may successfully be used in a pressure/vacuum swing adsorption process.

  12. Methanobactin and the Link between Copper and Bacterial Methane Oxidation.

    PubMed

    DiSpirito, Alan A; Semrau, Jeremy D; Murrell, J Colin; Gallagher, Warren H; Dennison, Christopher; Vuilleumier, Stéphane

    2016-06-01

    Methanobactins (mbs) are low-molecular-mass (<1,200 Da) copper-binding peptides, or chalkophores, produced by many methane-oxidizing bacteria (methanotrophs). These molecules exhibit similarities to certain iron-binding siderophores but are expressed and secreted in response to copper limitation. Structurally, mbs are characterized by a pair of heterocyclic rings with associated thioamide groups that form the copper coordination site. One of the rings is always an oxazolone and the second ring an oxazolone, an imidazolone, or a pyrazinedione moiety. The mb molecule originates from a peptide precursor that undergoes a series of posttranslational modifications, including (i) ring formation, (ii) cleavage of a leader peptide sequence, and (iii) in some cases, addition of a sulfate group. Functionally, mbs represent the extracellular component of a copper acquisition system. Consistent with this role in copper acquisition, mbs have a high affinity for copper ions. Following binding, mbs rapidly reduce Cu(2+) to Cu(1+). In addition to binding copper, mbs will bind most transition metals and near-transition metals and protect the host methanotroph as well as other bacteria from toxic metals. Several other physiological functions have been assigned to mbs, based primarily on their redox and metal-binding properties. In this review, we examine the current state of knowledge of this novel type of metal-binding peptide. We also explore its potential applications, how mbs may alter the bioavailability of multiple metals, and the many roles mbs may play in the physiology of methanotrophs. PMID:26984926

  13. Systems biology approach in Chlamydomonas reveals connections between copper nutrition and multiple metabolic steps.

    PubMed

    Castruita, Madeli; Casero, David; Karpowicz, Steven J; Kropat, Janette; Vieler, Astrid; Hsieh, Scott I; Yan, Weihong; Cokus, Shawn; Loo, Joseph A; Benning, Christoph; Pellegrini, Matteo; Merchant, Sabeeha S

    2011-04-01

    In this work, we query the Chlamydomonas reinhardtii copper regulon at a whole-genome level. Our RNA-Seq data simulation and analysis pipeline validated a 2-fold cutoff and 10 RPKM (reads per kilobase of mappable length per million mapped reads) (~1 mRNA per cell) to reveal 63 CRR1 targets plus another 86 copper-responsive genes. Proteomic and immunoblot analyses captured 25% of the corresponding proteins, whose abundance was also dependent on copper nutrition, validating transcriptional regulation as a major control mechanism for copper signaling in Chlamydomonas. The impact of copper deficiency on the expression of several O₂-dependent enzymes included steps in lipid modification pathways. Quantitative lipid profiles indicated increased polyunsaturation of fatty acids on thylakoid membrane digalactosyldiglycerides, indicating a global impact of copper deficiency on the photosynthetic apparatus. Discovery of a putative plastid copper chaperone and a membrane protease in the thylakoid suggest a mechanism for blocking copper utilization in the chloroplast. We also found an example of copper sparing in the N assimilation pathway: the replacement of copper amine oxidase by a flavin-dependent backup enzyme. Forty percent of the targets are previously uncharacterized proteins, indicating considerable potential for new discovery in the biology of copper.

  14. Zeolite in horizontal permeable reactive barriers for artificial groundwater recharge

    NASA Astrophysics Data System (ADS)

    Leal, María; Martínez-Hernández, Virtudes; Lillo, Javier; Meffe, Raffaella; de Bustamante, Irene

    2013-04-01

    The Spanish Water Reuse Royal Decree 1620/2007 considers groundwater recharge as a feasible use of reclaimed water. To achieve the water quality established in the above-mentioned legislation, a tertiary wastewater treatment is required. In this context, the infiltration of effluents generated by secondary wastewater treatments through a Horizontal Permeable Reactive Barrier (HPRB) may represent a suitable regeneration technology. Some nutrients (phosphate and ammonium) and some Pharmaceutical and Personal Care Products (PPCPs) are not fully removed in conventional wastewater treatment plants. To avoid groundwater contamination when effluents of wastewater treatments plants are used in artificial recharge activities, these contaminants have to be removed. Due to its sorption capacities, zeolite is among the most used reactive materials in Permeable Reactive Barrier (PRB). Therefore, the main goal of this study is to evaluate the zeolite retention effectiveness of nutrients and PPCPs occurring in treated wastewater. Batch sorption experiments using synthetic wastewater (SWW) and zeolite were performed. A 1:4 zeolite/SWW ratio was selected due to the high sorption capacity of the reactive material.The assays were carried out by triplicate. All the bottles containing the SWW-zeolite mixture were placed on a mechanical shaker during 24 hours at 140 rpm and 25 °C. Ammonium and phosphate, as main nutrients, and a group of PPCPs were selected as compounds to be tested during the experiments. Nutrients were analyzed by ion chromatography. For PPCPs determination, Solid Phase Extraction (SPE) was applied before their analysis by liquid chromatography-mass spectrometry time of flight (LC-MS/ TOF). The experimental data were fitted to linearized Langmuir and Freundlich isotherm equations to obtain sorption parameters. In general, Freundlich model shows a greater capability of reproducing experimental data. To our knowledge, sorption of the investigated compounds on zeolite

  15. Mixed-Metal Zeolitic Imidazolate Frameworks and their Selective Capture of Wet Carbon Dioxide over Methane.

    PubMed

    Nguyen, Nhung T T; Lo, Tien N H; Kim, Jaheon; Nguyen, Huong T D; Le, Toan B; Cordova, Kyle E; Furukawa, Hiroyasu

    2016-06-20

    A presynthesized, square planar copper imidazole complex, [Cu(imidazole)4](NO3)2, was utilized as a precursor in the synthesis of a new series of zeolitic imidazolate frameworks, termed ZIF-202, -203, and -204. The structures of all three members were solved by single-crystal X-ray diffraction analysis, which revealed ZIF-203 and -204 having successfully integrated square planar units within the backbones of their respective frameworks. As a result of this unit, the structures of both ZIF-203 and -204 were found to adopt unprecedented three-dimensional nets, namely, ntn and thl, respectively. One member of this series, ZIF-204, was demonstrated to be highly porous, exhibit exceptional stability in water, and selectively capture CO2 over CH4 under both dry and wet conditions without any loss in performance over three cycles. Remarkably, the regeneration of ZIF-204 was performed under the mild conditions of flowing a pure N2 gas through the material at ambient temperature. PMID:27248714

  16. Deactivation Mechanisms of Base Metal/Zeolite Urea Selective Catalytic Reduction Materials, and Development of Zeolite-Based Hydrocarbon Adsorber Materials

    SciTech Connect

    Kwak, Ja Hun; Lee, Jong H.; Kim, Do Heui; Li, Xiaohong S.; Tran, Diana N.; Peden, Charles HF

    2011-12-22

    This annual report describes recent progress on a collaborative project between scientists and engineers in the Institute for Integrated Catalysis at PNNL and at Ford Motor Company, involving investigations of laboratory- and engine-aged SCR catalysts, containing mainly base metal zeolites. These studies are leading to a better understanding of various aging factors that impact the long-term performance of SCR catalysts and improve the correlation between laboratory and engine aging, saving experimental time and cost. We are investigating SCR catalysts with reduced ammonia slip, increased low temperature activity, and increased product selectivity to N2. More recent recognition that high temperature performance, under regimes that sometimes cause deactivation, also needs to be improved is driving current work focused on catalyst materials modifications needed to achieve this enhanced performance. We are also studying materials effective for the temporary storage of HC species during the cold-start period. In particular, we examine the adsorption and desorption of various HC species produced during the combustion with different fuels (e.g., gasoline, E85, diesel) over potential HC adsorber materials, and measure the kinetic parameters to update Ford’s HC adsorption model.

  17. Facile synthesis of hollow zeolite microspheres through dissolution–recrystallization procedure in the presence of organosilanes

    SciTech Connect

    Tao, Haixiang; Ren, Jiawen; Liu, Xiaohui; Wang, Yanqin; Lu, Guanzhong

    2013-04-15

    Hollow zeolite microspheres have been hydrothermally synthesized in the presence of organosilanes via a dissolution–recrystallization procedure. In the presence of organosilanes, zeolite particles with a core/shell structure formed at the first stage of hydrothermal treatment, then the core was consumed and recrystallized into zeolite framework to form the hollow structure during the second hydrothermal process. The influence of organosilanes was discussed, and a related dissolution–recrystallization mechanism was proposed. In addition, the hollow zeolite microspheres exhibited an obvious advantage in catalytic reactions compared to conventional ZSM-5 catalysts, such as in the alkylation of toluene with benzyl chloride. - Graphical abstract: Hollow zeolite spheres with aggregated zeolite nanocrystals were synthesized via a dissolution–recrystallization procedure in the presence of organosiline. Highlights: ► Hollow zeolite spheres with aggregated zeolite nanocrystals were synthesized via a dissolution–recrystallization procedure. ► Organosilane influences both the morphology and hollow structure of zeolite spheres. ► Hollow zeolite spheres showed an excellent catalytic performance in alkylation of toluene with benzyl chloride.

  18. Exploitation of unique properties of zeolites in the development of gas sensors.

    PubMed

    Zheng, Yangong; Li, Xiaogan; Dutta, Prabir K

    2012-01-01

    The unique properties of microporous zeolites, including ion-exchange properties, adsorption, molecular sieving, catalysis, conductivity have been exploited in improving the performance of gas sensors. Zeolites have been employed as physical and chemical filters to improve the sensitivity and selectivity of gas sensors. In addition, direct interaction of gas molecules with the extraframework cations in the nanoconfined space of zeolites has been explored as a basis for developing new impedance-type gas/vapor sensors. In this review, we summarize how these properties of zeolites have been used to develop new sensing paradigms. There is a considerable breadth of transduction processes that have been used for zeolite incorporated sensors, including frequency measurements, optical and the entire gamut of electrochemical measurements. It is clear from the published literature that zeolites provide a route to enhance sensor performance, and it is expected that commercial manifestation of some of the approaches discussed here will take place. The future of zeolite-based sensors will continue to exploit its unique properties and use of other microporous frameworks, including metal organic frameworks. Zeolite composites with electronic materials, including metals will lead to new paradigms in sensing. Use of nano-sized zeolite crystals and zeolite membranes will enhance sensor properties and make possible new routes of miniaturized sensors.

  19. Exploitation of Unique Properties of Zeolites in the Development of Gas Sensors

    PubMed Central

    Zheng, Yangong; Li, Xiaogan; Dutta, Prabir K.

    2012-01-01

    The unique properties of microporous zeolites, including ion-exchange properties, adsorption, molecular sieving, catalysis, conductivity have been exploited in improving the performance of gas sensors. Zeolites have been employed as physical and chemical filters to improve the sensitivity and selectivity of gas sensors. In addition, direct interaction of gas molecules with the extraframework cations in the nanoconfined space of zeolites has been explored as a basis for developing new impedance-type gas/vapor sensors. In this review, we summarize how these properties of zeolites have been used to develop new sensing paradigms. There is a considerable breadth of transduction processes that have been used for zeolite incorporated sensors, including frequency measurements, optical and the entire gamut of electrochemical measurements. It is clear from the published literature that zeolites provide a route to enhance sensor performance, and it is expected that commercial manifestation of some of the approaches discussed here will take place. The future of zeolite-based sensors will continue to exploit its unique properties and use of other microporous frameworks, including metal organic frameworks. Zeolite composites with electronic materials, including metals will lead to new paradigms in sensing. Use of nano-sized zeolite crystals and zeolite membranes will enhance sensor properties and make possible new routes of miniaturized sensors. PMID:22666081

  20. Catalase-like activity studies of the manganese(II) adsorbed zeolites

    NASA Astrophysics Data System (ADS)

    ćiçek, Ekrem; Dede, Bülent

    2013-12-01

    Preparation of manganese(II) adsorbed on zeolite 3A, 4A, 5A. AW-300, ammonium Y zeolite, organophilic, molecular sieve and catalase-like enzyme activity of manganese(II) adsorbed zeolites are reported herein. Firstly zeolites are activated at 873 K for two hours before contact manganese(II) ions. In order to observe amount of adsorption, filtration process applied for the solution. The pure zeolites and manganese(II) adsorbed zeolites were analysed by FT-IR. As a result according to the FT-IR spectra, the incorporation of manganese(II) cation into the zeolite structure causes changes in the spectra. These changes are expected particularly in the pseudolattice bands connected with the presence of alumino and silicooxygen tetrahedral rings in the zeolite structure. Furthermore, the catalytic activities of the Mn(II) adsorbed zeolites for the disproportionation of hydrogen peroxide were investigated in the presence of imidazole. The Mn(II) adsorbed zeolites display efficiency in the disproportion reactions of hydrogen peroxide, producing water and dioxygen in catalase-like activity.

  1. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template

    NASA Astrophysics Data System (ADS)

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  2. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template.

    PubMed

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  3. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template.

    PubMed

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  4. The influence of chemisorbed molecules on mass transfer in H-ZSM-5-type zeolites and the location of Broensted acid sites

    SciTech Connect

    Caro, J.; Buelow, M. ); Kaerger, J.; Pfeifer, H. )

    1988-11-01

    Heterogeneous catalysis is one of the most important applications of zeolites. Therefore, various methods have been developed to determine the strength and concentration of Bronsted acid sites in zeolites. Among them, in the last few years, {sup 1}H MAS NMR has become a powerful tool. In addition to the accessibility of the acid sites probed by chemisorption of N-bases, the steric environment of these catalytically active sites is of importance since it imposes constraints on the geometry of the transition state. However, only a few studies have been reported on this topic. Information was obtained from quantum chemical calculations, catalytic experiments, I.R. spectroscopy, and the arrangement of guest molecules. From these investigations it has been concluded that in H-ZSM-5 the channel intersections should be preferential location centers for the Bronsted acid sites. In adsorption technology, in the use of zeolites as shape-selective adsorbents, modification of the molecular sieve properties by chemisorption of nitrogen-containing bases (N-compounds) has become a common technique. The authors have applied the NMR pulsed field gradient technique to study the influence of chemisorbed N-compounds on transport properties of molecular sieves, considering the chemisorbed compounds as transport obstacles.

  5. Copper as a biocidal tool.

    PubMed

    Borkow, Gadi; Gabbay, Jeffrey

    2005-01-01

    Copper ions, either alone or in copper complexes, have been used to disinfect liquids, solids and human tissue for centuries. Today copper is used as a water purifier, algaecide, fungicide, nematocide, molluscicide as well as an anti-bacterial and anti-fouling agent. Copper also displays potent anti-viral activity. This article reviews (i) the biocidal properties of copper; (ii) the possible mechanisms by which copper is toxic to microorganisms; and (iii) the systems by which many microorganisms resist high concentrations of heavy metals, with an emphasis on copper. PMID:16101497

  6. Fabricating Copper Nanotubes by Electrodeposition

    NASA Technical Reports Server (NTRS)

    Yang, E. H.; Ramsey, Christopher; Bae, Youngsam; Choi, Daniel

    2009-01-01

    Copper tubes having diameters between about 100 and about 200 nm have been fabricated by electrodeposition of copper into the pores of alumina nanopore membranes. Copper nanotubes are under consideration as alternatives to copper nanorods and nanowires for applications involving thermal and/or electrical contacts, wherein the greater specific areas of nanotubes could afford lower effective thermal and/or electrical resistivities. Heretofore, copper nanorods and nanowires have been fabricated by a combination of electrodeposition and a conventional expensive lithographic process. The present electrodeposition-based process for fabricating copper nanotubes costs less and enables production of copper nanotubes at greater rate.

  7. [Copper and the human body].

    PubMed

    Krízek, M; Senft, V; Motán, J

    1997-11-19

    Copper is one of the essential trace elements. It is part of a number of enzymes. Deficiency of the element is manifested by impaired haematopoesis, bone metabolism, disorders of the digestive, cardiovascular and nervous system. Deficiency occurs in particular in patients suffering from malnutrition, malabsorption, great copper losses during administration of penicillamine. Sporadically copper intoxications are described (suicidal intentions or accidental ingestion of beverages with a high copper content). Acute exposure to copper containing dust is manifested by metal fume fever. Copper salts can produce local inflammations. Wilson's disease is associated with inborn impaired copper metabolism. In dialyzed patients possible contaminations of the dialyzate with copper must be foreseen as well as the possible release of copper from some dialyzation membranes. With the increasing amount of copper in the environment it is essential to monitor the contamination of the environment.

  8. Fabrication of superhydrophobic-superoleophilic copper mesh via thermal oxidation and its application in oil-water separation

    NASA Astrophysics Data System (ADS)

    Yanlong, Shi; Wu, Yang; Xiaojuan, Feng; Yongsheng, Wang; Guoren, Yue; Shuping, Jin

    2016-03-01

    A copper mesh with superhydrophobicity and superoleophilicity was fabricated via thermal oxidation and subsequent surface modification. After surface treatment, the copper mesh exhibited self-cleaning properties, striking loading capacities, and superior anticorrosion. In addition, the copper mesh could be used in a separator for separating oil from oily water with high efficiency. The presented approach may provide a promising strategy for the design and construction of superhydrophobic-superoleophilic materials which can be used for separating oil from oily water.

  9. Targeting copper in cancer therapy: 'Copper That Cancer'.

    PubMed

    Denoyer, Delphine; Masaldan, Shashank; La Fontaine, Sharon; Cater, Michael A

    2015-11-01

    Copper is an essential micronutrient involved in fundamental life processes that are conserved throughout all forms of life. The ability of copper to catalyze oxidation-reduction (redox) reactions, which can inadvertently lead to the production of reactive oxygen species (ROS), necessitates the tight homeostatic regulation of copper within the body. Many cancer types exhibit increased intratumoral copper and/or altered systemic copper distribution. The realization that copper serves as a limiting factor for multiple aspects of tumor progression, including growth, angiogenesis and metastasis, has prompted the development of copper-specific chelators as therapies to inhibit these processes. Another therapeutic approach utilizes specific ionophores that deliver copper to cells to increase intracellular copper levels. The therapeutic window between normal and cancerous cells when intracellular copper is forcibly increased, is the premise for the development of copper-ionophores endowed with anticancer properties. Also under investigation is the use of copper to replace platinum in coordination complexes currently used as mainstream chemotherapies. In comparison to platinum-based drugs, these promising copper coordination complexes may be more potent anticancer agents, with reduced toxicity toward normal cells and they may potentially circumvent the chemoresistance associated with recurrent platinum treatment. In addition, cancerous cells can adapt their copper homeostatic mechanisms to acquire resistance to conventional platinum-based drugs and certain copper coordination complexes can re-sensitize cancer cells to these drugs. This review will outline the biological importance of copper and copper homeostasis in mammalian cells, followed by a discussion of our current understanding of copper dysregulation in cancer, and the recent therapeutic advances using copper coordination complexes as anticancer agents.

  10. Copper in diet

    MedlinePlus

    ... at the Institute of Medicine recommends the following dietary intake for copper: Infants 0 to 6 months: 200 ... Institute of Medicine, Food and Nutrition Board. Dietary Reference ... and Zinc. National Academy Press . Washington, DC, 2001. ...

  11. Volatility of copper

    SciTech Connect

    Palmer, D.A.; Simonson, J.M.; Joyce, D.B.

    1996-08-01

    The relevant aqueous thermodynamics of copper and its oxides are evaluated and summarized with emphasis on solubility, hydrolysis, and complexation. The solubilities of metallic copper, solid cuprous and cupric oxides in steam measured by Pocock and Stewart in 1963 are discussed and the latter data are fitted in the form of established empirical equations and compared to other existing results. No other sources of data were found for the solubility of copper and cupric oxide in steam and even these data are very limited. Discussion of corresponding available solubility data on both oxide phases in liquid water is given. The possible effects of complexing agents are considered. A brief discussion is provided of the role of surface adsorption in determining the fate of dissolved copper in the boiler. 37 refs., 5 figs., 3 tabs.

  12. Understanding Mechanism and Designing Strategies for Sustainable Synthesis of Zeolites: A Personal Story.

    PubMed

    Wang, Yeqing; Xiao, Feng-Shou

    2016-06-01

    Zeolites with intricate micropores have been widely studied for a long time as an important class of porous materials in different areas of industrial processes such as gas adsorption and separation, ion exchange, and shape-selective catalysis. However, their industrial syntheses are not sustainable, and normally require the presence of expensive organic templates and a large amount of solvents such as water. The presence of organic templates not only increases zeolite cost but also produces harmful gases during the removal of these templates by calcination, while the use of solvents significantly increases the amount of polluted water. This Personal Account briefly summarizes recent sustainable routes for the synthesis of zeolites in our group according to our understanding of the synthetic mechanism, and mainly focuses on the organotemplate-free synthesis of zeolites in the presence of zeolite seeds, the design of environmentally friendly templates, and solvent-free synthesis of zeolites. PMID:27009872

  13. Heterogeneities of the nanostructure of platinum/zeolite y catalysts revealed by electron tomography.

    PubMed

    Zečević, Jovana; van der Eerden, Ad M J; Friedrich, Heiner; de Jongh, Petra E; de Jong, Krijn P

    2013-04-23

    To develop structure-performance relationships for important catalysts, a detailed characterization of their morphology is essential. Using electron tomography, we determined in three dimensions the structure of Pt/zeolite Y bifunctional catalysts. Optimum experimental conditions enabled for the first time high-resolution 3D imaging of Pt particles as small as 1 nm located inside zeolite micropores. Semiautomated image analysis of 3D reconstructions provided an efficient study of numbers, size distributions, and interparticle distances of thousands of Pt particles within individual zeolite crystals. Upon extending this approach to a number of zeolite crystals of one batch of Pt/zeolite Y catalyst, heterogeneities were revealed. The Pt loading, an important parameter for catalyst performance, varied between zeolite crystals up to a factor of 35. This discovery calls for re-evaluation of catalyst preparation methods and suggests potential for lowering the nominal loading with noble metals.

  14. Understanding Mechanism and Designing Strategies for Sustainable Synthesis of Zeolites: A Personal Story.

    PubMed

    Wang, Yeqing; Xiao, Feng-Shou

    2016-06-01

    Zeolites with intricate micropores have been widely studied for a long time as an important class of porous materials in different areas of industrial processes such as gas adsorption and separation, ion exchange, and shape-selective catalysis. However, their industrial syntheses are not sustainable, and normally require the presence of expensive organic templates and a large amount of solvents such as water. The presence of organic templates not only increases zeolite cost but also produces harmful gases during the removal of these templates by calcination, while the use of solvents significantly increases the amount of polluted water. This Personal Account briefly summarizes recent sustainable routes for the synthesis of zeolites in our group according to our understanding of the synthetic mechanism, and mainly focuses on the organotemplate-free synthesis of zeolites in the presence of zeolite seeds, the design of environmentally friendly templates, and solvent-free synthesis of zeolites.

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

    SciTech Connect

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

    2007-02-02

    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.

  16. Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective Membrane

    SciTech Connect

    Varoon, Kumar; Zhang, Xueyi; Elyassi, Bahman; Brewer, Damien D.; Gettel, Melissa; Kumar, Sandeep; Lee, J. Alex; Maheshwari, Sundeep; Mittal, Anudha; Sung, Chun-Yi; Cococcioni, Matteo; Francis, Lorraine F.; McCormick, Alon V.; Mkhoyan, K. Andre; Tsapatsis, Michael

    2011-10-06

    Thin zeolite films are attractive for a wide range of applications, including molecular sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielectric-constant materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphological damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure determination of highly crystalline nanosheets of zeolite frameworks MWW and MFI. The purity and morphological integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of molecular sieve membranes.

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

    PubMed

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

    2016-02-01

    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.

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

    PubMed

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

    2016-02-01

    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. PMID:26691750

  19. Composting domestic sewage sludge with natural zeolites in a rotary drum reactor.

    PubMed

    Villaseñor, J; Rodríguez, L; Fernández, F J

    2011-01-01

    This work aimed the influence of zeolites addition on a sludge-straw composting process using a pilot-scale rotary drum reactor. The type and concentration of three commercial natural zeolites were considered: a mordenite and two clinoptilolites (Klinolith and Zeocat). Mordenite caused the greatest carbon removal (58%), while the clinoptilolites halved losses of ammonium. All zeolites removed 100% of Ni, Cr, Pb, and significant amounts (more than 60%) of Cu, Zn and Hg. Zeocat displayed the greatest retention of ammonium and metals, and retention efficiencies increased as Zeocat concentration increased. The addition of 10% Zeocat produced compost compliant with Spanish regulations. Zeolites were separated from the final compost, and leaching studies suggested that zeolites leachates contained very low metals concentrations (<1 mg/kg). Thus, the final compost could be applied directly to soil, or metal-polluted zeolites could be separated from the compost prior to application. The different options have been discussed. PMID:20951578

  20. Effects of Surface and Morphological Properties of Zeolite on Impedance Spectroscopy-Based Sensing Performance

    PubMed Central

    Zhang, Jianwei; Li, Xiaogan; White, Jeremy; Dutta, Prabir K.

    2012-01-01

    Measurement by impedance spectroscopy of the changes in intrazeolitic cation motion of pressed pellets of zeolite particles upon adsorption of dimethylmethylphosphonate (DMMP) provides a strategy for sensing DMMP, a commonly used simulant for highly toxic organophosphate nerve agents. In this work, two strategies for improving the impedance spectroscopy based sensing of DMMP on zeolites were investigated. The first one is the use of cerium oxide (CeO2) coated on the zeolite surface to neutralize acidic groups that may cause the decomposition of DMMP, and results in better sensor recovery. The second strategy was to explore the use of zeolite Y membrane. Compared to pressed pellets, the membranes have connected supercages of much longer length scales. The zeolite membranes resulted in higher sensitivity to DMMP, but recovery of the device was significantly slower as compared to pressed zeolite pellets. PMID:23201996

  1. The Ameliorative Effect of Artificial Zeolite on Barley under Saline Conditions

    NASA Astrophysics Data System (ADS)

    Al-Busaidi, A.; Yamamoto, T.; Irshad, M.

    This investigation was aimed to evaluate the effects of zeolite in conjunction with seawater irrigation on barley (Hordeum vulgare L.) growth and salt composition of soil. A sand dune soil was amended with Ca-type zeolite at the rate of 1 and 5% and the seawater was diluted up to the electrical conductivity of 3 and 16 dS mG1. Present results showed that zeolite application significantly increased water holding capacity of the soil and accumulated more salts. The zeolite mixed soils improved plant growth compared to the un-amended control. Higher saline water significantly suppressed the growth of barley than the water with low salinity. The restricted plant growth due to the effects of specific ion or Na+/Ca2+ imbalance may be ameliorated using Ca-type zeolite. We may conclude that soil amendment with zeolite could alleviate the adverse effects of salts on plants following irrigation with higher saline water.

  2. Effective solidification/stabilisation of mercury-contaminated wastes using zeolites and chemically bonded phosphate ceramics.

    PubMed

    Zhang, Shaoqing; Zhang, Xinyan; Xiong, Ya; Wang, Guoping; Zheng, Na

    2015-02-01

    In this study, two kinds of zeolites materials (natural zeolite and thiol-functionalised zeolite) were added to the chemically bonded phosphate ceramic processes to treat mercury-contaminated wastes. Strong promotion effects of zeolites (natural zeolite and thiol-functionalised zeolite) on the stability of mercury in the wastes were obtained and these technologies showed promising advantages toward the traditional Portland cement process, i.e. using Portland cement as a solidification agent and natural or thiol-functionalised zeolite as a stabilisation agent. Not only is a high stabilisation efficiency (lowered the Toxicity Characteristic Leaching Procedure Hg by above 10%) obtained, but also a lower dosage of solidification (for thiol-functionalised zeolite as stabilisation agent, 0.5 g g(-1) and 0.7 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) and stabilisation agents (for natural zeolite as stabilisation agent, 0.35 g g(-1) and 0.4 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) were used compared with the Portland cement process. Treated by thiol-functionalised zeolite and chemically bonded phosphate ceramic under optimum parameters, the waste containing 1500 mg Hg kg(-1) passed the Toxicity Characteristic Leaching Procedure test. Moreover, stabilisation/solidification technology using natural zeolite and chemically bonded phosphate ceramic also passed the Toxicity Characteristic Leaching Procedure test (the mercury waste containing 625 mg Hg kg(-1)). Moreover, the presence of chloride and phosphate did not have a negative effect on the chemically bonded phosphate ceramic/thiol-functionalised zeolite treatment process; thus, showing potential for future application in treatment of 'difficult-to-manage' mercury-contaminated wastes or landfill disposal with high phosphate and chloride content.

  3. Ammonium removal from high-strength aqueous solutions by Australian zeolite.

    PubMed

    Wijesinghe, D Thushari N; Dassanayake, Kithsiri B; Sommer, Sven G; Jayasinghe, Guttila Y; J Scales, Peter; Chen, Deli

    2016-07-01

    Removal of ammonium nitrogen (NH4(+)-N) particularly from sources which are highly rich in nitrogen is important for addressing environmental pollution. Zeolites, aluminosilicate minerals, are commonly used as commercial adsorbents and ion-exchange medium in number of commercial applications due to its high adsorption capacity of ammonium (NH4(+)). However, detailed investigations on NH4(+) adsorption and ion exchange capacities of Australian natural zeolites are rare, particularly under higher NH4(+) concentrations in the medium. Therefore, this study was conducted to determine NH4(+) adsorption characteristics of Australian natural zeolites at high NH4(+) concentrations with and without other chemical compounds in an aqueous solution. Results showed that initial NH4(+) concentration, temperature, reaction time, and pH of the solution had significant effects on NH4(+) adsorption capacity of zeolite. Increased retention time and temperature generally had a positive impact on adsorption. Freundlich model fitted well with adsorption process of Australian natural zeolites; however, Langmuir model had best fitted for the adsorption process of sodium (Na(+)) treated zeolites. NaCl treatment increased the NH4(+) adsorption capacity of Australian zeolites by 25% at 1000 mg-N, NH4(+) solution. The maximum adsorption capacity of both natural Australian zeolites and Na(+) treated zeolites were estimated as 9.48 and 11.83 mg-N/g, respectively, which is lower than many zeolites from other sources. Compared to the NH4(+) only medium, presence of other competitive ions and acetic acid in the medium (resembling composition in digested swine manure slurries) reduced NH4(+) removal of natural and Na(+) treated zeolites by 44% and 57%, respectively. This suggests detailed investigations are required to determine practically achievable NH4(+) -N removal potential of zeolites for applications in complex mediums such as animal manure slurries.

  4. Synthesis and characterization of zeolites prepared from industrial fly ash.

    PubMed

    Franus, Wojciech; Wdowin, Magdalena; Franus, Małgorzata

    2014-09-01

    In this paper, we present the possibility of using fly ash to produce synthetic zeolites. The synthesis class F fly ash from the Stalowa Wola SA heat and power plant was subjected to 24 h hydrothermal reaction with sodium hydroxide. Depending on the reaction conditions, three types of synthetic zeolites were formed: Na-X (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 75 °C), Na-P1 (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 95 °C), and sodalite (20 g fly ash, 0.8 dm(3) of 5 mol · dm(-3) NaOH + 0.4 dm(3) of 3 mol · dm(-3) NaCl, 95 °C). As synthesized materials were characterized to obtain mineral composition (X-ray diffractometry, Scanning electron microscopy-energy dispersive spectrometry), adsorption properties (Brunauer-Emmett-Teller surface area, N2 isotherm adsorption/desorption), and ion exchange capacity. The most effective reaction for zeolite preparation was when sodalite was formed and the quantitative content of zeolite from X-ray diffractometry was 90 wt%, compared with 70 wt% for the Na-X and 75 wt% for the Na-P1. Residues from each synthesis reaction were the following: mullite, quartz, and the remains of amorphous aluminosilicate glass. The best zeolitic material as characterized by highest specific surface area was Na-X at almost 166 m(2) · g(-1), while for the Na-P1 and sodalite it was 71 and 33 m(2) · g(-1), respectively. The ion exchange capacity decreased in the following order: Na-X at 1.8 meq · g(-1), Na-P1 at 0.72 meq · g(-1), and sodalite at 0.56 meq · g(-1). The resulting zeolites are competitive for commercially available materials and are used as ion exchangers in industrial wastewater and soil decontamination. PMID:24838802

  5. Synthesis and characterization of various zeolites and study of dynamic adsorption of dimethyl methyl phosphate over them

    SciTech Connect

    Khanday, Waheed Ahmad; Majid, Sheikh Abdul; Chandra Shekar, S.; Tomar, Radha

    2013-11-15

    Graphical abstract: Thermal desorption pattern of DMMP over various zeolites (a) 1st desorption and (b) 2nd desorption. - Highlights: • Synthesis of Zeolite-A, MCM-22, Zeolite-X and Erionite by hydrothermal method. • Zeolites were characterized by using XRD, FTIR, BET, NH{sub 3}-TPD, SEM and EDS techniques. • Dynamic adsorption of DMMP on zeolites was carried out using TPD plus chemisorption system. • Thermal desorption of DMMP on zeolites was carried using the same system. - Abstract: Zeolite-A, MCM-22, Zeolite-X and Erionite were synthesized successfully under hydrothermal conditions and were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Brunauer–Emmett–Teller (BET) surface area analysis and thermal programmed desorption (TPD). Dynamic adsorption of dimethyl methyl phosphate (DMMP) was carried out on these zeolites. Zeolite-X having high surface area among all four zeolites shows highest adsorption capacity followed by Erionite and MCM-22 where as Zeolite-A shows the least. For all zeolites adsorption was found to be high initially and it then decreases with increase in injected volume. Then desorption pattern was analyzed which shows two types of peaks, sharp peak representing desorption of physisorbed DMMP and a broad peak representing desorption of strongly chemisorbed DMMP.

  6. Assessing different zeolitic adsorbents for their potential use in Kr and Xe separation

    NASA Astrophysics Data System (ADS)

    Alagappan, Breetha

    Separation of Kr from Xe is an important problem in spent nuclear fuel fission gas management. The energy intensive and expensive cryogenic distillation method is currently used to separate these gases. In this thesis, we have carried out the research into appropriate sorbents for the separation of Kr and Xe using pressure swing adsorption. We have examined zeolites using gas adsorption studies as they have the potential to be more cost effective than other sorbents. Zeolites are microporous aluminosilicates and have ordered pore structures. The pores in zeolites have extra-framework cations are substantially free to move. The mobility of cations and the uniformity in pore size permits the separation and removal of gases in zeolites. In our experiment, first, we have measured adsorption isotherms with same zeolitic framework but with different cations. Second, we have measured the adsorption isotherm with different zeolitic frameworks but with same cation. Using these adsorption isotherms, we have calculated the initial heats of adsorption to find out the strength of interaction between the zeolitic framework and the gases. Finally, we have compared the difference in the initial heats of adsorption to find the suitable zeolite that has the highest selectivity of Xe over Kr. In conclusion, we have found out that K LSX seems to have higher potential among the zeolites that we have compared for the separation of Kr from Xe with the differential heats of adsorption for Xe vs Kr as ˜7.4 kJ/mol.

  7. Fabrication of silver nanoparticles doped in the zeolite framework and antibacterial activity

    PubMed Central

    Shameli, Kamyar; Ahmad, Mansor Bin; Zargar, Mohsen; Yunus, Wan Md Zin Wan; Ibrahim, Nor Azowa

    2011-01-01

    Using the chemical reduction method, silver nanoparticles (Ag NPs) were effectively synthesized into the zeolite framework in the absence of any heat treatment. Zeolite, silver nitrate, and sodium borohydride were used as an inorganic solid support, a silver precursor, and a chemical reduction agent, respectively. Silver ions were introduced into the porous zeolite lattice by an ion-exchange path. After the reduction process, Ag NPs formed in the zeolite framework, with a mean diameter of about 2.12–3.11 nm. The most favorable experimental condition for the synthesis of Ag/zeolite nanocomposites (NCs) is described in terms of the initial concentration of AgNO3. The Ag/zeolite NCs were characterized by ultraviolet-visible spectroscopy, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray fluorescence, and Fourier transform infrared. The results show that Ag NPs form a spherical shape with uniform homogeneity in the particle size. The antibacterial activity of Ag NPs in zeolites was investigated against Gram-negative bacteria (ie, Escherichia coli and Shigella dysentriae) and Gram-positive bacteria (ie, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus) by disk diffusion method using Mueller–Hinton agar at different sizes of Ag NPs. All of the synthesized Ag/zeolite NCs were found to have antibacterial activity. These results show that Ag NPs in the zeolite framework can be useful in different biological research and biomedical applications. PMID:21383858

  8. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-09-30

    The objective of this project is to synthesize nanocrystals of highly acidic zeolite Y nanoclusters, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates, and evaluate the 'zeolite Y/Nanoporous host' composites as catalysts for the upgrading of heavy petroleum feedstocks. In comparison to conventionally-used zeolite Y catalysts of micron size particles, the nanocrystals (< 100 nm particle size) which contain shorter path lengths, are expected to allow faster diffusion of large hydrocarbon substrates and the catalysis products within and out of the zeolite's channels and cages (<1 nm size). This is expected to significantly reduce deactivation of the catalyst and to prolong their period of reactivity. Encapsulating zeolite Y nanocrystals within the nanoporous materials is expected to protect its external surfaces and pore entrances from being blocked by large hydrocarbon substrates, since these substrates will initially be converted to small molecules by the nanoporous host (a catalyst in its own right). The project consisted of four major tasks as follows: (1) synthesis of the nanoparticles of zeolite Y (of various chemical compositions) using various techniques such as the addition of organic additives to conventional zeolite Y synthesis mixtures to suppress zeolite Y crystal growth; (2) synthesis of nanoporous silicate host materials of up to 30 nm pore diameter, using poly (alkylene oxide) copolymers which when removed will yield a mesoporous material; (3) synthesis of zeolite Y/Nanoporous Host composite materials as potential catalysts; and (4) evaluation of the catalyst for the upgrading of heavy petroleum feedstocks.

  9. Ammonium removal from groundwater using a zeolite permeable reactive barrier: a pilot-scale demonstration.

    PubMed

    Li, Shengpin; Huang, Guoxin; Kong, Xiangke; Yang, Yingzhao; Liu, Fei; Hou, Guohua; Chen, Honghan

    2014-01-01

    In situ remediation of ammonium-contaminated groundwater is possible through a zeolite permeable reactive barrier (PRB); however, zeolite's finite sorption capacity limits the long-term field application of PRBs. In this paper, a pilot-scale PRB was designed to achieve sustainable use of zeolite in removing ammonium (NH(4)(+)-N) through sequential nitrification, adsorption, and denitrification. An oxygen-releasing compound was added to ensure aerobic conditions in the upper layers of the PRB where NH(4)(+)-N was microbially oxidized to nitrate. Any remaining NH(4)(+)-N was removed abiotically in the zeolite layer. Under lower redox conditions, nitrate formed during nitrification was removed by denitrifying bacteria colonizing the zeolite. During the long-term operation (328 days), more than 90% of NH(4)(+)-N was consistently removed, and approximately 40% of the influent NH(4)(+)-N was oxidized to nitrate. As much as 60% of the nitrate formed in the PRB was reduced in the zeolite layer after 300 days of operation. Removal of NH(4)(+)-N from groundwater using a zeolite PRB through bacterial nitrification and abiotic adsorption is a promising approach. The zeolite PRB has the advantage of achieving sustainable use of zeolite and immediate NH(4)(+)-N removal.

  10. Molecular recognition on acoustic wave devices: Sorption in chemically anchored zeolite monolayers

    SciTech Connect

    Yan, Yongan; Bein, T.

    1992-11-12

    Zeolite crystals were attached to the gold electrodes of quartz crystal microbalances (QCM). Monolayers of thiol-alkoxysilanes on the gold surface served as interfacial layers for the subsequent adhesion of the zeolite crystals to the QCM. The process of anchoring the zeolite crystals via the thiol-silane monolayers was studied by reflection adsorption infrared (IR) spectroscopy, contact angle, and scanning electron microscopy (SEM). The siloxane linkages between the microporous zeolite crystals and the terminal cross-linked polysiloxane groups of the interfacial monolayer play an important role in enhancing the packing density of microporous crystals and the thermal stability (up to at least 350 {degrees}C) of the film on the gold surface. Dynamic sorption isotherms of organic vapors and nitrogen as well as the transient sorption behavior of organic vapor pulses were studied to characterize the zeolite-coated QCMs. The resonance frequency response of zeolite-coated QCMs to vapor pulses could be increased up to 500-fold compared to the bare sensor. The regular micropores (0.3-0.75 nm) of the QCM-attached zeolite crystals were found to efficiently control molecular access into the coating. Selectivity of the frequency response in excess of 100:1 toward molecules of different size and/or shape could be demonstrated. The kinetics of vapor desorption from the zeolite layers are strongly dependent on the adsorbate/zeolite combination, thus providing an additional capability for molecular recognition. 33 refs., 11 figs., 2 tabs.

  11. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    PubMed

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling. PMID:26138977

  12. Application of zeolites for radium removal from mine water.

    PubMed

    Chałupnik, Stanisław; Franus, Wojciech; Wysocka, Małgorzata; Gzyl, Grzegorz

    2013-11-01

    For removal of radium from saline waters in Upper Silesian mines, several methods of purification have been developed. The most efficient one is based on application of barium chloride, which was implemented in full technical scale in two Polish coal mines several years ago. Very good results of purification have been achieved-the removal efficiency exceeding 95% of the initial activity. Another possibility for the removal of different ions from salty waters and brines is the application of zeolites. We found that technique as a very promising method for removal of not only radium isotopes from mine waters but also other ions (barium, iron, manganese). Treatment of several various water samples has been done to assess the removal efficiency for natural radionuclides. Preliminary results show very good effects for radium isotopes as well as for barium ions. In the paper, a short description of laboratory results of the purification of mine waters with application of synthetic zeolites is presented.

  13. Shape-selective zeolite catalysis for bioplastics production

    NASA Astrophysics Data System (ADS)

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A.; Sels, Bert F.

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling.

  14. Modified Asphalt Binder with Natural Zeolite for Warm Mix Asphalt

    NASA Astrophysics Data System (ADS)

    Dubravský, Marián; Mandula, Ján

    2015-11-01

    In recent years, warm mix asphalt (WMA) is becoming more and more used in the asphalt industry. WMA provide a whole range of benefits, whether economic, environmental and ecological. Lower energy consumption and less pollution is the most advantages of this asphalt mixture. The paper deals with the addition of natural zeolite into the sub base asphalt layers, which is the essential constituent in the construction of the road. Measurement is focused on basic physic - mechanical properties declared according to the catalog data sheets. The aim of this article is to demonstrate the ability of addition the natural zeolite into the all asphalt layers of asphalt pavement. All asphalt mixtures were compared with reference asphalt mixture, which was prepared in reference temperature.

  15. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    PubMed

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling.

  16. Inelastic X-ray Scattering Studies of Zeolite Collapse

    SciTech Connect

    Greaves, G. Neville; Kargl, Florian; Ward, David; Holliman, Peter; Meneau, Florian

    2009-01-29

    In situ inelastic x-ray scattering (IXS) experiments have been used to probe heterogeneity and deformability in zeolte Y as this thermally collapses to a high density amorphous (HDA) aluminosilicate phase. The Landau-Placzek ratio R{sub LP} falls slowly as amorphisation advances, increasing in the later stages of collapse clearly showing how homogeneity improves non-linearly--behaviour linked closely with the decline in molar volume V{sub Molar}. The Brillouin frequency {omega}{sub Q} also decreases with amorphisation in a similar fashion, signifying a non-uniform decrease in the speed of sound v{sub l}. All of these changes with zeolite amorphisation infer formation of an intermediate low density amorphous (LDA) phase. This low entropy or 'perfect glass' has mechanical properties which are closer to the zeolite rather to the HDA glass--notably a very small value of Poisson's Ratio signifying unusually low resistance to deformation.

  17. Wastewater treatment in production of MgA zeolite

    SciTech Connect

    Barsukov, V.V.; Akopyants, T.V.; Rudova, S.A.; Shumovskii, A.V.

    1986-09-01

    This paper reports the development of zero-waste technology for treatment of chloride waste formed in the manufacture of MgA microbead zeolite, based on the method and flow plan used in treating similar wastes formed in the manufacture of bead zeolite. The first crystals of sodium chloride appeared at a magnesium chloride concentration of 8-9% by weight. With a magnesium chloride concentration of 35% by weight, at 50 C, the sodium chloride was almost completely precipitated. Under these conditions, the magnesium chloride did not precipitate. Sodium chloride crystals were washed with water in order to obtain a commercial product meeting the requirements of the specification Tu 6-12-33-78. This product is recommended for use in regenerating cation exchange filters in thermal power plants.

  18. Double rotation NMR studies of zeolites and aluminophosphate molecular sieves

    SciTech Connect

    Jelinek, R. |

    1993-07-01

    Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. {sup 27}Al and {sup 23}Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework {sup 27}Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na{sup +} cations are directly involved in adsorption processes and reactions in zeolite cavities.

  19. Computational studies of Bronsted acid sites in zeolites

    SciTech Connect

    Curtiss, L.A.; Iton, L.E.; Zygmunt, S.A.

    1995-01-01

    The authors have performed high-level ab initio calculations using both Hartree-Fock (HF) and Moller-Plesset perturbation theory (MP2) to study the geometry and energetics of the adsorption complex involving H{sub 2}O and the Bronsted acid site in the zeolite H-ZSM-5. In these calculations, which use aluminosilicate cluster models for the zeolite framework with as many a 28 T atoms (T = Si, Al), we included geometry optimization in the local vicinity of the acid site at the HF/6-31G(d) level of theory, and have calculated corrections for zero-point energies, extensions for zero-point energies, extensions to higher basis sets, and the influence of electron correlation. Results for the adsorption energy and geometry of this complex are reported and compared with previous theoretical and experimental values.

  20. Hierarchical zeolites and their catalytic performance in selective oxidative processes.

    PubMed

    Ojeda, Manuel; Grau-Atienza, Aida; Campos, Rafael; Romero, Antonio A; Serrano, Elena; Maria Marinas, Jose; García Martínez, Javier; Luque, Rafael

    2015-04-24

    Hierarchical ZSM-5 zeolites prepared using a simple alkali treatment and subsequent HCl washing are found to exhibit unprecedented catalytic activities in selective oxidation of benzyl alcohol under microwave irradiation. The metal-free zeolites promote the microwave-assisted oxidation of benzyl alcohol with hydrogen peroxide in yields ranging from 45-35 % after 5 min of reaction under mild reaction conditions as well as the epoxidation of cyclohexene to valuable products (40-60 % conversion). The hierarchically porous systems also exhibited an interesting catalytic activity in the dehydration of N,N-dimethylformamide (25-30 % conversion), representing the first example of transition-metal free catalysts in this reaction.

  1. Ammonia synthesis catalyzed by ruthenium supported on basic zeolites

    SciTech Connect

    Fishel, C.T.; Davis, R.J.; Garces, J.M.

    1996-09-15

    Ammonia synthesis was catalyzed by ruthenium metal clusters, promoted by alkali and alkaline earth elements, supported on zeolite X, magnesia, and pure silica MCM-41. At atmospheric total pressure and temperatures ranging from 623 to 723 K, the turnover frequencies of ammonia synthesis on Ru/KX varied significantly with Fu cluster size, demonstrating the known structure sensitivity of the reaction. Therefore, zeolite and magnesia catalysts were prepared with similar Ru cluster sizes, about 1 nm in diameter, in order to properly evaluate the effect of promoters. The same high degree of metal dispersion could not be obtained with Ru/MCM-41 catalysts. The turnover frequency for ammonia synthesis over Ru/CsX exceeded that over Ru/KX, consistent with the rank of promoter basicity. However, alkaline earth metals were more effective promoters than alkali metals for Ru supported on both zeolite X and MCM-41. Since alkaline earth metals are less basic; this promotional effect was unexpected. In addition, the turnover frequency for ammonia synthesis on Ru/BaX exceeded that of Ru/MgO, a nonzeolitic material. Pore volumes for Ru/BaX and Ru/KX measured by N{sub 2} adsorption were essentially identical, suggesting that pore blockage by ions within the zeolites does not account for the differences in reaction rates. The kinetics of ammonia synthesis over ruthenium differed considerably from what has been reported for industrial iron catalysts. Most significantly, the order of reaction in H{sub 2} was negative over Ru but is positive over Fe. A likely cause of this change in reaction order is that dissociated hydrogen atoms cover a greater fraction of the Ru clusters compared to Fe under reaction conditions. 49 refs., 8 figs., 10 tabs.

  2. Epitaxially grown layered MFI-bulk MFI hybrid zeolitic materials.

    PubMed

    Kim, Wun-gwi; Zhang, Xueyi; Lee, Jong Suk; Tsapatsis, Michael; Nair, Sankar

    2012-11-27

    The synthesis of hybrid zeolitic materials with complex micropore-mesopore structures and morphologies is an expanding area of recent interest for a number of applications. Here we report a new type of hybrid zeolite material, composed of a layered zeolite material grown epitaxially on the surface of a bulk zeolite material. Specifically, layered (2-D) MFI sheets were grown on the surface of bulk MFI crystals of different sizes (300 nm and 10 μm), thereby resulting in a hybrid material containing a unique morphology of interconnected micropores (∼0.55 nm) and mesopores (∼3 nm). The structure and morphology of this material, referred to as a "bulk MFI-layered MFI" (BMLM) material, was elucidated by a combination of XRD, TEM, HRTEM, SEM, TGA, and N(2) physisorption techniques. It is conclusively shown that epitaxial growth of the 2-D layered MFI sheets occurs in at least two principal crystallographic directions of the bulk MFI crystal and possibly in the third direction as well. The BMLM material combines the properties of bulk MFI (micropore network and mechanical support) and 2-D layered MFI (large surface roughness, external surface area, and mesoporosity). As an example of the uses of the BMLM material, it was incorporated into a polyimide and fabricated into a composite membrane with enhanced permeability for CO(2) and good CO(2)/CH(4) selectivity for gas separations. SEM-EDX imaging and composition analysis showed that the polyimide and the BMLM interpenetrate into each other, thereby forming a well-adhered polymer/particle microstructure, in contrast with the defective interfacial microstructure obtained using bare MFI particles. Analysis of the gas permeation data with the modified Maxwell model also allows the estimation of the effective volume of the BMLM particles, as well as the CO(2) and CH(4) gas permeabilities of the interpenetrated layer at the BMLM/polyimide interface.

  3. Generalized statistical model for multicomponent adsorption equilibria on zeolites

    SciTech Connect

    Rota, R.; Gamba, G.; Paludetto, R.; Carra, S.; Morbidelli, M. )

    1988-05-01

    The statistical thermodynamic approach to multicomponent adsorption equilibria on zeolites has been extended to nonideal systems, through the correction of cross coefficients characterizing the interaction between unlike molecules. Estimation of the model parameters requires experimental binary equilibrium data. Comparisons with the classical model based on adsorbed solution theory are reported for three nonideal ternary systems. The two approaches provide comparable results in the simulation of binary and ternary adsorption equilibrium data at constant temperature and pressure.

  4. Lanthanum-NaY zeolite ion exchange. 2; Kinetics

    SciTech Connect

    Lee, T.Y.; Lu, T.S.; Chen, S.H.; Chao, K.J. )

    1990-10-01

    This paper reports on La-NaY ion exchange breakthrough curves which were obtained experimentally at 27 and 60{degrees}C. A mathematical model of an ion exchanger was formulated and employed to calculate the ion exchanger coefficients. An ionic diffusion coefficient of the order of 10{sup {minus}8} cm{sup 2}/s was obtained. The effects of zeolite particle size, temperature, and column packing conditions on the kinetics of the exchange were investigated also.

  5. Hydrogenation properties of ruthenium sulfide clusters in acidic zeolites

    SciTech Connect

    Breysse, M.; Cattenot, M.; Kougionas, V.

    1997-06-01

    Catalysts of ruthenium sulfide, dispersed in a series of Y zeolites with various acidic properties, were prepared by ion exchange and subsequent sulfidation. The activities for the reactions of hydrogenation of tetralin and toluene, carried out in the presence of H{sub 2}S (1.9%), vary widely according to the nature of the zeolites. Ruthenium sulfide catalysts are much more active when using acidic zeolite, HY and HYd (dealuminated), and a partially potassium-exchanged KHYd sample, than when using the KY support. The acidic properties of the sulfided RuY catalysts were determined in situ using infrared spectroscopy and the conversion of isooctane. Both methods gave similar rankings of catalyst acidity. The electronic properties of the ruthenium sulfide phase were examined by means of the infrared study of the adsorption of CO. A low-frequency shift of 15 cm{sup -1} was observed for CO adsorbed on RuKY by reference to CO adsorbed on all other samples. The increase in activity for the hydrogenation of aromatics is related to the electron- deficient character of the sulfide particles in the acidic zeolites; as has been proposed, in the literature, for metal catalysts. A superimposed influence of the acidic sites on the adsorption of the aromatic molecule may also occur which could explain the amplitude of the effect (difference of activity between the most and less active catalysts {approximately}200 times) and the variations of activity observed within the series of the acidic catalysts. 33 refs., 10 figs., 7 tabs.

  6. Smart epoxy coating containing Ce-MCM-22 zeolites for corrosion protection of Mg-Li alloy

    NASA Astrophysics Data System (ADS)

    Wang, Yanli; Zhu, Yanhao; Li, Chao; Song, Dalei; Zhang, Tao; Zheng, Xinran; Yan, Yongde; Zhang, Meng; Wang, Jun; Shchukin, Dmitry G.

    2016-04-01

    The epoxy coatings containing MCM-22 and Ce-MCM-22 zeolites were prepared by coating method on the Mg-Li alloy surface. The influence of MCM-22 and Ce-MCM-22 zeolites on corrosion protection of the epoxy coating was studied. The epoxy coating containing Ce-MCM-22 zeolites showed high corrosion resistance. Artificial defects in the epoxy coating containing Ce-MCM-22 zeolites on the Mg-Li surface were produced by the needle punching. The results show that the epoxy coating containing Ce-MCM-22 zeolites exhibits self-healing corrosion inhibition capabilities. It is ascribed to the fact that the Ce3+ ions are released from MCM-22 zeolites based on ion exchange of zeolite in the corrosion process of the Mg-Li alloy substrate. MCM-22 zeolites as reservoirs provided a prolonged release of cerium ions.

  7. Urinary copper excretion and hepatic copper concentrations in liver disease.

    PubMed

    Frommer, D J

    1981-01-01

    Urinary copper excretion was found to be increased in patients with cholestasis, hepatitis and cirrhosis, but the penicillamine-induced increment was normal. Wilson's disease patients had increased copper excretion before and after penicillamine, especially in untreated cases. Hepatic copper concentrations correlated with urinary copper excretion in cholestasis and treated Wilson's disease, but not in hepatitis or cirrhosis. In treated Wilson's disease, measurement of urinary copper excretion should be valuable in estimating the degree of removal of copper from the body during therapy. Urinary copper clearances were raised in various liver conditions, maximally in untreated Wilson's disease. It is suggested that only part of the serum non-caeruloplasmin copper is available for excretion into urine.

  8. Catalytic reactions of cyclooctane and ethylcyclohexane on HY zeolite

    SciTech Connect

    Abbot, J.; Wojciechowski, B.W.

    1987-10-01

    Few systematic studies of the reactions of cycloparaffins on zeolites have been reported, considering their importance as a component of commercial crude feedstocks. Studies of small ring (C/sub 3/, C/sub 4/) cycloparaffins have shown that the primary reaction product is the corresponding olefin. It has not been established, however, that the corresponding olefin is produced as an initial product of the cracking of medium-sized (C/sub 5/, C/sub 6/) rings. Studies of cycloparaffin cracking on silica-alumina catalysts report that the degree of saturation of low-molecular-weight products is much greater than that observed in comparable n-paraffin cracking. Reactions of methylcyclohexane on HY zeolite at 450/sup 0/C have shown that dehydrogenation, isomerization, and cracking are all primary processes. Here the authors report product distributions in the cracking of ethylcyclohexane and cyclooctane on HY zeolite at 400/sup 0/C and compare product distributions for these cycloparaffins. 19 references.

  9. Synthetic zeolites and other microporous oxide molecular sieves

    PubMed Central

    Sherman, John D.

    1999-01-01

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow “tailoring” of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol. PMID:10097059

  10. Core-shell strain structure of zeolite microcrystals.

    PubMed

    Cha, Wonsuk; Jeong, Nak Cheon; Song, Sanghoon; Park, Hyun-jun; Thanh Pham, Tung Cao; Harder, Ross; Lim, Bobae; Xiong, Gang; Ahn, Docheon; McNulty, Ian; Kim, Jungho; Yoon, Kyung Byung; Robinson, Ian K; Kim, Hyunjung

    2013-08-01

    Zeolites are crystalline aluminosilicate minerals featuring a network of 0.3-1.5-nm-wide pores, used in industry as catalysts for hydrocarbon interconversion, ion exchangers, molecular sieves and adsorbents. For improved applications, it is highly useful to study the distribution of internal local strains because they sensitively affect the rates of adsorption and diffusion of guest molecules within zeolites. Here, we report the observation of an unusual triangular deformation field distribution in ZSM-5 zeolites by coherent X-ray diffraction imaging, showing the presence of a strain within the crystal arising from the heterogeneous core-shell structure, which is supported by finite element model calculation and confirmed by fluorescence measurement. The shell is composed of H-ZSM-5 with intrinsic negative thermal expansion whereas the core exhibits a different thermal expansion behaviour due to the presence of organic template residues, which usually remain when the starting materials are insufficiently calcined. Engineering such strain effects could have a major impact on the design of future catalysts. PMID:23832126

  11. The safety of synthetic zeolites used in detergents.

    PubMed

    Fruijtier-Pölloth, Claudia

    2009-01-01

    Synthetic zeolites are replacing phosphates as builders in laundry detergents; workers and consumers may, therefore, increasingly be exposed to these materials and it is important to assess their safety. This article puts mechanistic, toxicological and exposure data into context for a safety assessment. Zeolites are hygroscopic compounds with ion-exchanging properties. They may partially decompose under acidic conditions such as in the stomach releasing sodium ions, silicic acid and aluminum salts. The intact molecule is not bioavailable after oral intake or exposure through the dermal and inhalational routes. Under current conditions of manufacture and use, no systemic toxicity is to be expected from neither the intact molecule nor the degradation products; a significant effect on the bioavailability of other compounds is not likely. Zeolites may cause local irritation. It is, therefore, important to minimise occupational exposure. The co-operation of detergent manufacturers with the manufacturers of washing machines is necessary to find the right balance between environmental aspects such as energy and water savings and the occurrence of detergent residues on textiles due to insufficient rinsing.

  12. Zeolites on Mars: Possible environmental indicators in soils and sediments

    NASA Technical Reports Server (NTRS)

    Ming, D. W.; Gooding, J. L.

    1988-01-01

    Weathering products should serve as indicators of weathering environments and may provide the best evidence of the nature of climate change on Mars. No direct mineralogical measurements of Martian regolith were performed by the Viking missions, but the biology and X-ray fluorescence experiments provided some information on the physiochemical properties of Martian regolith. Most post-Viking studies of candidate weathering products have emphasized phyllosilicates and Fe-oxides; zeolites are potentially important, but overlooked, candidate Martian minerals. Zeolites would be important on Mars for three different reasons. First, they are major sinks of atmospheric gases and, per unit mass, are stronger and more efficient sorbents than are phyllosilicates. Secondly, they can be virtually unique sorbents and shelters for organic compounds and possible catalysts for organic-based reactions. Finally, their exchangeable ions are good indicators of the chemical properties of solutions with which they have communicated. Accordingly, the search for information on past compositions of the Martian atmosphere and hydrosphere should find zeolites to be rich repositories.

  13. Synthetic zeolites and other microporous oxide molecular sieves.

    PubMed

    Sherman, J D

    1999-03-30

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow "tailoring" of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol. PMID:10097059

  14. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    SciTech Connect

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; Dixon, David A.; Gates, Bruce C.

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.

  15. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    DOE PAGES

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; Dixon, David A.; Gates, Bruce C.

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridiummore » hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.« less

  16. Theoretical maximal storage of hydrogen in zeolitic frameworks.

    PubMed

    Vitillo, Jenny G; Ricchiardi, Gabriele; Spoto, Giuseppe; Zecchina, Adriano

    2005-12-01

    Physisorption and encapsulation of molecular hydrogen in tailored microporous materials are two of the options for hydrogen storage. Among these materials, zeolites have been widely investigated. In these materials, the attained storage capacities vary widely with structure and composition, leading to the expectation that materials with improved binding sites, together with lighter frameworks, may represent efficient storage materials. In this work, we address the problem of the determination of the maximum amount of molecular hydrogen which could, in principle, be stored in a given zeolitic framework, as limited by the size, structure and flexibility of its pore system. To this end, the progressive filling with H2 of 12 purely siliceous models of common zeolite frameworks has been simulated by means of classical molecular mechanics. By monitoring the variation of cell parameters upon progressive filling of the pores, conclusions are drawn regarding the maximum storage capacity of each framework and, more generally, on framework flexibility. The flexible non-pentasils RHO, FAU, KFI, LTA and CHA display the highest maximal capacities, ranging between 2.86-2.65 mass%, well below the targets set for automotive applications but still in an interesting range. The predicted maximal storage capacities correlate well with experimental results obtained at low temperature. The technique is easily extendable to any other microporous structure, and it can provide a method for the screening of hypothetical new materials for hydrogen storage applications.

  17. Hierarchical Porous Zeolite Structures for Pressure Swing Adsorption Applications.

    PubMed

    Besser, Benjamin; Tajiri, Henrique Akira; Mikolajczyk, Gerd; Möllmer, Jens; Schumacher, Thomas C; Odenbach, Stefan; Gläser, Roger; Kroll, Stephen; Rezwan, Kurosch

    2016-02-10

    Porous adsorbents with hierarchical structured macropores ranging from 1 to 100 μm are prepared using a combination of freeze casting and additional sacrificial templating of polyurethane foams, with a zeolite 13X powder serving as adsorbent. The pore system of the prepared monoliths features micropores assigned to the zeolite 13X particle framework, interparticular pores of ∼1-2 μm, lamellar pores derived from freeze casting of ∼10 μm, and an interconnected pore network obtained from the sacrificial templates ranging from around 100 to 200 μm with a total porosity of 71%. Gas permeation measurements show an increase in intrinsic permeability by a factor of 14 for monoliths prepared with an additional sacrificial templated foam compared to monoliths solely providing freeze casting pores. Cyclic CO2 adsorption and desorption tests where pressure swings between 8 and 140 kPa reveal constant working capacities over multiple cycles. Furthermore, the monoliths feature a high volumetric working capacity of ∼1.34 mmol/cm(3) which is competitive to packed beds made of commercially available zeolite 13X beads (∼1.28 mmol/cm(3)). Combined with the faster CO2 uptake showing an adsorption of 50% within 5-8 s (beads ∼10 s), the monoliths show great potential for pressure swing adsorption applications, where high volumetric working capacities, fast uptakes, and low pressure drops are needed for a high system performance. PMID:26760054

  18. Modifications of mitosis

    SciTech Connect

    1993-12-31

    Chapter 15, discusses modifications of mitosis, including endoreduplication, polyteny, endomitosis, C-mitosis, restitution, amitosis and multipolar mitoses. Apart from multipolar mitosis, all other mitotic modifications are characterized by an absent or defective spindle, and in most cases these result in the duplication of the chromosome number. 29 refs., 4 figs.

  19. Permit application modifications

    SciTech Connect

    1995-11-01

    This document contains the Permit Application Modifications for the Y-12 Industrial Landfill V site on the Oak Ridge Reservation. These modifications include the assessment of stability of the proposed Landfill V under static and loading conditions. Analyses performed include the general slope stability, veneer stability of the bottom liner and cover system, and a liquefaction potential assessment of the foundation soils.

  20. Lifestyle modifications for GDM.

    PubMed

    Dhingra, Atul; Ahuja, Kamlesh

    2016-09-01

    Prevalence of gestational diabetes mellitus (GDM) is increasing worldwide more so in Southeast Asian countries like India and Pakistan. 1 GDM is associated with various adverse foetal and maternal effects. The management of GDM aims at reducing blood glucose to reduce maternal and foetal morbidity and mortality. Various studies have shown that lifestyle modifications are an important tool for reducing blood glucose levels in patients with GDM. Lifestyle modifications consist of dietary modifications and daily physical activity. Dietary modifications aim to achieve glycaemic control by providing adequate calories to the mother and foetus. Exercise is an obvious adjunct to dietary modifications for management of GDM. Therefore the purpose of this review is to summarize the benefits of lifestyle interventions in patients with GDM. PMID:27582149

  1. Development of Zeolite Nonwoven for the Adsorption of Radioactive Cesium - 13288

    SciTech Connect

    Murao, Ayako; Nakai, Tomonori; Mimura, Hitoshi; Miura, Teruo; Aoyama, Yoshihito

    2013-07-01

    The zeolite nonwoven fabric produced by TDS (Totally Dry System) process has some advantages such as the control of zeolite content, flexibility, strength and water-resistant property depending on the purpose. Hence the zeolite nonwoven fabric is expected for the application in various fields of the decontamination of Cs-contaminated water. In this study, Cs adsorption properties of zeolite nonwoven fabrics were examined by batch experiments, and the radiation stability, thermal stability and chemical durability were evaluated. As for batch adsorption properties, relatively large uptake rate of Cs{sup +} was obtained; the uptake equilibrium attained within 20 min and the uptake (%) was above 95%. The differences in zeolite content had no effects on the Cs{sup +} uptake (%). The uptake (%) of Cs{sup +} in seawater was slightly lowered compared to that in the presence of HNO{sub 3}. The uptake (%) of Cs{sup +} in seawater was estimated to be above 90% after 2 h-shaking, indicating the considerable enhancement of uptake rate compared to the conventional granular zeolites. The uptake (%) of Cs{sup +} for the zeolite high content type was estimated to be above 99% by using {sup 137}Cs tracer. As for the comparison of sealing treatment, the uptake (%) for the zeolite sheet treated with edge sealing was larger than that with rapping treatment. The uptake (%) for the zeolite sheet (zeolite high content type) was estimated to be about 95%, which is independent of sealing treatment and NaOH concentration. As for the stability, the surface morphology and the structure of zeolite sheet were not altered by the treatment with acid and alkaline solutions under the experimental conditions. The zeolite sheets were also stable after {sup 60}Co-γ ray irradiation up to 7.01x10{sup 6} R. On the other hand, color change for both fiber and zeolite and the shrinkage of the fiber were observed after heat treatment at 150 deg. C for 2 h. Thus the considerable enhancement of adsorption

  2. Zeolite inorganic scaffolds for novel biomedical application: Effect of physicochemical characteristic of zeolite membranes on cell adhesion and viability

    NASA Astrophysics Data System (ADS)

    Tavolaro, Palmira; Catalano, Silvia; Martino, Guglielmo; Tavolaro, Adalgisa

    2016-09-01

    The design, preparation and selection of inorganic materials useful as functional scaffolds for cell adhesion is a complex question based both on the understanding of the chemical behavior of the materials and individual cells, and on their interactions. Pure zeolite membranes formed from synthetic crystals offer chemically-capable being modulated silanolic surfaces that are amenable to adhesion and growth of fibroblasts. We report the facile preparation of reusable, very longlasting, biocompatible, easily sterilized synthetic scaffolds in a zeolite membrane configuration, which are very stable in aqueous media (apart from ionic strength and pH values), able to adsorb pollutant species and to confine undesired toxic ions (present in culture media). This may ultimately lead to the development of cell supports for economic antibiotic-free culture media.

  3. Copper and copper-nickel alloys as zebra mussel antifoulants

    SciTech Connect

    Dormon, J.M.; Cottrell, C.M.; Allen, D.G.; Ackerman, J.D.; Spelt, J.K.

    1996-04-01

    Copper has been used in the marine environment for decades as cladding on ships and pipes to prevent biofouling by marine mussels (Mytilus edulis L.). This motivated the present investigation into the possibility of using copper to prevent biofouling in freshwater by both zebra mussels and quagga mussels (Dreissena polymorpha and D. bugensis collectively referred to as zebra mussels). Copper and copper alloy sheet proved to be highly effective in preventing biofouling by zebra mussels over a three-year period. Further studies were conducted with copper and copper-nickel mesh (lattice of expanded metal) and screen (woven wire with a smaller hole size), which reduced the amount of copper used. Copper screen was also found to be strongly biofouling-resistant with respect to zebra mussels, while copper mesh reduced zebra mussel biofouling in comparison to controls, but did not prevent it entirely. Preliminary investigations into the mechanism of copper antifouling, using galvanic couples, indicated that the release of copper ions from the surface of the exposed metal into the surrounding water is directly or indirectly responsible for the biofouling resistance of copper.

  4. Preparation of high purity copper fluoride by fluorinating copper hydroxyfluoride

    NASA Technical Reports Server (NTRS)

    King, R. B.; Lundquist, J. R.

    1969-01-01

    Copper fluoride containing no more than 50 ppm of any contaminating element was prepared by the fluorination of copper hydroxyfluoride. The impurity content was obtained by spark source mass spectrometry. High purity copper fluoride is needed as a cathode material for high energy density batteries.

  5. Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface‐Modified ZSM‐5

    PubMed Central

    Sheppard, Thomas; Daly, Helen; Goguet, Alex

    2015-01-01

    Abstract The mono(μ‐oxo) dicopper cores present in the pores of Cu‐ZSM‐5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM‐5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature‐programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu‐ZSM‐5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol. PMID:26925172

  6. Use of copper shavings to remove mercury from contaminated groundwater or wastewater by amalgamation.

    PubMed

    Huttenloch, Petra; Roehl, Karl Ernst; Czurda, Kurt

    2003-09-15

    The efficacy of copper shavings (Cu(0)) for the removal of Hg2+ from aqueous solution by amalgamation is demonstrated. Two kinds of copper shavings were investigated: (a) chemically processed shavings (Fluka) and (b) recycled shavings from scrap metal. Batch sorption experiments yielded very high retardation coefficients of 28 850-82 830 for the concentration range studied (1-10 000 microg/L Hg2+ dissolved in distilled water or in a 0.01 M CaCl2 matrix solution). Sorption data were well-described bythe Freundlich isotherm equation. Kinetic batch sorption experiments showed that 96-98% of Hg2+ was removed within 2 h. Column experiments were performed with a mercury solution containing 1000 microg/L Hg in a 0.01 M CaCl2 matrix with a flow rate of 0.5 m/d. No mercury breakthrough (c/c(0) = 0.5) could be detected after more than 2300 percolated pore volumes, and the high retardation coefficients determined in the batch studies could be confirmed. Copper was released from the shavings due to the amalgamation process and to copper corrosion by oxygen, resulting in concentrations of mobilized copper of 0.2-0.6 mg/L. Due to their high efficiency in removing Hg2+ from aqueous solution, the use of copper shavings for the removal of mercury from contaminated water is suggested, employing a sequential system of mercury amalgamation followed by the removal of mobilized copper by an ion exchanger such as zeolites. Possible applications could be in environmental technologies such as wastewater treatment or permeable reactive barriers for in situ groundwater remediation.

  7. Novel Zeolitic Imidazolate Framework/Polymer Membranes for Hydrogen Separations in Coal Processing

    SciTech Connect

    Musselman, Inga H.

    2013-01-31

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed-matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethylenediamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H2/CO2 selectivity similar to the uncrosslinked polymer.

  8. Ceruloplasmin, copper ions, and angiogenesis.

    PubMed

    Raju, K S; Alessandri, G; Ziche, M; Gullino, P M

    1982-11-01

    The ability to induce new formation of capillaries in the cornea was tested for ceruloplasmin, the copper carrier of serum, for fragments of the ceruloplasmin molecule with and without copper, for heparin, and for glycyl-L-histidyl-L-lysine, bound or not bound to copper ions. Male or female 2- to 3-kg New Zealand White rabbits were used. These experiments were prompted by the previous observation of copper accumulation in the cornea during angiogenesis and by the inability of copper-deficient rabbits to mount an angiogenic response. The results showed that the three different molecules were all able to induce angiogenesis provided that they were bound to copper. Fragments of the ceruloplasmin molecule also induced angiogenesis but only when copper was bound to the peptides. The data are interpreted to indicate that copper ions are involved in the sequence of events leading to angiogenesis and that the carrier molecules may be of quite a different nature. PMID:6182332

  9. Selective divalent copper chelation for the treatment of diabetes mellitus.

    PubMed

    Cooper, G J S

    2012-01-01

    latter probably undergoes AGE-modification itself. Defective copper regulation mediates organ damage through two general processes that occur simultaneously in the same individual: elevation of CuII-mediated pro-oxidant stress and impairment of copper-catalyzed antioxidant defence mechanisms. This author has proposed that diabetes-evoked copper dysregulation is an important new target for therapeutic intervention to prevent/reverse organ damage in diabetes, heart failure, and neurodegenerative diseases, and that triethylenetetramine (TETA) is the first in a new class of anti-diabetic molecules, which function by targetting these copper-mediated pathogenic mechanisms. TETA prevents tissue damage and causes organ regeneration by acting as a highly-selective CuII chelator which suppresses copper-mediated oxidative stress and restores anti-oxidant defenses. My group has employed TETA in a comprehensive programme of nonclinical studies and proof-of-principle clinical trials, thereby characterizing copper dysregulation in diabetes and identifying numerous linked cellular and molecular mechanisms though which TETA exerts its therapeutic actions. Many of the results obtained in nonclinical models with respect to the molecular mechanisms of diabetic organ damage have not yet been replicated in patients' tissues so their applicability to the human disease must be considered as inferential until the results of informative clinical studies become available. Based on evidence from the studies reviewed herein, trientine is now proceeding into the later stages of pharmaceutical development for the treatment of heart failure and other diabetic complications.

  10. Agricultural soils spiked with copper mine wastes and copper concentrate: implications for copper bioavailability and bioaccumulation.

    PubMed

    Ginocchio, Rosanna; Sánchez, Pablo; de la Fuente, Luz María; Camus, Isabel; Bustamante, Elena; Silva, Yasna; Urrestarazu, Paola; Torres, Juan C; Rodríguez, Patricio H

    2006-03-01

    A better understanding of exposure to and effects of copper-rich pollutants in soils is required for accurate environmental risk assessment of copper. A greenhouse experiment was conducted to study copper bioavailability and bioaccumulation in agricultural soils spiked with different types of copper-rich mine solid wastes (copper ore, tailing sand, smelter dust, and smelter slag) and copper concentrate. A copper salt (copper sulfate, CuSO4) that frequently is used to assess soil copper bioavailability and phytotoxicity also was included for comparison. Results showed that smelter dust, tailing sand, and CuSO4 are more likely to be bioavailable and, thus, toxic to plants compared with smelter slag, concentrate, and ore at equivalent total copper concentrations. Differences may be explained by intrinsic differences in copper solubilization from the source materials, but also by their capability to decrease soil pH (confounding effect). The copper toxicity and bioaccumulation in plants also varied according to soil physicochemical characteristics (e.g., pH and total organic carbon) and the available levels of plant nutrients, such as nitrogen, phosphorus, and potassium. Chemistry/mineralogy of mine materials, soil/pore-water chemistry, and plant physiological status thus should be integrated for building adequate models to predict phytotoxicity and environmental risk of copper. PMID:16566155

  11. Copper-phosphorus alloys offer advantages in brazing copper

    SciTech Connect

    Rupert, W.D.

    1996-05-01

    Copper-phosphorus brazing alloys are used extensively for joining copper, especially refrigeration and air-conditioning copper tubing and electrical conductors. What is the effect of phosphorus when alloyed with copper? The following are some of the major effects: (1) It lowers the melt temperature of copper (a temperature depressant). (2) It increases the fluidity of the copper when in the liquid state. (3) It acts as a deoxidant or a fluxing agent with copper. (4) It lowers the ductility of copper (embrittles). There is a misconception that silver improves the ductility of the copper-phosphorus alloys. In reality, silver added to copper acts in a similar manner as phosphorus. The addition of silver to copper lowers the melt temperature (temperature depressant) and decreases the ductility. Fortunately, the rate and amount at which silver lowers copper ductility is significantly less than that of phosphorus. Therefore, taking advantage of the temperature depressant property of silver, a Ag-Cu-P alloy can be selected at approximately the same melt temperature as a Cu-P alloy, but at a lower phosphorus content. The lowering of the phosphorus content actually makes the alloy more ductile, not the silver addition. A major advantage of the copper-phosphorus alloys is the self-fluxing characteristic when joining copper to copper. They may also be used with the addition of a paste flux on brass, bronze, and specialized applications on silver, tungsten and molybdenum. Whether it is selection of the proper BCuP alloy or troubleshooting an existing problem, the suggested approach is a review of the desired phosphorus content in the liquid metal and how it is being altered during application. In torch brazing, a slight change in the oxygen-fuel ratio can affect the joint quality or leak tightness.

  12. High adherence copper plating process

    DOEpatents

    Nignardot, H.

    1993-09-21

    A process is described for applying copper to a substrate of aluminum or steel by electrodeposition and for preparing the surface of an aluminum or steel substrate for the electrodeposition of copper. Practice of the invention provides good adhesion of the copper layer to either substrate.

  13. Synthesis, deposition and characterization of magnesium hydroxide nanostructures on zeolite 4A

    SciTech Connect

    Koh, Pei-Yoong; Yan, Jing; Ward, Jason; Koros, William J.; Teja, Amyn S.; Xu, Bo

    2011-03-15

    Research highlights: {yields} Reports a simple precipitation-growth method to produce nanostructures of Mg(OH){sub 2} on the surface of zeolite 4A. {yields} Able to control the growth of the nanostructures by manipulating the experimental procedure. {yields} Able to deposit Mg(OH){sub 2} onto specific sites namely bridging hydroxyl protons (SiOHAl) on the surface of zeolite 4A. -- Abstract: The precipitation and self-assembly of magnesium hydroxide Mg(OH){sub 2} nanopetals on dispersed zeolite 4A particles was investigated. Mg(OH){sub 2}/zeolite nanocomposites were produced from magnesium chloride solutions and characterized via X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared analysis (FTIR), and solid state NMR. It was determined that Mg(OH){sub 2} interacted with bridging hydroxyl protons (SiOHAl) on the zeolite surface, but not with silanol or aluminol groups. NMR analysis showed that 13% of the tetrahedral Al sites on the zeolite were converted to octahedral Al. The zeolite structure and crystallinity remained intact after treatment, and no dealumination reactions were detected. This suggests that the deposition-precipitation process at ambient conditions is a facile method for controlling Mg(OH){sub 2} nanostructures on zeolites.

  14. Facile synthesis of nano-sized hollow single crystal zeolites under mild conditions.

    PubMed

    Fodor, Daniel; Pacosová, Lucie; Krumeich, Frank; van Bokhoven, Jeroen A

    2014-01-01

    We report a method to synthesize hollow ZSM-5 single crystals of a size below 100 nm that could function as nanoreactors with access through the zeolite micropores only. In the first step, ZSM-5 is synthesized with the respective crystal size. In the second, the zeolite is base leached and acid washed under mild conditions.

  15. Study of Molecular-Shape Selectivity of Zeolites by Gas Chromatography

    ERIC Educational Resources Information Center

    Chao, Pei-Yu; Chuang, Yao-Yuan; Ho, Grace Hsiuying; Chuang, Shiow-Huey; Tsai, Tseng-Chang; Lee, Chi-Young; Tsai, Shang-Tien; Huang, Jun-Fu

    2008-01-01

    A sorption experiment using a gas chromatograph is described that can help students understand the "molecular-shape selectivity" behavior of zeolites in the subnano regime. Hexane isomers are used as probe molecules to demonstrate the sorption phenomena. In the experiment, a zeolite adsorbs certain hexane isomers with molecular sizes smaller than…

  16. One-pot synthesized hierarchical zeolite supported metal nanoparticles for highly efficient biomass conversion.

    PubMed

    Wang, Darui; Ma, Bing; Wang, Bo; Zhao, Chen; Wu, Peng

    2015-10-21

    Hierarchically porous zeolite supported metal nanoparticles are successfully prepared through a base-assisted chemoselective interaction between the silicon species on the zeolite crystal surface and metal salts, in which in situ construction of mesopores and high dispersion of metal species are realized simultaneously. PMID:26361087

  17. Removal of ammonium from swine wastewater by zeolite combined with chlorination for regeneration.

    PubMed

    Huang, Haiming; Yang, Liping; Xue, Qiang; Liu, Jiahui; Hou, Li; Ding, Li

    2015-09-01

    This study investigated a process using ammonium ion (NH4(+)) exchange on zeolite in combination with chlorination regeneration for the safe treatment of simulated swine wastewater. Two stages i) 120-min zeolite ion-exchange and ii) 10-min exchanged zeolite regeneration facilitated NH4(+) ion removal from wastewater. Solution pH, contact time, adsorbent dosage, and competitive cations were the significant factors influencing the entire process. The effect of competitive cations on NH4(+) removal effectively followed the order of preference as Na(+)>K(+)>Ca(2+)>Mg(2+) at equivalent concentrations. The chlorination method experimentally removed approximately 99% of the NH4(+) exchanged on the zeolite, without remaining NH4(+) in the regeneration solution. Our analysis revealed that, in this process, the NH4(+) exchanged on the zeolite was first replaced by Na(+) and then oxidized to nitrogen gas. Reuse of the regenerated zeolite (GZ) indicated that the removal efficiency of NH4(+) ions was equal to that of the fresh zeolite modified with NaCl. Results of kinetic analysis revealed that the NH4(+) exchange on the GZ followed the pseudo-second-order model and the intraparticle diffusion model only for the first 60 min. The ion-exchange isotherm results demonstrated that the Langmuir model provided a slightly more consistent fit to the equilibrium data as compared with the Freundlich model. Repetitive experimental results confirmed that the proposed zeolite recycling process was stable and usable in simulated swine wastewater treatment.

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

    SciTech Connect

    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.

  19. Photoinduced electron transfers in zeolites: impact of the aluminum content on the activation energies.

    PubMed

    Hureau, Matthieu; Moissette, Alain; Gaillard, Jeremy; Brémard, Claude

    2012-10-01

    We report the activation energy determination corresponding to the recombination of the radical cation electron moiety created through photoionization of the 1,6-diphenyl-1,3,5-hexatriene molecule incorporated in ZSM-5 zeolite channels. We demonstrate that the charge separated state stabilization in zeolite does not depend only on the Al content but also on the Al repartition.

  20. Experiments for the Undergraduate Laboratory that Illustrate the Size-Exclusion Properties of Zeolite Molecular Sieves

    ERIC Educational Resources Information Center

    Cooke, Jason; Henderson, Eric J.

    2009-01-01

    Experiments are presented that demonstrate the size-exclusion properties of zeolites and reveal the reason for naming zeolites "molecular sieves". If an IR spectrometer is available, the adsorption or exclusion of alcohols of varying sizes from dichloromethane or chloroform solutions can be readily demonstrated by monitoring changes in the…