Science.gov

Sample records for mesoporous fe-containing hzsm-5

  1. Selective transformation of syngas into gasoline-range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles.

    PubMed

    Cheng, Kang; Zhang, Lei; Kang, Jincan; Peng, Xiaobo; Zhang, Qinghong; Wang, Ye

    2015-01-26

    Bifunctional Fischer-Tropsch (FT) catalysts that couple uniform-sized Co nanoparticles for CO hydrogenation and mesoporous zeolites for hydrocracking/isomerization reactions were found to be promising for the direct production of gasoline-range (C5-11 ) hydrocarbons from syngas. The Brønsted acidity results in hydrocracking/isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the mesoporosity contributes to suppressing the formation of lighter (C1-4 ) hydrocarbons. The selectivity for C5-11 hydrocarbons could reach about 70 % with a ratio of isoparaffins to n-paraffins of approximately 2.3 over this catalyst, and the former is markedly higher than the maximum value (ca. 45 %) expected from the Anderson-Schulz-Flory distribution. By using n-hexadecane as a model compound, it was clarified that both the acidity and mesoporosity play key roles in controlling the hydrocracking reactions and thus contribute to the improved product selectivity in FT synthesis.

  2. Utilization of fly ash-derived HZSM-5: catalytic pyrolysis of Jatropha wastes in a fixed-bed reactor.

    PubMed

    Vichaphund, S; Sricharoenchaikul, V; Atong, D

    2017-07-01

    Fly ash-derived HZSM-5 catalyst was first applied in the catalytic pyrolysis of Jatropha residues in a semi-continuous fixed-bed reactor. The catalytic performance of HZSM-5 catalysts prepared from chemicals including conventional hydrothermal HZSM-5, Ni/HZSM-5 by ion exchange, and commercial HZSM-5 (Si/Al = 30) was evaluated for comparison. Catalytic pyrolysis of Jatropha residues with HZSM-5 catalysts was investigated in terms of product yields and qualities of bio-oil and bio-char. The liquid yield produced from fly ash-derived HZSM-5 was 29.4%, which was comparable to those obtained from chemicals and commercial (30.2-32.2%). Fly ash-derived HZSM-5 had high efficiency in increasing desirable compounds such as aliphatics and phenols as well as decreasing oxygenates and particularly N-containing compounds in bio-oils. The higher heating values and pH value of catalytic bio-oil achieved from fly ash-derived HZSM-5 were comparable to those achieved from HZSM-5 prepared from chemicals and commercial. The bio-char had 48-50 wt% carbon and was classified as mesoporous material. Overall, HZSM-5 derived from fly ash showed potentials to use as a catalyst for catalytic pyrolysis application.

  3. Kinetic modeling of propane aromatization reaction over HZSM-5 and GaHZSM-5

    SciTech Connect

    Lukyanov, D.B.; Gnep, N.S.; Guisnet, M.R. . Catalyse en Chimie Organique)

    1995-02-01

    A detailed kinetic model for a propane aromatization reaction over HZSM-5 and GaHZSM-5 is developed. Kinetic modeling results show that propane transformation over HZSM-5 occurs via protolytic cracking and hydrogen transfer routes. The contributions of both routes in propane conversion are established. Rate constants of propane transformation steps are found to be at least 1,000 times lower than the rate constants of diene formation steps, which, in turn, are the slowest among the acid-catalyzed olefin aromatization steps. Gallium introduced into ZSM-5 catalyst is active in dehydrogenation of propane into propene, of olefins into dienes, and of naphthenes into aromatics. At the same time, gallium species catalyze propane transformation into methane and ethene hydrogenation into ethane. Both latter reactions appear to be the main reasons for the limit to aromatics selectivity over GaHZSM-5 catalysts.

  4. Kinetic modeling of ethene and propene aromatization over HZSM-5 and GaHZSM-5

    SciTech Connect

    Lukyanov, D.B.; Gnep, N.S.; Guisnet, M.R. . Catalyse en Chimie Organique)

    1994-02-01

    A kinetic model for ethene and propene aromatization over HZSM-5 and GaHZSM-5 is developed. This model describes olefin oligomerization and cracking on zeolite catalytic sites (ZCS), diene formation via hydrogen transfer on ZCS and via dehydrogenation on gallium species, diene cyclization on ZCS, and formation of cyclic diolefins and aromatics via hydrogen transfer on ZCS and via dehydrogenation on gallium species. The rate constants of various reaction steps are compared, and the contribution of gallium in formation of dienes and aromatics is estimated. It is shown that aromatics formation accelerates olefin conversion due to the olefin consumption, on one hand, and inhibits olefin conversion due to the partial blocking of the zeolite catalytic sites, on the other hand. Because of this, both the increase and the decrease in olefin conversion over GaHZSM-5 can be observed (in comparison with HZSM-5), depending on the feed olefin and on the reaction conditions.

  5. Furan production from glycoaldehyde over HZSM-5

    SciTech Connect

    Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin; Bu, Lintao; Beckham, Gregg T.; Nimlos, Mark R.; Paton, Robert S.; Robichaud, David J.

    2016-04-03

    Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalytic fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.

  6. Furan production from glycoaldehyde over HZSM-5

    DOE PAGES

    Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin; ...

    2016-04-03

    Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalyticmore » fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.« less

  7. 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.

  8. IR characteristics of alcohol reactivity on HZSM-5 zeolites

    NASA Astrophysics Data System (ADS)

    Bezouhanova, C. P.; Kalvachev, Yu. A.; Lechert, H.

    1992-08-01

    The IR spectra of alcohols (1-butanol, 2-butanol, 1-hexanol, cyclopentanol, cyclohexanol, 3-methylcyclohexanol and benzylalcohol) in contact with HZSM-5 zeolites revealed bands characteristic of three types of adsorbed species. The bands at 3020, 1650 and 1515 cm -1 originate from olefins, obtained after dehydration of the primary and secondary alcohols. The band at 1515 cm -1 was related to perturbed double bonds interacting with the proton acid sites of the zeolite. A band at 1720-1765 cm -1 was assigned to a carbonyl compound obtained by alcohol dehydrogenation.

  9. Oligomerization of Biomass-Derived Light Olefins to Liquid Fuel: Effect of Alkali Treatment of HZSM-5 Catalyst

    DOE PAGES

    Wang, Xiaoxing; Hu, Xiaoyan; Song, Chunshan; ...

    2017-09-27

    As a part of a new approach to convert biomass to liquid fuels, we investigated the effects of alkali treatment on the property and performance of HZSM-5 for oligomerization of biomass-derived ethylene under atmospheric pressure. The characterization results showed that alkali treatment led to the increase in the total and mesopore volumes, but decrease in the surface area and micropore volume. Furthermore, when NaOH concentration was low (< 0.5 M), the ZSM-5 structure was largely preserved with the increase in the mesopores and acidity, while higher NaOH concentration can severely destroy the zeolite structure, resulting in a significant reduction inmore » the micropores and acidity. The ethylene oligomerization results showed that not only the ethylene conversion and the liquid yield increased, but also the catalyst stability was improved after proper NaOH treatment. Finally, we discussed the relationship between the structure and performance« less

  10. Towards a full understanding of the nature of Ni(II) species and hydroxyl groups over highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation method.

    PubMed

    Chen, Bao-Hui; Chao, Zi-Sheng; He, Hao; Huang, Chen; Liu, Ya-Juan; Yi, Wen-Jun; Wei, Xue-Ling; An, Jun-Fang

    2016-02-14

    Highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation (D-P) method were characterized by Fourier transform infrared (FT-IR), hydrogen temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), N2-absorption/desorption, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and (27)Al magic-angle nuclear magnetic resonance (MAS NMR) techniques. The results showed that the D-P of nickel species occurred predominantly on the internal surface of highly siliceous HZSM-5 zeolite, in which the internal silanol groups located on the hydroxylated mesopores or nanocavities played a key role. During the D-P process, nickel hydroxide was first deposited-precipitated via olation/polymerization of neutral hydroxoaqua nickel species over the HZSM-5 zeolite. With the progress of the D-P process, 1 : 1 nickel phyllosilicate was formed over the HZSM-5 via the hetero-condensation/polymerization between charged hydroxoaqua nickel species and monomer silicic species generated due to the partial dissolution of the HZSM-5 framework. The 1 : 1 nickel phyllosilicate could also be generated via the hydrolytic adsorption of hydroxoaqua nickel species and their subsequent olation condensation. After calcination, the deposited-precipitated nickel hydroxide was decomposed into nickel oxide, while the 1 : 1 nickel phyllosilicate was transformed into 2 : 1 nickel phyllosilicate. According to the above mechanism, Ni(ii) species were present both in the form of nickel oxide and 2 : 1 nickel phyllosilicate, which were mutually separated from each other, being highly dispersed over HZSM-5 zeolite.

  11. HZSM-5/MCM-41 composite molecular sieves for the catalytic cracking of endothermic hydrocarbon fuels: nano-ZSM-5 zeolites as the source

    NASA Astrophysics Data System (ADS)

    Sang, Yu; Jiao, Qingze; Li, Hansheng; Wu, Qin; Zhao, Yun; Sun, Kening

    2014-12-01

    A series of HZSM-5/MCM-41 composite molecular sieves (HZM-Ns ( x)) were prepared by employing nano-ZSM-5 zeolites with the SiO2/Al2O3 ratios ( x) of 50, 100 and 150 as the source. These materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, N2 adsorption-desorption measurement, and NH3 temperature-programmed desorption. The catalytic cracking of endothermic hydrocarbon fuels over the HZM-Ns with n-decane as model was evaluated at atmospheric pressure and 500 °C. The effect of the parent zeolite, mesopore and SiO2/Al2O3 ratio on the structure, acidity, and catalytic performance of HZM-Ns was investigated. The HZM-Ns exhibited a skeletal matrix with nano-sized HZSM-5 particles (200-300 nm) with a controllable acidity well dispersed in and microporous-mesoporous hierarchical pores. The mesoporous structure improved the diffusion of the reactants and products in the pores, and the HZSM-5 nanoparticles uniformly dispersed in the MCM-41 matrix supplied a proper acidity, shorter channels, and a higher specific surface area for reaction. These resulted in a high catalytic activity, a high selectivity to light olefins and a long lifetime for n-decane catalytic cracking. The HZM-N (150) exhibited the excellent conversion, a high selectivity to light olefins and a long lifetime due to low diffusion resistance, high specific surface area, and appropriate acid distribution and strength, with the increasing SiO2/Al2O3 ratio.

  12. Hydrothermal liquefaction of Chlorella pyrenoidosa for bio-oil production over Ce/HZSM-5.

    PubMed

    Xu, Yufu; Zheng, Xiaojing; Yu, Huiqiang; Hu, Xianguo

    2014-03-01

    This paper investigated a novel hydrothermal liquefaction process of Chlorella pyrenoidosa catalyzed by Ce/HZSM-5. The chemical groups and components of the residues of C. pyrenoidosa were analyzed by Fourier transform infrared spectrometry and Gas Chromatograph-Mass Spectrometer. The crystal structure and micro surface topography of C. pyrenoidosa before and after catalytic liquefaction were characterized by X-ray diffraction and Scanning electron microscopy, respectively. The experimental results showed that the catalytic cracking effects of Ce/HZSM-5 were superior to that of HZSM-5 as a liquefaction catalyst of C. pyrenoidosa. Compared with HZSM-5, Ce/HZSM-5 has a significantly enhanced Lewis acid active center, smaller particle size, larger specific surface, and highly dispersed Ce4O7 with trivalent and tetravalent cerium in the zeolite skeleton channel that accelerate the catalytic liquefaction of C. pyrenoidosa. The rare earth modified zeolite Ce/HZSM-5 exhibits good potential and a beneficial nature for the preparation of bio-oil from microalgae with high efficiency.

  13. Catalytic upgrading of bio-oil by HZSM-5 in sub- and super-critical ethanol.

    PubMed

    Peng, Jun; Chen, Ping; Lou, Hui; Zheng, Xiaoming

    2009-07-01

    The pyrolysis bio-oil from rice husk was upgraded in sub- and super-critical ethanol using HZSM-5 as catalyst. The results showed that super-critical upgrading process performed more effectively than sub-critical upgrading process. Acidic HZSM-5 facilitates esterification in super-critical ethanol to convert acids contained in crude bio-oil into various kinds of esters. Stronger acidic HZSM-5 (low Si/Al ratio) can facilitate cracking of heavy components of crude bio-oil more effectively in super-critical upgrading process. The residue of distillated upgraded bio-oil from super-critical upgrading process decreased evidently, compared with that of distillated crude bio-oil. This work proved that crude bio-oil can be effectively upgraded in super-critical upgrading process with the aid of acidic catalyst.

  14. Probing the surface of nanosheet H-ZSM-5 with FTIR spectroscopy.

    PubMed

    Bleken, Bjørn-Tore Lønstad; Mino, Lorenzo; Giordanino, Filippo; Beato, Pablo; Svelle, Stian; Lillerud, Karl Petter; Bordiga, Silvia

    2013-08-28

    Herein we report FTIR in situ adsorption of molecular hydrogen, carbon monoxide, water, methanol, pyridine and 2,4,6-trimethylpyridine (collidine) on nanosheet H-ZSM-5 which was recently studied in the methanol to hydrocarbons (MTH) reaction. The nature of the hydroxyl groups and surface species are described in detail. The IR spectrum of nanosheet H-ZSM-5 is dominated by silanols, which saturate the external surfaces. The acidity of Si(OH)Al is comparable to that observed in the case of standard microcrystalline H-ZSM-5. The study of the external surface allows the recognition of Si(OH)Al species located at the channel entrance, which are mostly all accessible to hindered molecules such as collidine.

  15. Accumulation of inorganic impurities on HZSM-5 during catalytic fast pyrolysis of switchgrass

    USDA-ARS?s Scientific Manuscript database

    The fate of inorganic species present in switchgrass during fluidized bed catalytic pyrolysis over HZSM-5 catalysts was studied with emphasis on their accumulation on the catalyst. Five catalytic pyrolysis experiments were performed in two series, reusing the catalyst after each sample. Catalysts w...

  16. Production of aromatic hydrocarbons via catalytic pyrolysis of biomass over fe-modified HZSM-5 zeolites

    USDA-ARS?s Scientific Manuscript database

    Iron modified HZSM-5 catalysts were prepared by partial ion exchange of NH4ZSM-5 with Fe (II) at three different loadings (1.4, 2.8 and 4.2 wt%), and their effectiveness for producing aromatic hydrocarbons from cellulose, cellobiose, lignin and switchgrass by catalytic pyrolysis were screened using ...

  17. Direct Conversion of Syngas-to-Hydrocarbons over Higher Alcohols Synthesis Catalysts Mixed with HZSM-5

    SciTech Connect

    Lebarbier Dagel, Vanessa M.; Dagle, Robert A.; Li, Jinjing; Deshmane, Chinmay A.; Taylor, Charles E.; Bao, Xinhe; Wang, Yong

    2014-09-10

    The synthesis of hydrocarbon fuels directly from synthesis gas (i.e. one step process) was investigated with a catalytic system comprised of HZSM-5 physically mixed with either a methanol synthesis catalyst or a higher alcohols synthesis (HAS) catalyst. The metal sites of the methanol or HAS synthesis catalyst enable the conversion of syngas to alcohols, whereas HZSM-5 provides acid sites required for methanol dehydration, and dimethyl ether-to-hydrocarbons reactions. Catalytic performance for HZSM-5 when mixed with either a 5 wt.% Pd/ZnO/Al2O3 methanol synthesis catalyst or a HAS catalyst was evaluated at 300°C, 70 bars, GHSV=700 h-1 and H2/CO=1 using a HZSM-5: alcohols synthesis catalyst weight ratio of 3:1. The major difference observed between the methanol synthesis and HAS catalyst mixtures was found in the production of durene which is an undesirable byproduct. While durene formation is negligible with any of the HAS catalysts mixed with the HZSM-5 evaluated in this study, it represents almost 50% of the C5+ fraction for the methanol synthesis catalyst (5 wt.% Pd/ZnO/Al2O3 ) mixed with HZSM-5. This presents an advantage for using HAS catalysts over the methanol synthesis catalyst to minimize the durene by-product. The yield toward the desired C5+ hydrocarbons is thus twice higher with selected HAS catalysts as compared to when HZSM-5 is mixed with 5 wt.% Pd/ZnO/Al2O3. Among all the HAS catalysts evaluated in this study, a catalyst with 0.5 wt.% Pd/FeCoCu catalyst was found the most promising due to higher production of C5+ hydrocarbons and low durene formation. The efficiency of the one-step process was thus further evaluated using the HZSM-5: 0.5 wt.% Pd/FeCoCu catalyst mixture under a number of process conditions to maximize liquid hydrocarbons product yield. At 300oC, 70 bars, GHSV = 700 h-1 and HZSM-5: 0.5 wt.% Pd/FeCoCu = 3:1 (wt.), the C5+ fraction represents 48.5% of the hydrocarbons. Unfortunately, it is more difficult to achieve higher selectivity

  18. Conversion to Aromatic Hydrocarbons Over Nano- and Micro-Sized Particle La/Zn/HZSM-5 Catalysts.

    PubMed

    Kim, Han-Gyu; Yang, Yoon-Cheol; Jeong, Kwang-Eun; Kim, Tae-Wan; Chae, Ho-Jeong; Jeong, Soon-Yong; Kim, Chul-Ung; Lee, Kwan-Young

    2015-01-01

    The effect of the template of HZSM-5 and its synthesis method on the catalytic conversions of ethanol to aromatic hydrocarbons has been investigated over a 0.8%Zn/0.6%La/HZSM-5 (Si/Al2 = 50) catalyst in a fixed-bed flow reactor under operating conditions of T = 710 K, P = 1 bar, and WHSV = 0.8 hr(-1). Nano- and micro-size HZSM-5 were prepared by hydrothermal and microwave synthesis with different templates: TPAOH, TPABr, and HMDA. Zinc and lanthanum modified HZSM-5 catalysts were prepared by a simple co-impregnation method. It was found that the size of the particles and the crystal structure of HZSM-5 were influenced by the template type and synthesis method. When using the TPAOH template, the nano-sized particles were prepared by microwave synthesis, whereas HZSM-5 prepared from TPABr and HMDA by a hydrothermal method, were composed of cubic shaped nanocrystals inside a micro-sized particle. The effect of the template on the selectivity to aromatics over a La/Zn/HZSM-5 catalyst was shown as follows: HMDA > TPABr > TPAOH.

  19. Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations

    SciTech Connect

    Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; Kim, Seonah

    2016-12-13

    Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5 zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p-xylene:o-xylene:m-xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.

  20. Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations

    DOE PAGES

    Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; ...

    2016-12-13

    Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5more » zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p-xylene:o-xylene:m-xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.« less

  1. Tailoring acidity of HZSM-5 nanoparticles for methyl bromide dehydrobromination by Al and Mg incorporation

    PubMed Central

    2014-01-01

    Three kinds of HZSM-5 nanoparticles with different acidity were tailored by impregnating MgO or varying Si/Al ratios. Both the textural and acidic properties of the as-prepared nanoparticles were characterized by nitrogen adsorption-desorption measurements, X-ray diffraction (XRD), scanning electron microscopy (SEM), ammonia temperature-programmed desorption (NH3-TPD) and Fourier transform infrared spectroscopy (FTIR or Py-FTIR). It was found that the intensity of Lewis acid sites with weak strength was enhanced by impregnating MgO or reducing Al concentration, and such an enhancement could be explained by the formation of Mg(OH)+ or charge unbalance of the MgO framework on the surface of HZSM-5 support. The effect of HZSM-5 nanoparticles' acidity on methyl bromide dehydrobromination as catalyst was evaluated. As the results, MgHZ-360 catalyst with the highest concentration of Lewis acid sites showed excellent stability, which maintained methyl bromide conversion of up 97% in a period of 400 h on stream. Coke characterization by BET measurements and TGA/DTA and GC/MS analysis revealed that polymethylated naphthalenes species were formed outside the channels of the catalyst with higher acid intensity and higher Brønsted acid concentration during the initial period of reaction, while graphitic carbon formed in the channels of catalyst with lower acid intensity and higher Lewis acid concentration during the stable stage. PMID:25328502

  2. n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

    NASA Astrophysics Data System (ADS)

    Thoa Dao, Thi Kim; Loc Luu, Cam

    2015-09-01

    A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 °C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

  3. Defect sites in highly siliceous HZSM-5 zeolites: A study performed by alumination and IR spectroscopy

    SciTech Connect

    Yamagishi, Kouji; Namba, Seitaro; Yashima, Tatsuaki )

    1991-01-24

    The concentration of oxygen atoms on defect sites in a highly siliceous HZSM-5 type zeolite was estimated by the {sup 18}O-exchange reaction between C{sup 18}O{sub 2} and the zeolite. The concentration of oxygen atoms on defect sites could be controlled by means of changes of the gel composition and of the use of various silica sources in the hydrothermal synthesis. The relationship between the concentration of oxygen atoms on defect sites in a highly siliceous HZSM-5 and the concentration of aluminum introduced into the framework of the HZSM-5 by an alumination was examined. The concentration of the framework aluminum was the same as one-fourth that of the oxygen atoms on defect sites. These results suggest that the defect sites into which aluminum atoms are introduced tetrahedrally can be identified with hydroxyl nests that consist of four silanol groups. The existence of hydroxyl nests could be confirmed by IR spectroscopy. From the {sup 18}O-exchange reaction and IR measurements, the authors conclude that the sharp band at 3,740 cm{sup {minus}1} can be attributed to both isolated SiOH groups on the external surface and intracrystalline isolated SiOH groups and that the broad band at 3,505 cm{sup {minus}1} can be attributed to the SiOH groups in hydroxyl nests.

  4. The cooperative effect of Zn on Co/HZSM-5 catalyst for NO reduction with methane

    NASA Astrophysics Data System (ADS)

    Ren, Lili

    2017-05-01

    The cooperation of Zn and Co in the Zn-Co/HZSM-5 catalyst was investigated. NO was selectively reduced by CH4 to N2 in the presence of excess O2, and the catalytic activity depended on both the activation of CH4 and the adsorption properties of NOx. It was found that the addition of Zn could effectually heighten the selectivity of methane to NOx. The results of H2-TPR, NH3-TPD and XPS proved that addition of Zn into Co/HZSM-5 could inhibit the formation of bulk Co3O4 on the outer surface of the catalyst. Reducing the bulk Co3O4 would restrain the combustion of methane and improve the selectivity of methane to NOx, which was very consistent with the experimental results. MS-TPD results showed that Zn contributed the form of NO2 and strengthened its adsorption on the Co/HZSM-5 catalyst. So the reaction mechanism is proposed to occur via two successive elementary steps. First NO is oxidized to NO2 on the dispersed CoOx sites or Co2+ active sites; then NO2 is adsorbed on Zn2+ sites, and further reacts with methane on proton acid sites. The key step is the adsorption of NO2. Zn directly participates in the reaction by adsorption of NO2.

  5. Interaction between Ni and HZSM-5 in aromatization-enhanced reactive adsorption desulfurization catalysts for FCC gasoline upgrading.

    PubMed

    Zhao, Jinchong; Zhang, Lulu; She, Nannan; Liu, Yunqi; Chai, Yongming; Liu, Chenguang

    A compound catalyst (RA) consisted of Ni, ZnO and HZSM-5 with functions of reactive adsorption desulfurization (RADS) and olefin aromatization for fluid catalytic cracking (FCC) gasoline upgrading was prepared. X-ray powder diffraction (XRD), temperature-programmed reduction and low-temperature N2 adsorption were used to characterize the properties of the catalysts. Performance evaluation by FCC gasoline was carried out, and the result showed that the catalyst RA performed well in desulfurization and aromatization. For comparison, RADS catalyst (represented by DS) consisted of Ni and ZnO and aromatization catalyst (represented by Ar) consisted of HZSM-5 were prepared, respectively. They were combined in different ways to help investigating interaction between Ni and HZSM-5. Performance evaluated by FCC gasoline showed that catalyst RA performed best in desulfurization with a slight octane number loss. Interaction between Ni and HZSM-5 is a significant factor which influences the performance of the catalyst.

  6. Pyrolysis of sawdust in a conical spouted-bed reactor with a HZSM-5 catalyst

    SciTech Connect

    Olazar, M.; Aguado, R.; Bilbao, J.; Barona, A.

    2000-05-01

    The effect was studied of using an in-situ catalyst based on a HZSM-5 zeolite in flash pyrolysis with an inert gas (N{sub 2}) of pinus insignis sawdust in a conical spouted-bed reactor in the 400--500 C range and for a gas residence time of 50 ms. The use of the catalyst increases the yield of gases and decreases the yields of liquid and char. Likewise, the yield of CO{sub 2} decreases, whereas the yield of C{sub 4{minus}} hydrocarbons increases (15.9 wt. % at 450 C). The catalyst is efficient for partial deoxygenation of the liquid product.

  7. Infrared study on the mechanism of olefins and alcohols conversions over H-ZSM-5 zeolite

    NASA Astrophysics Data System (ADS)

    Bezuhanova, C. P.; Lechert, H. T.; Dimitrov, C.; Nenova, V. V.

    1984-03-01

    The IR spectra of 1-hexene, 1-heptene, cyclohexene, n-propanol and tert.-butanol, adsorbed on H-ZSM-5 zeolite, evacuated at 675 K, revealed a band at 1520 cm -1 after contacting with the zeolite at 373 J. The band was absent in the case of adsorbed benzene and cyclohexane and of very low intensity by methanol and ethanol adsorption. Considerations are given in favour of very strong interaction either of the type of X-complex or of carbenium ion. The second assumption was confirmed by the subsequent disappearance of the zeolitic OH bands.

  8. Methanol and ethanol conversion into hydrocarbons over H-ZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Hamieh, S.; Canaff, C.; Tayeb, K. Ben; Tarighi, M.; Maury, S.; Vezin, H.; Pouilloux, Y.; Pinard, L.

    2015-07-01

    Ethanol and methanol are converted using H-ZSM-5 zeolite at 623 K and 3.0 MPa into identical hydrocarbons (paraffins, olefins and aromatics) and moreover with identical selectivities. The distribution of olefins as paraffins follows the Flory distribution with a growth probability of 0.53. Regardless of the alcohol, the catalyst lifetime and selectivity into hydrocarbons C3+ are high in spite of an important coke content. The coke that poisons the Brønsted acid sites without blocking their access is composed in part of radical polyalkylaromatics. The addition of hydroquinone, an inhibitor of radicals, to the feed, provokes an immediate catalyst deactivation.

  9. Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

    NASA Astrophysics Data System (ADS)

    Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

    2017-10-01

    Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.

  10. Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

    PubMed

    Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

    2015-07-15

    Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration. Copyright © 2015. Published by Elsevier B.V.

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

    SciTech Connect

    Mei, Donghai; Lercher, Johannes A.

    2016-10-06

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

  12. Conversion of Biomass-Derived Small Oxygenates over HZSM-5 and its Deactivation Mechanism

    SciTech Connect

    Ramasamy, Karthikeyan K.; Gerber, Mark A.; Flake, Matthew D.; Zhang, He; Wang, Yong

    2014-02-28

    HZSM-5 catalyst deactivation was studied using aqueous feed mixtures containing ethanol, ethanol+ acetic acid, ethanol+ethyl acetate, or ethanol+acetaldehyde in a fixed bed reactor at 360°C and 300psig. Compared to ethanol alone experiment, addition of other oxygenates reduced catalyst life in the order of: ethyl acetateHZSM-5 catalyst.

  13. Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

    DOE PAGES

    Petkovic, Lucia M.; Ginosar, Daniel M.

    2014-01-01

    Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

  14. Influence of alumina binder content on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone.

    PubMed

    Kong, Xiangjin; Liu, Junhai

    2014-01-01

    The influence of the amount of alumina binders on the catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone was investigated in a fixed-bed reactor. N2 sorption, X-ray diffraction, H2-chemisorption and temperature-programmed desorption of ammonia were used to characterize the catalysts. It can be observed that the Ni/HZSM-5 catalyst bound with 30 wt.% alumina binder exhibited the best catalytic performance. The high catalytic performance may be due to relatively good Ni metal dispersion, moderate mesoporosity, and proper acidity of the catalyst.

  15. Magic-angle-spinning NMR studies of acid sites in zeolite H-ZSM-5

    SciTech Connect

    Brunner, E.; Ernst, H.; Freude, D.; Froehlich, T.; Hunger, M.; Pfeifer, H. )

    1991-01-01

    {sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.

  16. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios.

  17. Catalytic hydrocracking of Kapuk seed oil (Ceiba pentandra) to produce biofuel using Zn-Mo supported HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Mirzayanti, Y. W.; Prajitno, D. H.; Roesyadi, A.

    2017-05-01

    In the present paper Kapuk seed oil (KSO) was considered as a potential biofuel for alternative fuel from inedible oil. Catalytic hydrocracking of Kapuk seed oil using Zn-Mo supported on the HZSM-5 catalyst in a slurry pressure batch reactor at various temperature with reactor pressure in range 10-15 bar. The Zn-Mo/HZSM-5 catalyst was prepared by incipient wetness impregnation. The physicochemical properties of the catalyst were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) method. The best catalyst performance on catalytic hydrocracking of KSO using Zn-Mo/HZSM-5 (Si/Al = 25) with loading 2.92%wt for Zn and 7.55%wt for Mo. It displayed the highest hydrocarbon content decarboxylation and/or decarbonylation were 35.51 area% of n-paraffins and the highest content for gasoil-range alkanes was 17.24 area% at 4000C. The liquid product predominant is n-C15, and the second component is n-C17. The catalyst Zn-Mo/HZSM-5 was helpful for the catalytic hydrocracking of KSO for hydrocarbon biofuel production.

  18. Solid-state nuclear magnetic resonance study of acetone oxime adsorbed on CuZSM-5 and on HZSM-5

    SciTech Connect

    Wu, J.; Larsen, S.C.

    1999-02-15

    The reactions of acetone oxime, a proposed reaction intermediate for the selective catalytic reduction (SCR) of NO with propane on CuZSM-5 and on HZSM-5, have been studied with {sup 13}C and {sup 15}N solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR). The carbon- and/or nitrogen-containing surface species, as well as the products formed under conditions of thermodynamic equilibrium, have been monitored and identified. In the absence of NO and after heating to 150--200 C, the main hydrolysis products of adsorbed acetone oxime on CuZSM-5 are acetone and hydroxylamine, while the main hydrolysis products on HZSM-5 are acetic acid and methylamine. In addition, N{sub 2} and N{sub 2}O are formed from acetone oxime adsorbed on both HZSM-5 and CuZSM-5. In the presence of {sup 15}NO, the observation of mixed-labeled {sup 14}N{sup 15}NO and {sup 15N}{sup 14}NO shows that new N-N bonds are formed over CuZSM-5 and HZSM-5 between two different nitrogen atoms: one from gaseous {sup 15}NO molecules and the other from adsorbed acetone oxime and/or acetone oxime hydrolysis products. When {sup 15}NO and unlabeled acetone oxime are reacted on CuZSM-5, the {sup 14}N{sup 15}NO/{sup 15}N{sup 14}NO ratio is approximately 3, suggesting that the NO bond of gas-phase NO remains intact when it reacts with acetone oxime to form N{sub 2}O. It is also found that the formation of new N-N bonds from the reaction of NO and acetone oxime occurs at room temperature on CuZSM-5, but not until {approximately}150 C on HZSM-5.

  19. Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

    SciTech Connect

    Quartieri, Simona; Montagna, Gabriele; Arletti, Rossella; Vezzalini, Giovanna

    2011-06-15

    The elastic behavior of H-ZSM-5 was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as 'non-penetrating' and 'penetrating' pressure transmitting media, respectively. From P{sub amb} to 6.2 GPa the volume reduction observed in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6 GPa is 14.6%. A strong increase in the total electron number of the extraframework system, due to the penetration of water/alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed in zeolites undergoing this phenomenon without cell volume expansion. The higher compressibility in s.o. than in m.e.w. can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffen the structure and contrast the channel deformations. - Graphical abstract: High-pressure behavior of H-ZSM-5 compressed in (16:3:1) methanol:ethanol:water: (a) projection of the structure along the [0 1 0] direction at P{sub amb}, 2 GPa and after pressure release to original ambient conditions (P{sub amb} (rev)), and (b) P-dependence of the extraframework content expressed as total number of electrons (gray square represents the number of the extraframework electrons at P{sub amb} after decompression). Highlights: > X-ray powder diffraction study of H-ZSM-5 compressibility. > H-ZSM-5 is one of the softest porous material compressed in silicon oil. > Penetration of additional water/alcohol molecules upon compression in m.e.w. > Extra molecules contribute to stiffen the structure and to contrast HP effects.

  20. Synthesis, structural characterization, and catalytic properties of tungsten-exchanged H-ZSM5

    SciTech Connect

    Ding, Weiping; Meitzner, George D.; Marler, David O.; Iglesia, Enrique

    2001-01-18

    W-exchanged H-ZSM5 was prepared by sublimation of WCl6 at 673 K followed by hydrolysis of exchanged WClx species at 523 K. D2 exchange with residual OH groups showed that each W initially replaced about two zeolitic protons for W/Al ratios of 0.29 and 0.44, consistent with the formation of (WO2)2+ containing W6+ species bridging two cation exchange sites. As temperatures reached973 K during D2-OH exchange, these species reduced to (WO2)+ with the concurrent formation of one OD group. CH4 conversion turnover rates (per W) and C2-C1 2 selectivities are very similar to those observed on a Mo/H-ZSM5 sample with similar cation exchange level. As in the case of Mo/H-ZSM5, WOx/H-ZSM5 precursors are initially inactive in CH4 reactions, but they activate during induction with the concurrent evolution of CO, H2O, and an excess amount of H2. The reduction and carburization processes occurring during CH4 reactions and the structure of the exchanged WOx precursors was probed using in situ X-ray absorption spectroscopy (XAS). XAS studies confirmed the isolated initial nature of the exchanged WOx precursors after hydrolysis and dehydration and the formation of WCx clusters 0.6 nm in diameter during CH4 reactions at 973 K. The structural and catalytic resemblance between W- and Mo-exchanged H-ZSM5 is not unexpected, in view of chemical similarities between oxides or carbides of Mo and W. The synthesis of exchanged WOx precursors and their subsequent carburization during CH4 reactions, however, are more difficult than the corresponding processes for the MoOx counterparts. This may account for previous reports of lower CH4 reaction rates and aromatics selectivities on W/H-ZSM5 compared with those observed on Mo/H-ZSM5 and with those reported here for rigorously exchanged W/H-ZSM5.

  1. Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

    SciTech Connect

    Cheng, Yu-Ting; Huber, George W.

    2011-06-03

    The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysis–mass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/Al ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO₂, aromatics, and olefins at temperatures from 400 to 600 °C. Aromatics (e.g., benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C₁₂{sub +} oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 min of time on-stream. We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO₂, allene, C₂–C₆ olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 °C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450–600 °C). At low temperatures (450 °C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include Diels–Alder condensation (e.g., two furans form benzofuran and water

  2. Ethanol dehydration in HZSM-5 studied by density functional theory: evidence for a concerted process.

    PubMed

    Kim, Seonah; Robichaud, David J; Beckham, Gregg T; Paton, Robert S; Nimlos, Mark R

    2015-04-16

    Dehydration over acidic zeolites is an important reaction class for the upgrading of biomass pyrolysis vapors to hydrocarbon fuels or to precursors for myriad chemical products. Here, we examine the dehydration of ethanol at a Brønsted acid site, T12, found in HZSM-5 using density functional theory (DFT). The geometries of both cluster and mixed quantum mechanics/molecular mechanics (QM:MM) models are prepared from the ZSM-5 crystal structure. Comparisons between these models and different DFT methods are conducted to show similar results among the models and methods used. Inclusion of the full catalyst cavity through a QM:MM approach is found to be important, since activation barriers are computed on average as 7 kcal mol(-1) lower than those obtained with a smaller cluster model. Two different pathways, concerted and stepwise, have been considered when examining dehydration and deprotonation steps. The current study shows that a concerted dehydration process is possible with a lower (4-5 kcal mol(-1)) activation barrier while previous literature studies have focused on a stepwise mechanism. Overall, this work demonstrates that fairly high activation energies (∼50 kcal mol(-1)) are required for ethanol dehydration. A concerted mechanism is favored over a stepwise mechanism because charge separation in the transition state is minimized. QM:MM approaches appear to provide superior results to cluster calculations due to a more accurate representation of charges on framework oxygen atoms.

  3. Fast microwave-assisted pyrolysis of microalgae using microwave absorbent and HZSM-5 catalyst.

    PubMed

    Borges, Fernanda Cabral; Xie, Qinglong; Min, Min; Muniz, Luis Antônio Rezende; Farenzena, Marcelo; Trierweiler, Jorge Otávio; Chen, Paul; Ruan, Roger

    2014-08-01

    Fast microwave-assisted pyrolysis (fMAP) in the presence of a microwave absorbent (SiC) and catalyst (HZSM-5) was tested on a Chlorella sp. strain and on a Nannochloropsis strain. The liquid products were characterized, and the effects of temperature and catalyst:biomass ratio were analyzed. For Chlorella sp., a temperature of 550 °C, with no catalyst were the optimal conditions, resulting in a maximum bio-oil yield of 57 wt.%. For Nannochloropsis, a temperature of 500 °C, with 0.5 of catalyst ratio were shown to be the optimal condition, resulting in a maximum bio-oil yield of 59 wt.%. These results show that the use of microwave absorbents in fMAP increased bio-oil yields and quality, and it is a promising technology to improve the commercial application and economic outlook of microwave pyrolysis technology. Additionally, the use of a different catalyst needs to be considered to improve the bio-oil characteristics. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Deposition and characteristics of coke over a H-ZSM5 zeolite-based catalyst in the MTG process

    SciTech Connect

    Benito, P.L.; Gayubo, A.G.; Aguayo, A.T.; Olazar, M.; Bilbao, J.

    1996-11-01

    The influence of reaction conditions in the transformation of methanol into gasoline (temperature, time on stream, and contact time) on the deposition and nature of coke (composition, H/C ratio) and on its location in the porous structure of a H-ZSM5 zeolite-based catalyst has been studied in an isothermal fixed-bed integral reactor. The distribution of the coke within the porous structure of the catalyst is similar to that proposed for other reactions on H-ZSM5 zeolites, and the highly hydrogenated character of coke and its instability is noteworthy. Coke deposition has been related to catalyst acidic site deterioration and to a kinetic model for catalyst deactivation in an integral reactor.

  5. Catalytic performances of HZSM-5, NaY and MCM-41 in two-stage catalytic pyrolysis of pinewood

    NASA Astrophysics Data System (ADS)

    Wang, Y. M.; Wang, J.

    2016-08-01

    Experiments were carried out in an atmospheric two-stage fixed bed reactor to investigate the catalytic cracking of pinewood pyrolysis vapour over three single catalysts, HZSM-5, NaY and MCM-41. The pinewood was pyrolyzed in the first stage reactor at a heating rate of 10 °C min-1 from room temperature to 700 °C, and the resultant vapour was cracked through the second reactor at a temperature of 500, 600 or 700 °C with and without catalyst. Both the gases and liquid compounds were thoroughly determined. It was found that all three catalysts had significant catalytic effects on the vapour cracking especially in the range of 500-600 °C. However, three catalysts showed dissimilarity to each other with respect to the distributions of products. Among three catalysts, HZSM-5 displayed the highest selectivity for the formation of olefins and light aromatics, with the least deposit of coke, though NaY showed the strongest capability of deoxygenation. The HZSM-5 cracking at 600 °C was preferred to balance the yield and quality of bio-products. MCM-41 behaved as a worse catalyst in the deoxygenation, and its resultant liquid product contained more heavy aromatics.

  6. Intrinsic Kinetics of Dimethyl Ether Synthesis from Plasma Activation of CO2 Hydrogenation over Cu-Fe-Ce/HZSM-5.

    PubMed

    Su, Tongming; Zhou, Xinhui; Qin, Zuzeng; Ji, Hongbing

    2017-02-02

    CO2 is activated in a plasma reactor followed by hydrogenation over a Cu-Fe-Ce/HZSM-5 catalyst, and the intrinsic kinetics of the plasma catalytic process are studied. Compared with CO2 hydrogenation using Cu-Fe-Ce/HZSM-5 alone, the CO2 conversion and the dimethyl ether selectivity for the plasma catalytic process are increased by 16.3 %, and 10.1 %, respectively, indicating that the CO2 was activated by the plasma to promote hydrogenation. A study of the intrinsic kinetics shows that the activation energies of methanol formation, the reverse water-gas shift reaction, and methanol dehydration to dimethyl ether are 149.34, 75.47, and 73.18 kJ mol(-1) , respectively, which are lower than if Cu-Fe-Ce/HZSM-5 is used without plasma, indicating that the activation of CO2 in the plasma reduces the activation energy of the hydrogenation reaction and improves the yield of dimethyl ether.

  7. Liquid-phase processing of fast pyrolysis bio-oil using platinum/HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Santos, Bjorn Sanchez

    Recent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200°C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 °C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.

  8. A computational study of ethane cracking in cluster models of zeolite H-ZSM-5.

    SciTech Connect

    Zygmunt, S. A.

    1998-08-21

    Protolytic cracking of ethane by zeolites has been studied using quantum-chemical techniques and a cluster model of the zeolite Broensted acid site. Previous computational studies have utilized small cluster models and have not accounted for the long-range effects of the zeolite lattice. These studies have found reaction barriers for cracking which are significantly higher than experimental values. In this work we used a larger zeolite cluster model containing five tetrahedral (Si, Al) atoms (denoted 5T) and searched for stationary points along one possible reaction path for cracking at the HF/6-31 G(d) level of theory. This path involves a multi-step cracking reaction, in which the proton is first transferred from the acid site to the adsorbed ethane molecule to form an ion-pair equilibrium complex. Subsequently the proton attacks the C-C bond to complete the cracking process. The activation barrier for cracking was calculated, including corrections for (i) vibrational energies at the experimental reaction temperature of 773 K; (ii) electron correlation and an extended basis set at the B3LYP/6-311+G(3df,2p) level; and (iii) the influence of the surrounding zeolite lattice in H-ZSM-5. The barrier we obtain, 53 {+-} 5 kcal/mol, is significantly smaller than previous theoretical results and is in good agreement with typical experimental values for small hydrocarbons. Work is currently in progress to extend this study by carrying out geometry optimization of these complexes using the B3LYP method of density functional theory.

  9. Effect of torrefaction temperature on lignin macromolecule and product distribution from HZSM-5 catalytic pyrolysis

    DOE PAGES

    Mahadevan, Ravishankar; Adhikari, Sushil; Shakya, Rajdeep; ...

    2016-10-27

    Torrefaction is a low-temperature process considered as an effective pretreatment technique to improve the grindability of biomass as well as enhance the production of aromatic hydrocarbons from Catalytic Fast Pyrolysis (CFP). For this paper, this study was performed to understand the effect of torrefaction temperature on structural changes in the lignin macromolecule and its subsequent influence on in-situ CFP process. Lignin extracted from southern pine and switchgrass (via organosolv treatment) was torrefied at four different temperatures (150, 175, 200 and 225 °C) in a tubular reactor. Between the two biomass types studied, lignin from pine appeared to have greater thermalmore » stability during torrefaction when compared with switchgrass lignin. The structural changes in lignin as a result of torrefaction were followed by using FTIR spectroscopy, solid state CP/MAS 13C NMR, 31P NMR spectroscopy and it was found that higher torrefaction temperature (200 and 225 °C) caused polycondensation and de-methoxylation of the aromatic units of lignin. Gel permeation chromatography analysis revealed that polycondensation during torrefaction resulted in an increase in the molecular weight and polydispersity of lignin. The torrefied lignin was subsequently used in CFP experiments using H+ZSM-5 catalyst in a micro-reactor (Py-GC/MS) to understand the effect of torrefaction on the product distribution from pyrolysis. It was observed that although the selectivity of benzene-toluene-xylene compounds from CFP of pine improved from 58.3% (torrefaction temp at 150 °C) to 69.0% (torrefaction temp at 225 °C), the severity of torrefaction resulted in a loss of overall aromatic hydrocarbon yield from 11.6% to 4.9% under same conditions. Torrefaction at higher temperatures also increased the yield of carbonaceous residues from 63.9% to 72.8%. Finally, overall, torrefying lignin caused structural transformations in both type of lignins (switchgrass and pine), which is ultimately detrimental to achieving a higher aromatic hydrocarbon yield from CFP.« less

  10. Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts

    SciTech Connect

    He, Jiayue; Zhao, Chen; Lercher, Johannes A.

    2014-01-01

    Impacts of water, methanol, and hexadecane solvents on the individual steps of phenol hydrodeoxygenation are investigated over Pd/C and HZSM-5 catalyst components at 473 Kin presence of H-2. Hydrodeoxygenation of phenol to cyclohexane includes four individual steps of phenol hydrogenation to cyclohexanone on Pd/C, cyclohexanone hydrogenation to cyclohexanol on Pd/C, cyclohexanol dehydration to cyclohexene on HZSM-5, and cyclohexene hydrogenation to cyclohexane on Pd/C. Individual phenol and cyclohexanone hydrogenation rates are much lower in methanol and hexadecane than in water, while rates of cyclohexanol dehydration and cyclohexene hydrogenation are similar in three solvents. The slow rate in methanol is due to the strong solvation of reactants and the adsorption of methanol on Pd, as well as to the reaction between methanol and the cyclohexanone intermediate. The low solubility of phenol and strong interaction of hexadecane with Pd lead to the slow rate in hexadecane. The apparent activation energies for hydrogenation follow the order E-a phenol > E-a cyclonexanone > E-a cyclohexene, and the sequences of individual reaction rates are reverse in three solvents. The dehydration rates (1.1-1.8 x 10(3) mol mol(BAS)(-1) h(-1))and apparent activation energies (115-124 kJ mol(-1)) are comparable in three solvents. In situ liquid-phase IR spectroscopy shows the rates consistent with kinetics derived from chromatographic evidence in the aqueous phase and verifies that hydrogenation of phenol and cyclohexanone follows reaction orders of 1.0 and 0.55 over Pd/C, respectively. Conversion of cyclohexanol with HZSM-5 shows first-order dependence in approaching the dehydration-hydration equilibrium in the aqueous phase.

  11. Photocatalytic oxidation of NOx over TiO2/HZSM-5 catalysts in the presence of water vapor: Effect of hydrophobicity of zeolites.

    PubMed

    Guo, Gaofei; Hu, Yun; Jiang, Shumei; Wei, Chaohai

    2012-07-15

    TiO(2) hybridized with HZSM-5 zeolites photocatalysts were prepared by a simple solid state dispersion method. The physicochemical properties of the catalysts were characterized by X-ray diffraction, UV-vis diffuse reflectance and FT-IR spectroscopy. The photocatalytic oxidation of NO(x) over TiO(2)/HZSM-5 having different Si/Al ratios was carried out under various levels of humidity and different pre-adsorption times in dark. The TiO(2)/HZSM-5 composite catalysts exhibited higher NO conversion and lower NO(2) formation than pure TiO(2). Pre-adsorption with water vapor and the high humidity during the photoreaction were harmful to the reactivity of TiO(2) hybridized with hydrophilic HZSM-5 zeolite. However, the photocatalytic reactivity of TiO(2) hybridized with hydrophobic zeolite varied little with increase in humidity. The results indicated that the high photocatalytic reactivity of TiO(2)/HZSM-5 catalysts is largely depended on the hydrophobicity of the zeolites. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Production of light olefins by catalytic conversion of lignocellulosic biomass with HZSM-5 zeolite impregnated with 6wt.% lanthanum.

    PubMed

    Huang, Weiwei; Gong, Feiyan; Fan, Minghui; Zhai, Qi; Hong, Chenggui; Li, Quanxin

    2012-10-01

    Catalytic conversion of rice husk, sawdust, sugarcane bagasse, cellulose, hemicellulose and lignin into olefins was performed with HZSM-5 containing 6 wt.% lanthanum. The olefins yields for different feedstocks decreased in the order: cellulose>hemicellulose>sugarcane bagasse>rice husk>sawdust>lignin. Biomass containing higher content of cellulose or hemicellulose produced more olefins than feedstocks with higher content of lignin. Among the biomass types, sugarcane bagasse provided the highest olefin yield of 0.12 kg olefins/(kg dry biomass) and carbon yield of 21.2C-mol%. Temperature, residence time and the catalyst/feed ratio influenced olefin yield and selectivity. While the HZSM-5 zeolite was catalytically active, the incorporation of lanthanum at 2.9, and 6.0 wt.% increased the production of olefins from rice husk by 15.6% and 26.5%, respectively. The conversion of biomass to light olefins potentially provides an alternative and sustainable route for production of the key petrochemicals.

  13. Adsorption and diffusion of fructose in zeolite HZSM-5: selection of models and methods for computational studies.

    SciTech Connect

    Cheng, L.; Curtiss, L. A.; Assary, R. S.; Greeley, J.; Kerber, T.; Sauer, J.

    2011-09-14

    The adsorption and protonation of fructose in HZSM-5 have been studied for the assessment of models for accurate reaction energy calculations and the evaluation of molecular diffusivity. The adsorption and protonation were calculated using 2T, 5T, and 46T clusters as well as a periodic model. The results indicate that the reaction thermodynamics cannot be predicted correctly using small cluster models, such as 2T or 5T, because these small cluster models fail to represent the electrostatic effect of a zeolite cage, which provides additional stabilization to the ion pair formed upon the protonation of fructose. Structural parameters optimized using the 46T cluster model agree well with those of the full periodic model; however, the calculated reaction energies are in significant error due to the poor account of dispersion effects by density functional theory. The dispersion effects contribute -30.5 kcal/mol to the binding energy of fructose in the zeolite pore based on periodic model calculations that include dispersion interactions. The protonation of the fructose ternary carbon hydroxyl group was calculated to be exothermic by 5.5 kcal/mol with a reaction barrier of 2.9 kcal/mol using the periodic model with dispersion effects. Our results suggest that the internal diffusion of fructose in HZSM-5 is very likely to be energetically limited and only occurs at high temperature due to the large size of the molecule.

  14. Adsorption and Diffusion of Fructose in Zeolite HZSM-5: Selection of Models and Methods for Computational Studies

    SciTech Connect

    Cheng, Lei; Curtiss, Larry A.; Assary, Rajeev S.; Greeley, Jeffrey P.; Kerber, Torsten; Sauer, Joachim

    2011-11-10

    The adsorption and protonation of fructose inHZSM-5 have been studied for the assessment of models for accurate reaction energy calculations and the evaluation of molecular diffusivity. The adsorption and protonation were calculated using 2T, 5T, and 46T clusters as well as a periodic model. The results indicate that the reaction thermodynamics cannot be predicted correctly using small cluster models, such as 2T or 5T, because these small cluster models fail to represent the electrostatic effect of a zeolite cage, which provides additional stabilization to the ion pair formed upon the protonation of fructose. Structural parameters optimized using the 46T cluster model agree well with those of the full periodic model; however, the calculated reaction energies are in significant error due to the poor account of dispersion effects by density functional theory. The dispersion effects contribute -30.5 kcal/mol to the binding energy of fructose in the zeolite pore based on periodic model calculations that include dispersion interactions. The protonation of the fructose ternary carbon hydroxyl group was calculated to be exothermic by 5.5 kcal/mol with a reaction barrier of 2.9 kcal/mol using the periodic model with dispersion effects. Our results suggest that the internal diffusion of fructose in HZSM-5 is very likely to be energetically limited and only occurs at high temperature due to the large size of the molecule.

  15. An experimental and density functional theory study of the interactions of CH4 with H-ZSM-5

    SciTech Connect

    Khaliullin, Rustam Z.; Bell, Alexis T.; Kazansky, Vladimir B.

    2001-08-25

    The interactions of methane with Bronsted acid sites in H-ZSM-5 were investigated both experimentally and theoretically. Diffuse reflectance infrared spectroscopy was used to acquire spectra for methane adsorbed on H-ZSM-5 at room temperature and at 77 K. Upon adsorption, the v1 and v3 vibrational bands of methane shift by -15 and -23 cm-1, respectively, and the vibrational band for OH groups associated with Bronsted acid sites shifts by -93 cm-1. Quantum chemical calculations conducted at the DFT level of theory with a 6-31g**++ basis set show that the observed shifts for methane are attributable to the effects of the electrostatic field created by the atoms of the zeolite. To represent the influence of the zeolite on the adsorbed methane correctly, it is essential to take into account the effects of the Madelung field, as well as the local effects of the acid center. The calculated shift in the vibrational frequency of the bridging OH group lies within the range observed experimentally. However, the quantitative agreement of the calculated and observed shift is not as good as that seen for the bands of CH4.

  16. Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO2/HZSM-5 catalysts.

    PubMed

    Jiang, Liying; Nie, Guofeng; Zhu, Runye; Wang, Jiade; Chen, Jianmeng; Mao, Yubo; Cheng, Zhuowei; Anderson, Willam A

    2017-05-01

    Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5 catalysts. The performance of catalysts was evaluated in terms of removal and energy efficiency. The decomposition products of chlorobenzene were analyzed. The results show that CeO2/HZSM-5 exhibited a good catalytic activity, which resulted in enhancements of chlorobenzene removal, energy efficiency, and the formation of lower amounts of by-products. With regards to CO2 selectivity, the presence of catalysts favors the oxidation of by-products, leading to a higher CO2 selectivity. With respect to ozone, which is considered as an unavoidable by-product in air plasma reactors, a noticeable decrease in its concentration was observed in the presence of catalysts. Furthermore, the stability of the catalyst was investigated by analyzing the evolution of conversion in time. The experiment results indicated that CeO2/HZSM-5 catalysts have excellent stability: chlorobenzene conversion only decreased from 78% to 60% after 75hr, which means that the CeO2/HZSM-5 suffered a slight deactivation. Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses of the catalyst before and after the reaction, revealing the cause of catalyst deactivation. Copyright © 2016. Published by Elsevier B.V.

  17. Origin of carbon in aromatic and olefin products derived from HZSM-5 catalyzed co-pyrolysis of cellulose and plastics via isotopic labeling

    USDA-ARS?s Scientific Manuscript database

    Catalytic pyrolysis over HZSM-5 is an effective method for the conversion of biomass to aromatic hydrocarbons, albeit with low yield and short catalyst lifetimes. Addition of co-reactants rich in carbon and hydrogen can enhance yield and possibly increase catalyst lifetimes by reducing coke formati...

  18. Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst.

    PubMed

    Liu, Shiyu; Xie, Qinglong; Zhang, Bo; Cheng, Yanling; Liu, Yuhuan; Chen, Paul; Ruan, Roger

    2016-03-01

    This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2.

  19. Catalytic Oxidation of Chlorobenzene over MnxCe1-xO2/HZSM-5 Catalysts: A Study with Practical Implications.

    PubMed

    Weng, Xiaole; Sun, Pengfei; Long, Yu; Meng, Qingjie; Wu, Zhongbiao

    2017-07-18

    Industrial-use catalysts usually encounter severe deactivation after long-term operation for catalytic oxidation of chlorinate volatile organic compounds (CVOCs), which becomes a "bottleneck" for large-scale application of catalytic combustion technology. In this work, typical acidic solid-supported catalysts of MnxCe1-xO2/HZSM-5 were investigated for the catalytic oxidation of chlorobenzene (CB). The activation energy (Ea), Brønsted and Lewis acidities, CB adsorption and activation behaviors, long-term stabilities, and surficial accumulation compounds (after aging) were studied using a range of analytical techniques, including XPS, H2-TPR, pyridine-IR, DRIFT, and O2-TP-Ms. Experimental results revealed that the Brønsted/Lewis (B/L) ratio of MnxCe1-xO2/HZSM-5 catalysts could be adjusted by ion exchange of H• (in HZSM-5) with Mn(n+) (where the exchange with Ce(4+) did not distinctly affect the acidity); the long-term aged catalysts could accumulate ca. 14 organic compounds at surface, including highly toxic tetrachloromethane, trichloroethylene, tetrachloroethylene, o-dichlorobenzene, etc.; high humid operational environment could ensure a stable performance for MnxCe1-xO2/HZSM-5 catalysts; this was due to the effective removal of Cl• and coke accumulations by H2O washing, and the distinct increase of Lewis acidity by the interaction of H2O with HZSM-5. This work gives an in-depth view into the CB oxidation over acidic solid-supported catalysts and could provide practical guidelines for the rational design of reliable catalysts for industrial applications.

  20. Fe-containing phases in hydrated cements

    SciTech Connect

    Dilnesa, B.Z.; Wieland, E.; Lothenbach, B.; Dähn, R.; Scrivener, K.L.

    2014-04-01

    In this study synchrotron X-ray absorption spectroscopy (XAS) has been applied, an element specific technique which allows Fe-containing phases to be identified in the complex mineral mixture of hydrated cements. Several Fe species contributed to the overall Fe K-edge spectra recorded on the cement samples. In the early stage of cement hydration ferrite was the dominant Fe-containing mineral. Ferrihydrite was detected during the first hours of the hydration process. After 1 day the formation of Al- and Fe-siliceous hydrogarnet was observed, while the amount of ferrihydrite decreased. The latter finding agrees with thermodynamic modeling, which predicts the formation of Fe-siliceous hydrogarnet in Portland cement systems. The presence of Al- and Fe-containing siliceous hydrogarnet was further substantiated in the residue of hydrated cement by performing a selective dissolution procedure. - Highlights: • Fe bound to ferrihydrite at early age hydration • Fe found to be stable in siliceous hydrogarnet at longer term age hydration • Fe-containing AFt and AFm phases are less stable than siliceous hydrogarnet. • The study demonstrates EXAFS used to identify amorphous or poorly crystalline phases.

  1. Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5

    DOE PAGES

    Alexopoulos, Konstantinos; Lee, Mal -Soon; Liu, Yue; ...

    2016-03-21

    Here, to account for thermal and entropic effects caused by the dynamics of the motion of the reaction intermediates, ethanol adsorption on the Brønsted acid site of the H-ZSM-5 catalyst has been studied at different temperatures and ethanol loadings using ab initio molecular dynamics (AIMD) simulations, infrared (IR) spectroscopy and calorimetric measurements. At low temperatures (T ≤ 400 K) and ethanol loading, a single ethanol molecule adsorbed in H-ZSM-5 forms a Zundel-like structure where the proton is equally shared between the oxygen of the zeolite and the oxygen of the alcohol. At higher ethanol loading, a second ethanol molecule helpsmore » to stabilize the protonated ethanol at all temperatures by acting as a solvating agent. The vibrational density of states (VDOS), as calculated from the AIMD simulations, are in excellent agreement with measured IR spectra for C2H5OH, C2H5OD and C2D5OH isotopomers and support the existence of both monomers and dimers. A quasi-harmonic approximation (QHA), applied to the VDOS obtained from the AIMD simulations, provides estimates of adsorption free energy within ~10 kJ/mol of the experimentally determined quantities, whereas the traditional approach, employing harmonic frequencies from a single ground state minimum, strongly overestimates the adsorption free energy by at least ~30 kJ/mol. This discrepancy is traced back to the inability of the harmonic approximation to represent the contributions to the vibrational motions of the ethanol molecule upon confinement in the zeolite. KA, MFR, GBM were supported by the Long Term Structural Methusalem Funding by the Flemish Government – grant number BOF09/01M00409. MSL, VAG, RR and JAL were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL, the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory and the Stevin Supercomputer Infrastructure at Ghent University.« less

  2. Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5

    SciTech Connect

    Alexopoulos, Konstantinos; Lee, Mal -Soon; Liu, Yue; Zhi, Yuchun; Liu, Yuanshuai; Reyniers, Marie -Francoise; Marin, Guy B.; Glezakou, Vassiliki -Alexandra; Rousseau, Roger; Lercher, Johannes A.

    2016-03-21

    Here, to account for thermal and entropic effects caused by the dynamics of the motion of the reaction intermediates, ethanol adsorption on the Brønsted acid site of the H-ZSM-5 catalyst has been studied at different temperatures and ethanol loadings using ab initio molecular dynamics (AIMD) simulations, infrared (IR) spectroscopy and calorimetric measurements. At low temperatures (T ≤ 400 K) and ethanol loading, a single ethanol molecule adsorbed in H-ZSM-5 forms a Zundel-like structure where the proton is equally shared between the oxygen of the zeolite and the oxygen of the alcohol. At higher ethanol loading, a second ethanol molecule helps to stabilize the protonated ethanol at all temperatures by acting as a solvating agent. The vibrational density of states (VDOS), as calculated from the AIMD simulations, are in excellent agreement with measured IR spectra for C2H5OH, C2H5OD and C2D5OH isotopomers and support the existence of both monomers and dimers. A quasi-harmonic approximation (QHA), applied to the VDOS obtained from the AIMD simulations, provides estimates of adsorption free energy within ~10 kJ/mol of the experimentally determined quantities, whereas the traditional approach, employing harmonic frequencies from a single ground state minimum, strongly overestimates the adsorption free energy by at least ~30 kJ/mol. This discrepancy is traced back to the inability of the harmonic approximation to represent the contributions to the vibrational motions of the ethanol molecule upon confinement in the zeolite. KA, MFR, GBM were supported by the Long Term Structural Methusalem Funding by the Flemish Government – grant number BOF09/01M00409. MSL, VAG, RR and JAL were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL, the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory and the Stevin Supercomputer Infrastructure at Ghent University.

  3. Photobioreactor cultivation and catalytic pyrolysis of the microalga Desmodesmus communis (Chlorophyceae) for hydrocarbons production by HZSM-5 zeolite cracking.

    PubMed

    Conti, Roberto; Pezzolesi, Laura; Pistocchi, Rossella; Torri, Cristian; Massoli, Patrizio; Fabbri, Daniele

    2016-12-01

    The study evaluated the growth of Desmodesmus communis on column photobioreactor and its thermochemical treatment by catalytic pyrolysis using HZSM-5 zeolite. D. communis showed good results in terms of growth (0.05gL(-1)d(-1)). Analytical pyrolysis of original algae and derived bio-oil mixed with zeolite was used as a screening method in order to gather information on the cracking process. Preparative pyrolysis on bench scale reactor was performed on algae biomass over a zeolite bed at 1:10 ratio (wt/wt). Py-GC-MS of biomass/catalyst mixture showed that the denitrogenation/deoxygenation increased with increasing zeolite load from 1:5 to 1:20 ratio and became significant at 1:10 ratio. The composition observed by analytical pyrolysis was featured by the predominance of alkylated monoaromatic hydrocarbons. The scaling-up to bench scale confirmed the results obtained with analytical pyrolysis in terms of monoaromatic hydrocarbons. However, low yield of catalytic oil (8% by weight) was observed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Catalytic fast pyrolysis of mushroom waste to upgraded bio-oil products via pre-coked modified HZSM-5 catalyst.

    PubMed

    Wang, Jia; Zhong, Zhaoping; Ding, Kuan; Xue, Zeyu

    2016-07-01

    In this paper, HZSM-5 catalyst was modified by pre-coked to cover the strong external acid sites by methanol to olefins reaction, and the modified catalysts were then applied to conduct the catalyst fast pyrolysis of mushroom waste for upgraded bio-fuel production. Experiment results showed that the strong external acid sites and specific surface area decreased with pre-coked percentage increasing from 0% to 5.4%. Carbon yields of hydrocarbons increased at first and then decreased with a maximum value of 53.47%. While the obtained oxygenates presented an opposite variation tendency, and the minimum values could be reached when pre-coked percentage was 2.7%. Among the achieved hydrocarbons, toluene and p-xylene were found to be the main products, and the selectivity of p-xylene increased at first and then decreased with a maximum value of 34.22% when the pre-coked percentage was 1.3%, and the selectivity of toluene showed the opposite tendency with a minimum value of 25.47%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Ethanol Conversion to Hydrocarbons on HZSM-5: Effect of Reaction Conditions and Si/Al Ratio on the Product Distributions

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2014-11-17

    The Conversion of ethanol to hydrocarbon over HZSM-5 zeolite with different Si/Al ratios was investigated under various reaction conditions. The catalyst with a higher Si/Al ratio (low acid density) deactivated faster and generated more unsaturated compounds at a similar time-on-stream. Temperature affects the catalytic activity with respect to liquid hydrocarbon generation and the hydrocarbon product composition. At lower temperatures (~300°C), the catalyst deactivated faster with respect to the liquid hydrocarbon formation. Higher temperatures (~400°C) reduced the formation of liquid range hydrocarbons and formed more gaseous fractions. Weight hourly space velocity was also found to affect product selectivity with higher weight hourly space velocity leading to a higher extent of ethylene formation. The experimental results were analyzed in terms of the product composition and the coke content with respect to catalyst time-on-stream and compared with the catalyst lifetime with respect to the variables tested on the conversion of ethanol to hydrocarbon.

  6. Investigation of the catalytic pyrolysis of high-density polyethylene over a HZSM-5 catalyst in a laboratory fluidized-bed reactor

    SciTech Connect

    Sharratt, P.N.; Lin, Y.H.; Garforth, A.A.; Dwyer, J.

    1997-12-01

    High-density polyethylene (HDPE) was pyrolyzed over HZSM-5 catalyst using a specially developed laboratory fluidized-bed reactor operating isothermally at ambient pressure. The influence of reaction conditions including temperature, ratios of HDPE to catalyst feed, and flow rates of fluidizing gas was examined. The sodium form of siliceous ZSM-5, silicalite, containing very few or no catalytically active sites, gave very low conversions of polymer to volatile hydrocarbons compared with HZSM-5 gave good yields of volatile hydrocarbons with differing selectivities in the final products dependent on reaction conditions. Catalytic pyrolysis of HDPE performed in the fluidized-bed reactor was shown to produce valuable hydrocarbons in the range of C{sub 3}-C{sub 5} carbon number with a high olefinic content. The production of olefins with potential value as a chemical feedstock is potentially attractive and may offer greater profitability than production of saturated hydrocarbons and aromatics.

  7. Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5

    PubMed Central

    Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

    2016-01-01

    We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example. PMID:27585356

  8. Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

    PubMed

    Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

    2016-08-25

    We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

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

    PubMed Central

    2015-01-01

    Optimizing the number, distribution, and accessibility of Brønsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by ensemble-averaging characterization methods. In this work, a detailed 3D single molecule, single turnover sensitive fluorescence microscopy study is presented to quantify the reactivity of Brønsted acid sites in zeolite H-ZSM-5 crystals upon steaming. This approach, in combination with the oligomerization of furfuryl alcohol as a probe reaction, allowed the stochastic behavior of single catalytic turnovers and temporally resolved turnover frequencies of zeolite domains smaller than the diffraction limited resolution to be investigated with great precision. It was found that the single turnover kinetics of the parent zeolite crystal proceeds with significant spatial differences in turnover frequencies on the nanoscale and noncorrelated temporal fluctuations. Mild steaming of zeolite H-ZSM-5 crystals at 500 °C led to an enhanced surface reactivity, with up to 4 times higher local turnover rates than those of the parent H-ZSM-5 crystals, and revealed remarkable heterogeneities in surface reactivity. In strong contrast, severe steaming at 700 °C significantly dealuminated the zeolite H-ZSM-5 material, leading to a 460 times lower turnover rate. The differences in measured turnover activities are explained by changes in the 3D aluminum distribution due to migration of extraframework Al-species and their subsequent effect on pore accessibility, as corroborated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) sputter depth profiling data. PMID:25867455

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

    PubMed

    Ristanović, Zoran; Hofmann, Jan P; De Cremer, Gert; Kubarev, Alexey V; Rohnke, Marcus; Meirer, Florian; Hofkens, Johan; Roeffaers, Maarten B J; Weckhuysen, Bert M

    2015-05-27

    Optimizing the number, distribution, and accessibility of Brønsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by ensemble-averaging characterization methods. In this work, a detailed 3D single molecule, single turnover sensitive fluorescence microscopy study is presented to quantify the reactivity of Brønsted acid sites in zeolite H-ZSM-5 crystals upon steaming. This approach, in combination with the oligomerization of furfuryl alcohol as a probe reaction, allowed the stochastic behavior of single catalytic turnovers and temporally resolved turnover frequencies of zeolite domains smaller than the diffraction limited resolution to be investigated with great precision. It was found that the single turnover kinetics of the parent zeolite crystal proceeds with significant spatial differences in turnover frequencies on the nanoscale and noncorrelated temporal fluctuations. Mild steaming of zeolite H-ZSM-5 crystals at 500 °C led to an enhanced surface reactivity, with up to 4 times higher local turnover rates than those of the parent H-ZSM-5 crystals, and revealed remarkable heterogeneities in surface reactivity. In strong contrast, severe steaming at 700 °C significantly dealuminated the zeolite H-ZSM-5 material, leading to a 460 times lower turnover rate. The differences in measured turnover activities are explained by changes in the 3D aluminum distribution due to migration of extraframework Al-species and their subsequent effect on pore accessibility, as corroborated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) sputter depth profiling data.

  11. Multifaceted effects of HZSM-5 (Proton-exchanged Zeolite Socony Mobil-5) on catalytic cracking of pinewood pyrolysis vapor in a two-stage fixed bed reactor.

    PubMed

    Wang, Yimeng; Wang, Jie

    2016-08-01

    The pinewood was pyrolyzed in the first reactor at a heating rate of 10°Cmin(-1) from room temperature to 700°C, and the vapor was allowed to be cracked through the second reactor in a temperature range of 450-750°C without and with HZSM-5. Attempts were made to determine a wide spectrum of gaseous and liquid products, as well as the mass and element partitions to gas, water, bio-oil, coke and char. HZSM-5 showed a preferential deoxygenation effect via the facilitated decarbonylation and decarboxylation with the inhibited dehydration at 550-600°C. This catalyst also displayed a high selectivity for the formations of aromatic hydrocarbons and olefins by the promoted hydrogen transfer to these products at 550-600°C. The bio-oil produced with HZSM-5 at 500-600°C had the yields of 14.5-16.8%, the high heat values of 39.1-42.4MJkg(-1), and the energy recoveries of 33-35% (all dry biomass basis).

  12. Preparation of HZSM-5 membrane packed CuO-ZnO-Al2O3 nanoparticles for catalysing carbon dioxide hydrogenation to dimethyl ether

    NASA Astrophysics Data System (ADS)

    Liu, Rong; Tian, Haifeng; Yang, Aimei; Zha, Fei; Ding, Jian; Chang, Yue

    2015-08-01

    Spherical carbons were prepared successfully from aqueous glucose using hydrothermal method. After covered with aqueous Cu2+, Zn2+ and Al3+ ions during the co-precipitation treatment, carbons were removed via calcination to yield CuO-ZnO-Al2O3 nanoparticles. HZSM-5 membrane, which was synthesized using tetrapropylammonium hydroxide as templating agent, was packed onto CuO-ZnO-Al2O3 nanoparticles hydrothermally to form HZSM-5 packed CuO-ZnO-Al2O3 nanoparticles. It was characterized by the method of X-ray powder diffraction (XRD), scanning electronic microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen sorption measurement. HZSM-5 packed CuO-ZnO-Al2O3 nanoparticles were used as catalysts for the CO2 hydrogenation to dimethyl ether. The catalyst activity was investigated in a fixed-bed reactor. Under the reaction conditions of pressure at 3.0 MPa, space velocity (SV) of 1800 mL gcat-1 h-1, volume ratio of CO2/H2 to 1:3 and temperature at 270 °C, the conversion of CO2 could reach to 48.3%, with a dimethyl ether yield and selectivity of 23.4% and 48.5%, respectively.

  13. Quantum chemical modeling of benzene ethylation over H-ZSM-5 approaching chemical accuracy: a hybrid MP2:DFT study.

    PubMed

    Hansen, Niels; Kerber, Torsten; Sauer, Joachim; Bell, Alexis T; Keil, Frerich J

    2010-08-25

    The alkylation of benzene by ethene over H-ZSM-5 is analyzed by means of a hybrid MP2:DFT scheme. Density functional calculations applying periodic boundary conditions (PBE functional) are combined with MP2 energy calculations on a series of cluster models of increasing size which allows extrapolation to the periodic MP2 limit. Basis set truncation errors are estimated by extrapolation of the MP2 energy to the complete basis set limit. Contributions from higher-order correlation effects are accounted for by CCSD(T) coupled cluster calculations. The sum of all contributions provides the "final estimates" for adsorption energies and energy barriers. Dispersion contributes significantly to the potential energy surface. As a result, the MP2:DFT potential energy profile is shifted downward compared to the PBE profile. More importantly, this shift is not the same for reactants and transition structures due to different self-interaction correction errors. The final enthalpies for ethene, benzene, and ethylbenzene adsorption on the Brønsted acid site at 298 K are -46, -78, and -110 kJ/mol, respectively. The intrinsic enthalpy barriers at 653 K are 117 and 119/94 kJ/mol for the one- and two-step alkylation, respectively. Intrinsic rate coefficients calculated by means of transition state theory are converted to apparent Arrhenius parameters by means of the multicomponent adsorption equilibrium. The simulated apparent activation energy (66 kJ/mol) agrees with experimental data (58-76 kJ/mol) within the uncertainty limit of the calculations. Adsorption energies obtained by adding a damped dispersion term to the PBE energies (PBE+D), agree within +/-7 kJ/mol, with the "final estimates", except for physisorption (pi-complex formation) and chemisorption of ethene (ethoxide formation) for which the PBE+D energies are 12.4 and 26.0 kJ/mol, respectively larger than the "final estimates". For intrinsic energy barriers, the PBE+D approach does not improve pure PBE results.

  14. Core-shell H-ZSM-5/silicalite-1 composites: Brønsted acidity and catalyst deactivation at the individual particle level.

    PubMed

    Mores, Davide; Stavitski, Eli; Verkleij, Suzanna P; Lombard, Antoinette; Cabiac, Amandine; Rouleau, Loïc; Patarin, Joël; Simon-Masseron, Angélique; Weckhuysen, Bert M

    2011-09-21

    A combination of in situ UV-Vis and confocal fluorescence micro-spectroscopy is applied to investigate the influence of an external silicalite-1 shell on the Brønsted acidity and coke formation process of individual H-ZSM-5 zeolite crystals. Three probe reactions were used: oligomerization of styrene, methanol-to-olefin (MTO) conversion and aromatization of light naphtha (LNA) derivatives. Oligomerization of styrene leads to the formation of optically active carbocationic oligomers. Different styrene substitutions indicate the conversion ability of the catalyst acid core, a preferred alignment of the oligomers within the straight zeolite channels and a Brønsted acidity gradient throughout the zeolite crystal. Both the MTO conversion and the LNA process lead to limited carbonaceous deposition within the external silicalite-1 layer. This outer shell furthermore prevents the growth of extended coke species at the zeolite external surface. During MTO, the formation of carbonaceous compounds initiates at the center of the H-ZSM-5 zeolite core and expands towards the zeolite exterior. This coke build-up starts with a 420 nm UV-Vis absorption band, assigned to methyl-substituted aromatic carbocations, and a second band around 550 nm, which is indicative of their growth towards larger conjugated systems. Aromatization of linear and branched C5 paraffins causes negligible darkening of the zeolite crystals though it forms fluorescent coke deposits and their precursors within the H-ZSM-5 catalyst. Olefin homologues on the contrary cause pronounced darkening of the zeolite composite. Methyl-branching of these reactants slows down the coke formation rate and produces carbonaceous species that are more restricted in their molecular size.

  15. A density functional study on the effect of the zeolite cavity on its catalytic activity: The dehydrogenation and cracking reactions of isobutane over HZSM-5 and HY zeolites

    NASA Astrophysics Data System (ADS)

    Milas, Ivan; Chaer Nascimento, Marco Antonio

    2006-02-01

    The dehydrogenation and cracking reactions of isobutane over HZMS-5 and HY were studied at the DFT level of calculation to verify the influence of the cavity on the energetics and mechanism of the reactions. The zeolites were represented by the 20T and 32T clusters, respectively. The results indicate that the reactions follow the same mechanism in both zeolites but the activation energies are reduced by ˜10 kcal/mol relative to the values with smaller clusters. Activation energies for the dehydrogenation reactions were similar in both zeolites, but for the cracking reaction in HY, the activation energy is ˜5 kcal/mol higher than in HZSM-5.

  16. Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst.

    PubMed

    Zhang, Bo; Zhong, Zhaoping; Xie, Qinglong; Liu, Shiyu; Ruan, Roger

    2016-07-01

    A novel technology of two-step fast microwave-assisted pyrolysis (fMAP) of corn stover for bio-oil production was investigated in the presence of microwave absorbent (SiC) and HZSM-5 catalyst. Effects of fMAP temperature and catalyst-to-biomass ratio on bio-oil yield and chemical components were examined. The results showed that this technology, employing microwave, microwave absorbent and HZSM-5 catalyst, was effective and promising for biomass fast pyrolysis. The fMAP temperature of 500°C was considered the optimum condition for maximum yield and best quality of bio-oil. Besides, the bio-oil yield decreased linearly and the chemical components in bio-oil were improved sequentially with the increase of catalyst-to-biomass ratio from 1:100 to 1:20. The elemental compositions of bio-char were also determined. Additionally, compared to one-step fMAP process, two-step fMAP could promote the bio-oil quality with a smaller catalyst-to-biomass ratio.

  17. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    SciTech Connect

    Liu, Cong; Evans, Tabitha J.; Cheng, Lei; Nimlos, Mark R.; Mukarakate, Calvin; Robichaud, David J.; Assary, Rajeev S.; Curtiss, Larry A.

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  18. Theoretical insights into the mechanism of olefin elimination in the methanol-to-olefin process over HZSM-5, HMOR, HBEA, and HMCM-22 zeolites.

    PubMed

    Wang, Sen; Chen, Yanyan; Wei, Zhihong; Qin, Zhangfeng; Chen, Jialing; Ma, Hong; Dong, Mei; Li, Junfen; Fan, Weibin; Wang, Jianguo

    2014-10-02

    The mechanism of olefin elimination in the process of methanol-to-olefins (MTO) over a series of zeolites like HZSM-5, HMOR, HBEA, and HMCM-22 was investigated by DFT-D calculations, which is a crucial step that controls the MTO product distribution. The results demonstrate that the manners of olefin elimination are related to the pore structure of zeolite catalyst and the interaction between proton transfer reagent (water or methanol) and zeolite acidic framework. The indirect spiro mechanism is preferable to the direct mechanism over HMOR, HBEA, and HMCM-22 zeolites with large pores, as suggested by the energy barrier of rate-determining step and the potential energy surface (PES), but is unfavorable over HZSM-5 with medium-sized pores due to the steric hindrance of spiro intermediates. Over various zeolites, water and methanol perform differently in proton transfer to form the spiro intermediates; over HMOR and HBEA with strong acidity, water is superior to methanol in promoting propene elimination, whereas over HMCM-22 with relatively weaker acidity, methanol is more favorable as a proton transfer reagent.

  19. Toward a reliable computational description of hydrocarbon activation in zeolites : a study of cracking, dehydrogenation, and H/D Exchange of alkanes in H-ZSM-5.

    SciTech Connect

    Zygmunt, S. A.; Bootz, B. L.; Miller, A. W.; Curtiss, L. A.; Iton, L. E.

    2000-11-01

    During the past decade, quantum-chemical calculations have been used to model hydrocarbon reactions in zeolite acid catalysts. In the interest of computational feasibility, the zeolite has often been represented by a very small cluster model, at times including only one tetrahedrally-coordinated atom (a 1T cluster). The results of such calculations have given important qualitative insights such as possible reaction pathways and transition state geometries, but the calculated activation energies for hydrocarbon reactions have usually been 50 percent or more higher than experimental values. In our recent work we developed a methodology of quantum-chemical techniques and corrections that allowed us to calculate a quantitatively accurate activation energy for protolytic cracking of ethane in H-ZSM-5 [1]. In order to test the limits of our computational method, we have carried out a study of protolytic cracking, dehydrogenation, and H/D exchange of the n-alkanes ethane, propane, and butane using a cluster model of H-ZSM-5. Our goal is to study the dependence of the activation energy on the alkane chain length in these reactions and to determine whether this method can produce results in quantitative agreement with available experimental results [2-5].

  20. Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene with HZSM-5 and MgO for improved bio-oil yield and quality.

    PubMed

    Fan, Liangliang; Chen, Paul; Zhang, Yaning; Liu, Shiyu; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Ruan, Roger

    2017-02-01

    Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene (LDPE) with HZSM-5 and MgO was investigated. Effects of pyrolysis temperature, lignin to LDPE ratio, MgO to HZSM-5 ratio, and feedstock to catalyst ratio on the products yields and chemical profiles were examined. 500°C was the optimal co-pyrolysis temperature in terms of the maximum bio-oil yield. The proportion of aromatics increased with increasing LDPE content. In addition, with the addition of LDPE (lignin/LDPE=1/2), methoxyl group in the phenols was completely removed. A synergistic effect was found between lignin and LDPE. The proportion of aromatics increased and alkylated phenols decreased with increasing HZSM-5 to MgO ratio. The bio-oil yield increased with the addition of appropriate amount of catalyst and the proportion of alkylated phenols increased with increasing catalyst to feedstock ratio.

  1. Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

    PubMed Central

    Nordvang, Emily C; Borodina, Elena; Ruiz-Martínez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M

    2015-01-01

    The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results. PMID:26463581

  2. Sandwich-like PdO/CeO2 nanosheet@HZSM-5 membrane hybrid composite for methane combustion: self-redispersion, sintering-resistance and oxygen, water-tolerance

    NASA Astrophysics Data System (ADS)

    Dai, Qiguang; Bai, Shuxing; Lou, Yang; Wang, Xingyi; Guo, Yun; Lu, Guanzhong

    2016-05-01

    PdO/CeO2 nanosheets encapsulated by a monolayer of a continuous and dense HZSM-5 zeolite membrane were prepared by a facile in situ hydrothermal growth process and used as a highly efficient and thermally stable catalyst for methane combustion. Uncoated PdO/CeO2 suffered severe sintering at high temperature or high oxygen concentration. However, the encapsulation of HZSM-5 significantly improved sintering resistance by the suppressing effects of the HZSM-5 coating for the agglomeration of PdOx nanoparticles, resulting in the outstanding thermal stability of PdO/CeO2. Furthermore, the synthesized hybrid materials also exhibited good oxygen- and water-tolerance for methane combustion due to the oxygen or water barrier. In addition, a reactivation behavior was observed due to the self-redispersion of PdOx on CeO2 nanosheets in the reaction atmosphere at high temperature.PdO/CeO2 nanosheets encapsulated by a monolayer of a continuous and dense HZSM-5 zeolite membrane were prepared by a facile in situ hydrothermal growth process and used as a highly efficient and thermally stable catalyst for methane combustion. Uncoated PdO/CeO2 suffered severe sintering at high temperature or high oxygen concentration. However, the encapsulation of HZSM-5 significantly improved sintering resistance by the suppressing effects of the HZSM-5 coating for the agglomeration of PdOx nanoparticles, resulting in the outstanding thermal stability of PdO/CeO2. Furthermore, the synthesized hybrid materials also exhibited good oxygen- and water-tolerance for methane combustion due to the oxygen or water barrier. In addition, a reactivation behavior was observed due to the self-redispersion of PdOx on CeO2 nanosheets in the reaction atmosphere at high temperature. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01800a

  3. Methanol conversion to hydrocarbons over zeolite H-ZSM-5: Investigation of the role of CO and ketene in the formation of the initial C-C bond

    SciTech Connect

    Hutchings, G.J.; Johnston, P. ); Hunter, R. ); Van Rensburg, L.J. )

    1993-08-01

    Mechanistic studies concerning the formation of the initial carbon-carbon bond in the methanol conversion reaction over zeolite H-ZSM-5 are described and discussed. In particular, the possible roles of CO as a reaction intermediate or as a catalyst, via the formation of ketene, are evaluated. Experiments using [sup 13]CH[sub 3]OH/[sup 12]CO reactant mixtures demonstrate that no CO is incorporated into ethene, the primary product of this reaction. In addition, CO is found to have no significant effect on the induction period for this reaction. Model experiments for the methylation of ketene by reaction with Me[sub 2]SO[sub 4] and Me[sub 3]O[sup +]SbCl[sub 6][sup [minus

  4. In situ (1)H and (13)C MAS NMR kinetic study of the mechanism of H/D exchange for propane on zeolite H-ZSM-5.

    PubMed

    Arzumanov, Sergei S; Reshetnikov, Sergei I; Stepanov, Alexander G; Parmon, Valentin N; Freude, Dieter

    2005-10-27

    The kinetics of hydrogen (H/D) exchange between Brønsted acid sites of zeolite H-ZSM-5 and variously deuterated propanes (propane-d(8), propane-1,1,1,3,3,3-d(6), propane-2,2-d(2)) have been monitored in situ by (1)H MAS NMR spectroscopy within the temperature range of 503-556 K. The contribution of intramolecular hydrogen transfer to the H/D exchange in the adsorbed propane was estimated by monitoring the kinetics of (13)C-labeled carbon scrambling in propane-2-(13)C in situ with (13)C MAS NMR at 543-573 K. Possible mechanisms of the exchange have been verified on the basis of the analysis of the variation of protium concentration in both the methyl and the methylene groups of propane in dependence of the reaction time. The main route of the exchange consists of a direct exchange of the acidic OH groups of the zeolite with either the methyl groups or the methylene group presumably with a pentacoordinated carbonium ion intermediate. The assumption that the intramolecular H scrambling between the methyl groups and the methylene group of propane via carbenium-ion-type intermediates is the fastest process among the other possible routes does not account for the experimental kinetics of H/D exchange for propanes with different initial contents and locations of deuterium in a propane molecule. The rate constant (k(3)) for intramolecular H/D exchange between the methyl and the methylene groups is 4-5 times lower compared to those of the direct exchange of both the methyl (k(1)) and the methylene (k(2)) groups with Brønsted acid sites of the zeolite, the k(1) being ca. 1.5 times higher than k(2). At lower temperature (473 K), the exchange is slower, and the expected difference between k(1) and k(2) is more essential, k(1) = 3k(2). This accounts for earlier observed regioselectivity of the exchange for propane on H-ZSM-5 at 473 K. Faster direct exchange with the methyl groups compared to that with the methylene groups was attributed to a possible, more spatial accessibility of the methyl groups for the exchange. Similar activation energies for H and C scramblings with a 2 times more rapid rate of H scrambling was rationalization by the proceeding of these two processes through an isopropyl cation intermediate, as in classical carbenium ion chemistry.

  5. Formation of hydrocarbon compounds during the hydrocracking of non-edible vegetable oils with cobalt-nickel supported on hierarchical HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Marlinda, L.; Al-Muttaqii, M.; Roesyadi, A.; Prajitno, D. H.

    2017-05-01

    The hierarchical Co-Ni/HZSM-5 catalyst with hierarchical pore structure was prepared by desilication and incipient wetness impregnation. Hydrocracking of non-edible vegetable oils at temperature of 400 °C, 20±5 bar for 2 h was performed in the presence of this type of catalyst under hydrogen initial pressure in pressured batch reactor. Non-edible vegetable oils, such as Reutealis trisperma (Blanco) airy shaw (sunan candlenut) and Hevea brasiliensis (rubber seed) were chosen to study the effect of the degree of saturation and lateral chain length on hydrocarbon compounds obtained through hydrocracking. Cerbera manghas oil was also tested for comparison because the composition of fatty acid was different with the other oils The hydrocracking test indicated that liquid product produced has a similar hydrocarbon compounds with petroleum diesel. The most abundant hydrocarbon is pentadecane (n-C15) and heptadecane (n-C17). The high aromatic compounds were found in liquid product produced in hydrocracking of Sunan candlenut oil.

  6. Mechanistic insight into the formation of acetic acid from the direct conversion of methane and carbon dioxide on zinc-modified H-ZSM-5 zeolite.

    PubMed

    Wu, Jian-Feng; Yu, Si-Min; Wang, Wei David; Fan, Yan-Xin; Bai, Shi; Zhang, Chuan-Wei; Gao, Qiang; Huang, Jun; Wang, Wei

    2013-09-11

    Methane and carbon dioxide are known greenhouse gases, and the conversion of these two C1-building blocks into useful fuels and chemicals is a subject of great importance. By solid-state NMR spectroscopy, we found that methane and carbon dioxide can be co-converted on a zinc-modified H-ZSM-5 zeolite (denoted as Zn/H-ZSM-5) to form acetic acid at a low temperature range of 523-773 K. Solid-state (13)C and (1)H MAS NMR investigation indicates that the unique nature of the bifunctional Zn/H-ZSM-5 catalyst is responsible for this highly selective transformation. The zinc sites efficiently activate CH4 to form zinc methyl species (-Zn-CH3), the Zn-C bond of which is further subject to the CO2 insertion to produce surface acetate species (-Zn-OOCCH3). Moreover, the Brønsted acid sites play an important role for the final formation of acetic acid by the proton transfer to the surface acetate species. The results disclosed herein may offer the new possibility for the efficient activation and selective transformation of methane at low temperatures through the co-conversion strategy. Also, the mechanistic understanding of this process will help to the rational design of robust catalytic systems for the practical conversion of greenhouse gases into useful chemicals.

  7. The impact of CrOx loading on reaction behaviors of dichloromethane (DCM) catalytic combustion over Cr-O/HZSM-5 catalysts

    NASA Astrophysics Data System (ADS)

    Su, Jie; Yao, Weiyuan; Liu, Yue; Wu, Zhongbiao

    2017-02-01

    A series of HZSM-5 supported CrOx catalysts at different loadings were prepared by wet impregnation method for catalytic combustion of dichloromethane (DCM) in this paper. The catalytic activity tests indicated that both DCM conversion and product selectivity varied greatly with Cr doping contents. The sample at 2 wt% loading showed the highest DCM conversion, while the selectivity toward CO/CO2 increased at an elevated CrOx loading. The characterization results revealed that the surface acidity and the chemical states of Cr were strongly affected by the doping content. The surface acidity would decline at an elevated Cr loading owing to the interactions between surface OH groups and chromium ions. And higher surface Cr(VI)/Cr(III) ratios could be observed on the catalysts at lower CrOx doping, leading to the improvement of reducibility. The activity and selectivity of DCM catalytic degradation were found to be highly depended on the balance of surface acidity and redox property. The increased surface acidity could result in the enhancement of dissociated adsorption of DCM, which are beneficial to the catalytic activity. However, higher surface acidity meant lower Cr loading, which might lead the adsorbed intermediates incompletely oxidized and the decrease in COx selectivity due to the limit redox ability.

  8. One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

    PubMed

    Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

    2017-01-25

    For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C6-C8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C6-C8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

  9. Ultrasound assisted co-precipitation of nanostructured CuO-ZnO-Al2O3 over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME.

    PubMed

    Allahyari, Somaiyeh; Haghighi, Mohammad; Ebadi, Amanollah; Hosseinzadeh, Shahin

    2014-03-01

    Nanostructured CuO-ZnO-Al2O3/HZSM-5 was synthesized from nitrate and acetate precursors using ultrasound assisted co-precipitation method under different irradiation powers. The CuO-ZnO-Al2O3/HZSM-5 nanocatalysts were characterized using XRD, FESEM, BET, FTIR and EDX Dot-mapping analyses. The results indicated precursor type and irradiation power have significant influences on phase structure, morphology, surface area and functional groups. It was observed that the acetate formulated CuO-ZnO-Al2O3/HZSM-5 nanocatalyst have smaller CuO crystals with better dispersion and stronger interaction between components in comparison to nitrate based nanocatalysts. Ultrasound assisted co-precipitation synthesis method resulted in nanocatalyst with more uniform morphology compared to conventional method and increasing irradiation power yields smaller particles with better dispersion and higher surface area. Additionally the crystallinity of CuO is lower at high irradiation powers leading to stronger interaction between metal oxides. The nanocatalysts performance were tested at 200-300 °C, 10-40 bar and space velocity of 18,000-36,000 cm(3)/g h with the inlet gas composition of H2/CO = 2/1 in a stainless steel autoclave reactor. The acetate based nanocatalysts irradiated with higher levels of power exhibited better reactivity in terms of CO conversion and DME yield. While there is an optimal temperature for CO conversion and DME yield in direct synthesis of DME, CO conversion and DME yield both increase with the pressure increase. Furthermore ultrasound assisted co-precipitation method yields more stable CuO-ZnO-Al2O3/HZSM-5 nanocatalyst while conventional precipitated nanocatalyst lost their activity ca. 18% and 58% in terms of CO conversion and DME yield respectively in 24 h time on stream test.

  10. Adsorption and Desorption Behavior of NO on H-ZSM-5, Na-ZSM-5, and Na-A as Studied by EPR

    NASA Astrophysics Data System (ADS)

    Rudolf, Thomas; Böhlmann, Winfried; Pöppl, Andreas

    2002-03-01

    Nitric monoxide probe molecules are used to characterize the Lewis acid properties of sodium cations and aluminum defect centers in various zeolite materials. The adsorption-desorption behavior of NO probe molecules is studied at different temperatures for Na-A, Na-ZSM-5, H-ZSM-5, and silicalite. Adsorbed NO molecules form paramagnetic adsorption complexes with Lewis acid sites which can be examined by EPR transitions (ΔmS±1) at g≈2.0. Otherwise the desorption of NO into the gas phase can be monitored by the typical nine-line EPR spectrum (ΔmJ±1) of the 2Π3/2 state at g≈0.7776. This gas-phase signal is used to study the overall adsorption-desorption properties of the zeolites in the temperature range 150 K≲T≲300 K. At lower temperatures the probe molecules are adsorbed at the Lewis acid sites inside the nanoporous materials and produce an intensive spectrum at T≲110 K. But at intermediate temperatures 110 K≲T≲150 K the NO molecules are adsorbed only for a few hundred picoseconds because the lifetime of the adsorption complexes is limited by the beginning desorption processes. The decreasing lifetime of the adsorption complex with rising temperature results in an increasing homogeneous line broadening of their EPR signals. An analysis of the line-broadening effects provides an opportunity for determining the specific desorption energies EA(H-ZSM-5)=(20.2±7.3) kJ/mol, EA(Na-ZSM-5)=(4.1±1.5) kJ/mol, and EA(Na-A)=(7.1±2.1) kJ/mol for NO probe molecules at sodium cations and aluminum defect centers just below the desorption temperature.

  11. The adsorption of benzene on industrially important nanostructured catalysts (H-BEA, H-ZSM-5, and H-FAU): confinement effects

    NASA Astrophysics Data System (ADS)

    Rungsirisakun, Ratana; Jansang, Bavornpon; Pantu, Piboon; Limtrakul, Jumras

    2005-01-01

    The structure of industrially important zeolitic catalysts (H-BEA, H-ZSM-5, and H-FAU) and their interactions with benzene have been investigated within the framework of our-own-N-layered integrated molecular orbital+molecular mechanics (ONIOM) approach utilizing the three-layer ONIOM scheme (B3LYP/6-31G(d,p):HF/3-21G:UFF). Inclusion of the extended zeolitic framework covering the nanocavity has an effect on adsorption properties and leads to differentiation of different types of zeolite, unlike the small cluster models which are not able to make this differentiation. The ONIOM adsorption energies of benzene on ZSM-5, BEA, and FAU zeolites are -19.23, -16.11, and -15.22 kcal/mol, respectively, which agrees well with the known adsorption trend of these three zeolites. On the other hand, the small cluster models underestimate the adsorption energies and even yield an unreasonable trend of adsorption energies (-8.09, -8.48, and -8.93 kcal/mol for ZSM-5, BEA, and FAU, respectively). With the inclusion of basis set superposition error (BSSE) and the MP2 corrections, the ONIOM3(MP2/6-31G(d,p):HF/3-21G:UFF) adsorption energies are predicted to be -18.96, -16.34, and -15.18 kcal/mol, for ZSM-5, BEA, and FAU, respectively. The last value can be compared well with the experimental data (-15.31 kcal/mol) for benzene adsorption on a FAU zeolite. The results derived in this study suggest that the ONIOM3(MP2/6-31G(d,p):HF/3-21G:UFF) scheme provides a more accurate method for investigating the adsorption of aromatic hydrocarbons on these zeolites.

  12. A {sup 13}C NMR study of the condensation chemistry of acetone and acetaldehyde adsorbed at the Bronsted acid sites in H-ZSM-5

    SciTech Connect

    Biaglow, A.I.; Sepa, J.; Gorte, R.J.

    1995-02-01

    Several bimolecular, acid-catalyzed condensation reactions of acetone and acetaldehyde have been examined in H-ZSM-5, along with the adsorption complexes formed by the products, using {sup 13}C NMR. For acetone, the hydrogen-bonded adsorption complex is stable at room temperature and coverages below one molecule per Broensted acid site. Reaction to mesityl oxide occurs only at higher coverages or temperatures, which are necessary to induce site exchange. The adsorption complex exhibits reaction chemistry analogous to that observed in solution phase, forming adsorption complexes of chloroacetone upon exposure to Cl{sub 2} and of imines upon exposure to NH{sub 3} or dimethylamine. The reactions of acetaldehyde to crotonaldehyde and imines are similar, although they occur at a faster rate due to the higher mobility of this molecule. The adsorption complexes formed by acetone, acetaldehyde, and their condensation products can all be described as rigid, hydrogen-bonded complexes at low coverages. Complexes formed from imines and enamines exhibit isotropic chemical shifts nearly identical to those observed in magic acids, indicating that proton transfer is nearly complete for these molecules. The extent of proton transfer for the remaining molecules varies with the proton affinity of the molecule, ranging from close to complete proton transfer for mesityl oxide and crotonaldehyde to almost complete absence of proton transfer for the chloroacetones. The differences and similarities between these reactions in the zeolite and in solution phase are discussed, along with the implications for understanding the primary processes responsible for these reactions in zeolites. 34 refs., 16 figs., 1 tab.

  13. Direct synthesis of dimethyl ether as a green fuel from syngas over nanostructured CuO-ZnO-Al2O3/HZSM-5 catalyst: Influence of irradiation time on nanocatalyst properties and catalytic performance

    NASA Astrophysics Data System (ADS)

    Allahyari, Somaiyeh; Haghighi, Mohammad; Ebadi, Amanollah; Qavam Saeedi, Habib

    2014-12-01

    CuO-ZnO-Al2O3/HZSM-5 (CZAZ) nanocatalyst is prepared by ultrasound-assisted co-precipitation method at different irradiation times, characterized and tested for direct synthesis of DME from syngas. Synthesized nanocatalysts were characterized using XRD, FESEM, PDS, EDX and BET techniques. Direct synthesis of DME is carried out at 200-300 °C and 10-40 bar using a mixture of CO:H2 = 2:1. The catalyst with the longest sonication time showed the smallest degree of aggregates, the highest dispersion and surface area. Although the long irradiated nanocatalyst has slightly bigger CuO crystal size but the size of particle aggregates was small and less populated. The sonicated catalyst with longest irradiation presented a high CO conversion of ca. 40%. It seems that, not the CuO crystal size but the size of particle aggregates and nanocatalyst surface had a great effect on the CZAZ nanocatalyst performance. While there was an optimal temperature for CO conversion and DME yield in direct synthesis of DME, both the CO conversion and the DME yield increased with the pressure increase. Long irradiated nanocatalyst yielded more stable CuO-ZnO-Al2O3/HZSM-5 nanocatalyst while conventional co-precipitated nanocatalyst lost its activity ca. 11% and 58% in terms of CO conversion and DME yield, respectively, in 24 h time on stream test.

  14. A cluster DFT study of NH3 and NO adsorption on the (MoO2)2+/HZSM-5 surface: Lewis versus Brønsted acid sites

    NASA Astrophysics Data System (ADS)

    Yan, Zhifeng; Zuo, Zhijun; Li, Zhe; Zhang, Jinshan

    2014-12-01

    A systematic DFT study was carried out to investigate NH3 and NO adsorption on both Lewis and Brønsted acid sites of (MoO2)2+/HZSM-5 catalyst by using cluster models. The adsorption energy results indicate that NH3 could strongly adsorb on both Lewis and Brønsted acid sites in the form of coordinated NH3 and NH4+, respectively, whereas NO represents poorer adsorption ability. It is also found that Lewis and Brønsted acid sites are competitive energetically for NH3 adsorption. According to the difference in the proposed mechanisms for NH3 adsorption on different acid sites, particular attention has been focused on the first dissociation of coordinated NH3 for Lewis acid site and the effect of Mo site on the introduction of NO for Brønsted acid site. For the coordinated NH3 on Lewis acid site, the more electron donation from NH3 is, the greater its adsorption stability is and the higher active its H atoms are. In addition, DOS results show that stability of the H atoms is enhanced by interacting with framework oxygen and especially the H atoms chemical-bonded with framework oxygen. For the NH4+ on Brønsted acid site, reduced-state Mo5+ holds stronger reducibility and oxidizability than terminal oxygen, which is suggested to play a key role in adsorption and activation of NOx together with the adsorbed NH4+.

  15. Formation of carboxylic acids from alcohols and olefins in zeolite H-ZSM-5 under mild conditions via trapping of alkyl carbenium ions with carbon monoxide: An in situ {sup 13}C solid state NMR study

    SciTech Connect

    Stepanov, A.G.; Luzgin, M.V.; Romannikov, V.N.; Sidelnikov, V.N.; Zamaraev K.I.

    1996-12-01

    Using in situ {sup 13}C solid state MAS NMR (for some reagents in combination with ex situ GC-MS), it is shown that butyl alcohols and olefins (ethene, isobutene, octene-1) undergo carbonylation to form carboxylic acids (the Koch reaction) with high conversion on zeolite H-ZSM-5 at 296-373 K. The reactions proceed without application of pressurized conditions, just upon coadsorption of CO and alcohols or CO, H{sub 2}O, and olefins on zeolite. The observed Koch reaction under mild conditions provides strong evidence for the formation of alkyl carbenium ions from alcohols and olefins on the zeolites as crucial reaction intermediates. Of the family of carbenium ions, CO reacts selectively with tertiary cations to produce tertiary carboxylic acids, unless the carbonylated molecule is too large for more bulky tertiary moieties to be accommodated and carbonylated in the narrow pores of H-ZSM05. Thus, t-BuOH, i-BuOH, and isobutene produce trimethylacetic acid with high selectivity and conversion, while ethene transforms selectively into 2-methyl-2-ethyl butyric acid. Reaction of octene-1 molecules with CO and H{sub 2}O results in acids of the C{sub 8}H{sub 17}COOH and C{sub 16}H{sub 33}COOH families with predominantly linear hydrocarbon chains. The data obtained may open up new possibilities in using solid acids in organic synthesis as carbonylation catalysts under mild conditions i.e., low temperature and normal atmospheric pressure. 55 refs., 8 figs.

  16. Mesoporous carbon materials

    DOEpatents

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

    2014-09-09

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

  17. Production of hydroxyl radicals from Fe-containing fine particles in Guangzhou, China

    NASA Astrophysics Data System (ADS)

    Ma, Shexia; Ren, Ke; Liu, Xiaowen; Chen, Laiguo; Li, Mei; Li, Xiaoying; Yang, Jian; Huang, Bo; Zheng, Mei; Xu, Zhencheng

    2015-12-01

    Reactive oxygen species (ROS) production from ambient fine particles has been correlated with the soluble transition metal content of PM2.5, which also has clear association with particle-mediated cardiopulmonary toxicity. Hydroxyl radical (rad OH) is the most harmful ROS species through chemical reactions of redox-active particle components. Atmospheric Fe, as the dominant species of the transition metals in the atmosphere, is associated with rad OH generation in ambient particle extracts. Our results revealed that Fe-containing particles (18,730 in total number) contributed approximately 3.7% on average to all detected particles throughout the summer and winter sampling period in Guangzhou, which was clustered into four distinct particle classes, including Fe-rich, Metal-rich, NaK-rich and Dust-rich. Fe-rich class was the dominant one with a fraction of 61%, followed by Dust-rich (14%), Metal-rich (13%). and NaK-rich (12%). The iron oxide was enriched in the Fe-rich class. rad OH generation induced by Fe-containing fine particles collected in Guangzhou (GZ) was quantified in a surrogate lung fluid (SLF), and it was found that Fe-containing fine particles were generally much reactive in generating rad OH in the presence of four antioxidants (200 μM ascorbate, 300 μM citrate, 100 μM reduced L-glutathione, and 100 μM uric acid). The annual average rad OH amount produced in our samples was 132.98 ± 27.43 nmol rad OH mg-1 PM2.5. rad OH production had a clear seasonal pattern with higher amount in summer and lower in winter. By measuring the amount of total and SLF-soluble metal in our PM2.5 samples using ICP-MS, we found that ROS activities were associated with the ionizable Fe through Fenton type reactions in the Guangzhou PM2.5. Expected burdens of PM2.5 derived rad OH in human lung lining fluid suggests that typical daily particulate matter exposure in Guangzhou is already a concern, and it could produce much higher levels of rad OH, leading to higher

  18. Multifunctional mesoporous silica catalyst

    DOEpatents

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

    2015-03-31

    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  19. Cluster formula of Fe-containing Monel alloys with high corrosion-resistance

    SciTech Connect

    Li Baozeng; Gu Junjie; Wang Qing; Ji Chunjun; Wang Yingmin; Qiang Jianbing; Dong Chuang

    2012-06-15

    The cluster-plus-glue-atom model is applied in the composition interpretation of Monel alloys. This model considers ideal atomic nearest neighbor configurations among the constituent elements and has been used in understanding compositions of complex alloys like quasicrystals, amorphous alloys, and cupronickels. According to this model, any structure can be expressed by cluster formula [cluster](glue atom){sub x}, x denoting the number of glue atoms matching one cluster. According to this model, two groups of experimental composition series [Fe{sub 1}Ni{sub 12}]Cu{sub x} and [Fe{sub y}Ni{sub 12}]Cu{sub 5} were designed which fell close to conventional Fe-containing Monel alloys. The designed alloys after solution treatment plus water quenching, are monolithic FCC Ni-based solid solutions. Among them, the [Fe{sub 1}Ni{sub 12}]Cu{sub 5} alloy has the highest corrosion resistance in simulated sea water, and its performance is superior to that of industrial Monel 400 alloy. - Highlights: Black-Right-Pointing-Pointer A stable solid solution model is proposed using our 'cluster-plus-glue-atom model'. Black-Right-Pointing-Pointer This model is used to develop Monel corrosion resistant alloys. Black-Right-Pointing-Pointer Single FCC structure is easily retained. Black-Right-Pointing-Pointer The alloys show good corrosion properties. Black-Right-Pointing-Pointer This work contributes to the general understanding of engineering alloys.

  20. Evaporation Mechanism of Cu from Liquid Fe Containing C and S

    NASA Astrophysics Data System (ADS)

    Jung, Sung-Hoon; Kang, Youn-Bae

    2016-08-01

    A number of liquid-gas experiments were carried out in order to elucidate evaporation mechanism of Cu from liquid Fe containing C and S. Rate of Cu evaporation in liquid Fe droplets at 1873 K (1600 °C) was determined using electromagnetic levitation equipment. Evaporation rate of the Cu under various conditions (flow rate of gas mixtures, initial C, and S concentrations) was examined. It was found from a series of kinetic analyses of the experimental data that Cu evaporates in forms of Cu(g) and CuS(g). As was reported for the Sn evaporation from liquid iron (Jung et al. Met. Mater. Trans. 46B, 250-258, 2014), S plays two roles for the evaporation of Cu: accelerating the rate by forming CuS(g) and decelerating the rate by blocking evaporation sites. As a result of these combinatorial effects, the evaporation of Cu is decelerated at low S content, but is accelerated at high S content. Based on the elucidated mechanism, an evaporation model equation for Cu was developed in the present study, which takes into account (1) evaporation of Cu in the two forms (Cu(g) and CuS(g)), (2) surface blocking by S using ideal Langmuir adsorption, and (3) effect of C. The obtained rate constant of a reaction Cu i + S i = CuS i (g), k CuS R , is 1.37 × 10-9 m4 mol-1 s-1, and the residual rate constant, k CuS r , is 4.11 × 10-10 m4 mol-1 s-1 at 1873 K (1600 °C). Both of them were found to be one order lower than those for Sn evaporation.

  1. Photochromic mesoporous hybrid coatings

    NASA Astrophysics Data System (ADS)

    Raboin, L.; Matheron, M.; Gacoin, T.; Boilot, J.-P.

    2008-09-01

    Spirooxazine (SO) photochromic molecules were trapped in sol-gel matrices. In order to increase the colourability and improve mechanical properties of sol-gel photochromic films, we present an original strategy in which SO photochromic molecules were dispersed in mesoporous organized films using the impregnation technique. Well-ordered organosilicate mesoporous coatings with the 3D-hexagonal symmetry were prepared by the sol-gel technique. These robust mesoporous films, which contain high amounts of hydrophobic methyl groups at the pore surface, offer optimized environments for photochromic dyes dispersed by impregnation technique. After impregnation by a spirooxazine solution, the photochromic response is only slightly slower when compared with mesostructured or soft sol-gel matrices, showing that mesoporous organized hybrid matrix are good host for photochromic dyes. Moreover, the molecular loading in films is easily adjustable in a large range using multi-impregnation procedure and increasing the film thickness leading to coatings for optical switching devices.

  2. Fe-containing ionic liquids as effective and recoverable oxidants for dissolution of UO2 in the presence of imidazolium chlorides.

    PubMed

    Yao, Aining; Chu, Taiwei

    2013-06-21

    Imidazolium-based Fe-containing ionic liquids (ILs) can directly dissolve UO2 in the presence of their corresponding imidazolium chlorides without additional oxidants. The dissolution process follows pseudo first-order kinetics initially. Raman spectroscopic studies indicate that FeCl4(2-) is the predominant reduction product after UO2 dissolution, and attenuated total reflection-Fourier transform infrared spectroscopy indicates that the UO2(2+) complex is the principal product in the ILs. The dissolved uranyl species can be successfully separated from the Fe-containing ILs via a combination of centrifugation and solvent extraction, and also, the Fe-containing ILs can be recovered easily. In conclusion, imidazolium-based Fe-containing ionic liquids in the presence of imidazolium chlorides could be used as effective and recoverable oxidants for the dissolution of UO2.

  3. Mesoporous metallic rhodium nanoparticles

    NASA Astrophysics Data System (ADS)

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

    2017-05-01

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

  4. Mesoporous carbon materials

    SciTech Connect

    Dai, Sheng; Wang, Xiqing

    2012-02-14

    The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

  5. Surface-functionalized mesoporous carbon materials

    DOEpatents

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

    2016-02-02

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

  6. Carbocation Stability in H-ZSM5 at High Temperature

    SciTech Connect

    Ferguson, Glen A.; Cheng, Lei; Bu, Lintao; Kim, Seonah; Robichaud, David J.; Nimlos, Mark R.; Curtiss, Larry A.; Beckham, Gregg T.

    2015-10-26

    Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 °C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and Tkatchenko–Scheffler van der Waals corrections. Additionally, the embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tert-butyl cations exhibit significant populations (>10%). Furthermore, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are possible at high temperatures relevant to some industrial uses of zeolite catalysts, although as the minority species in most cases.

  7. Carbocation Stability in H-ZSM5 at High Temperature

    SciTech Connect

    Ferguson, Glen A.; Cheng, Lei; Bu, Lintao; Kim, Seonah; Robichaud, David J.; Nimlos, Mark R.; Curtiss, Larry A.; Beckham, Gregg T.

    2015-10-26

    Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 °C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and Tkatchenko-Scheffler van der Waals corrections. The embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tertbutyl cations exhibit significant populations (>10%). Moreover, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are possible at high temperatures relevant to some industrial uses of zeolite catalysts, although as the minority species in most cases.

  8. Mesoporous carbons and polymers

    DOEpatents

    Bell, William; Dietz, Steven

    2001-01-01

    A mesoporous material prepared by polymerizing a resorcinol/formaldehyde system from an aqueous solution containing resorcinol, formaldehyde and a surfactant and optionally pyrolyzing the polymer to form a primarily carbonaceous solid. The material has an average pore size between 4 and 75 nm and is suitable for use in liquid-phase surface limited applications, including sorbent, catalytic, and electrical applications.

  9. Engineered monodisperse mesoporous materials

    SciTech Connect

    Saunders, R.S.; Small, J.H.; Lagasse, R.R.; Schroeder, J.L.; Jamison, G.M.

    1997-08-01

    Porous materials technology has developed products with a wide variety of pore sizes ranging from 1 angstrom to 100`s of microns and beyond. Beyond 15{angstrom} it becomes difficult to obtain well ordered, monodisperse pores. In this report the authors describe efforts in making novel porous material having monodisperse, controllable pore sizes spanning the mesoporous range (20--500 {angstrom}). They set forth to achieve this by using unique properties associated with block copolymers--two linear homopolymers attached at their ends. Block copolymers phase separate into monodisperse mesophases. They desired to selectively remove one of the phases and leave the other behind, giving the uniform monodisperse pores. To try to achieve this the authors used ring-opening metathesis polymerization to make the block copolymers. They synthesized a wide variety of monomers and surveyed their polymers by TGA, with the idea that one phase could be made thermally labile while the other phase would be thermally stable. In the precipitated and sol-gel processed materials, they determined by porosimetry measurements that micropores, mesopores, and macropores were created. In the film processed sample there was not much porosity present. They moved to a new system that required much lower thermal treatments to thermally remove over 90% of the labile phase. Film casting followed by thermal treatment and solvent extraction produced the desired monodisperse materials (based solely on SEM results). Modeling using Density Functional Theory was also incorporated into this project. The modeling was able to predict accurately the domain size and spacing vs. molecular weight for a model system, as well as accurate interfacial thicknesses.

  10. Aligned mesoporous architectures and devices.

    SciTech Connect

    Brinker, C. Jeffrey; Lu, Yunfeng

    2011-03-01

    This is the final report for the Presidential Early Career Award for Science and Engineering - PECASE (LDRD projects 93369 and 118841) awarded to Professor Yunfeng Lu (Tulane University and University of California-Los Angeles). During the last decade, mesoporous materials with tunable periodic pores have been synthesized using surfactant liquid crystalline as templates, opening a new avenue for a wide spectrum of applications. However, the applications are somewhat limited by the unfavorabe pore orientation of these materials. Although substantial effort has been devoted to align the pore channels, fabrication of mesoporous materials with perpendicular pore channels remains challenging. This project focused on fabrication of mesoporous materials with perpendicularly aligned pore channels. We demonstrated structures for use in water purification, separation, sensors, templated synthesis, microelectronics, optics, controlled release, and highly selective catalysts.

  11. Mesoporous Silicate Materials in Sensing

    PubMed Central

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

    2008-01-01

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

  12. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, Allon; Dargas, Daniel; Hwang, Yun Jeong; Yang, Peidong

    2009-08-18

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. The photoluminescence of these nanowires suggest they are composed of crystalline silicon with small enough dimensions such that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices. A better understanding of this electroless route to mesoporous silicon could lead to facile and general syntheses of different narrow bandgap semiconductor nanostructures for various applications.

  13. THE BIOCOMPATIBILITY OF MESOPOROUS SILICATES

    PubMed Central

    Hudson, Sarah; Padera, Robert F.; Langer, Robert; Kohane, Daniel S.

    2008-01-01

    Micro- and nano- mesoporous silicate particles are considered potential drug delivery systems because of their ordered pore structures, large surface areas and the ease with which they can be chemically modified. However, few cytotoxicity or biocompatibility studies have been reported, especially when silicates are administered in the quantities necessary to deliver low-potency drugs. The biocompatibility of mesoporous silicates of particle sizes ~ 150 nm, ~ 800 nm and ~ 4 µm and pore sizes of 3 nm, 7 nm and 16 nm respectively are examined here. In vitro, mesoporous silicates showed a significant degree of toxicity at high concentrations with mesothelial cells. Following subcutaneous injection of silicates in rats, the amount of residual material decreased progressively over three months, with good biocompatibility on histology at all time points. In contrast, intra peritoneal and intra venous injections in mice resulted in death or euthanasia. No toxicity was seen with subcutaneous injection of the same particles in mice. Microscopic analysis of the lung tissue of the mice indicates that death may be due to thrombosis. Although local tissue reaction to mesoporous silicates was benign, they caused severe systemic toxicity. This toxicity could be mitigated by modification of the materials. PMID:18675454

  14. Mesoporous Silicon-Based Anodes

    NASA Technical Reports Server (NTRS)

    Peramunage, Dharmasena

    2015-01-01

    For high-capacity, high-performance lithium-ion batteries. A new high-capacity anode composite based on mesoporous silicon is being developed. With a structure that resembles a pseudo one-dimensional phase, the active anode material will accommodate significant volume changes expected upon alloying and dealloying with lithium (Li).

  15. Magnetic mesoporous material for the sequestration of algae

    DOEpatents

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

    2014-09-09

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

  16. Mesoporous metal oxide graphene nanocomposite materials

    DOEpatents

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

    2016-05-24

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

  17. Cellular membrane trafficking of mesoporous silica nanoparticles

    SciTech Connect

    Fang, I-Ju

    2012-01-01

    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  18. Assemblies of biomaterials in mesoporous media.

    PubMed

    Vinu, Ajayan; Miyahara, Masahiko; Ariga, Katsuhiko

    2006-06-01

    Assemblies of biomaterials onto mechanically stable inorganic structure are advantageous for the practical applications because of the potential to improve the stability and performance of biomaterials in the biocatalytic processes. Among many kinds of inorganic materials, mesoporous materials such as mesoporous silica and mesoporous carbon have attracted special attention owing to their well-defined structures and perfectly controlled pore geometries, which would lead to unique functions such as size selective adsorption of biomaterials. In the first part of this review, adsorption behaviors of proteins, enzymes, vitamins, and amino acids in aqueous solutions onto mesoporous media are systematically explained. Pore geometries (pore diameter and volume) of mesoporous materials are the crucial factors for the size selective adsorption of biomaterials, especially proteins, which often have a size comparable to pore dimension. The studies on the adsorption of biomaterials on the mesoporous carbon reveal that hydrophobic interaction between guest molecules and surface of the mesoporous materials is an important parameter which controls the amount of biomaterials adsorption. Enhanced adsorption of biomaterials was commonly observed at their isoelectric point, where electrostatic repulsion is minimized between the biomaterials. In addition, several functions such as biomolecular separation, reactor function, controlled drug release, and photochemical properties are discussed in the latter sections. Studies on assemblies of biomaterials in mesoporous media are still in initial stage, but the development of appropriately designed mesoporous materials would powerfully promote researches in these fascinating unexplored fields.

  19. Mesoporous carbonates and method of making

    DOEpatents

    Fryxell, Glen; Liu, Jun; Zemanian, Thomas S.

    2004-06-15

    Mesoporous metal carbonate structures are formed by providing a solution containing a non-ionic surfactant and a calcium acetate salt, adding sufficient base to react with the acidic byproducts to be formed by the addition of carbon dioxide, and adding carbon dioxide, thereby forming a mesoporous metal carbonate structure containing the metal from said metal salt.

  20. Non-destructively shattered mesoporous silica for protein drug delivery

    SciTech Connect

    Lei, Chenghong; Chen, Baowei; Li, Xiaolin; Qi, Wen N.; Liu, Jun

    2013-07-15

    Mesoporous silicas have been extensively used for entrapping small chemical molecules and biomacromolecules. We hypothesize that the loading density of biomacromlecules such as proteins in mesoporous silicas could be limited due to mesopore disorderness and depth because of some pore volume inaccessible. We innovatively shattered mesoporous silicas resulting in reduced particle sizes and improved intramesoporous structures in aqueous solution by a powerful sonication, where the mesoporous structures were still well maintained. The sonication-shattered mesoporous silicas can allow protein loading densities to be increased by more than 170%, demonstrating that significantly more mesoporous room of the silicas could become accessible for biomacromolecule loading after the sonication-shattering.

  1. Chemical preparation of ferroelectric mesoporous barium titanate thin films: drastic enhancement of Curie temperature induced by mesopore-derived strain.

    PubMed

    Suzuki, Norihiro; Jiang, Xiangfen; Salunkhe, Rahul R; Osada, Minoru; Yamauchi, Yusuke

    2014-09-01

    Mesoporous barium titanate (BT) thin films are synthesized by a surfactant-assisted sol-gel method. The obtained mesoporous BT thin films show enhanced ferroelectricity due to the effective strains induced by mesopores. The Curie temperature (T(c)) of the mesoporous BT reaches approximately 470 °C.

  2. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, A.I.; Gargas, Daniel; Jeong Hwang, Yun; Yang, Peidong

    2009-08-04

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. These porous nanowires also retain the crystallographic orientation of the wafer from which they are etched. Electron microscopy and diffraction confirm their single-crystallinity and reveal the silicon surrounding the pores is as thin as several nanometers. Confocal fluorescence microscopy showed that the photoluminescence (PL) of these arrays emanate from the nanowires themselves, and their PL spectrum suggests that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices.

  3. Single crystalline mesoporous silicon nanowires.

    PubMed

    Hochbaum, Allon I; Gargas, Daniel; Hwang, Yun Jeong; Yang, Peidong

    2009-10-01

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. These porous nanowires also retain the crystallographic orientation of the wafer from which they are etched. Electron microscopy and diffraction confirm their single-crystallinity and reveal the silicon surrounding the pores is as thin as several nanometers. Confocal fluorescence microscopy showed that the photoluminescence (PL) of these arrays emanate from the nanowires themselves, and their PL spectrum suggests that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices.

  4. Synthesis and characterization of mesoporous zirconia and aluminated mesoporous zirconia

    NASA Astrophysics Data System (ADS)

    Zhao, Elizabeth Sun

    Synthesis of mesoporous zirconia has been performed by slowly hydrolyzing zirconium propoxide in the presence of anionic surfactants: namely, dodecyl phosphate or sulfate (P12 and Sf12) and hexadecyl sulfonate (So16) The zirconia. outgassed at 140--150°C has T-plot surface areas higher than 400 M2/g. This outgassing does not remove the surfactant. After calcination in air at 500°C and combustion of the surfactant, the mesoporous volume is reduced by a factor of about 2, whereas the pore wall material crystallizes in the tetragonal phase. The high-resolution electron microscopic study reveals the presence of a disorganized network of polygonal pores structure. It is suggested that the chemistry of the hydrolysis solution is instrumental in determining the pore structure. A schematic model in which the surfactant is a scaffold component is suggested in order to explain these results and the fixation of PO4, or SO4 in the walls may help to preserve the porous structure. It is very different from the templating mechanism. From the density obtained from phase transition temperature, and from the mesoporous volume (N2 adsorption), the thickness of the wall can be calculated as well as the pseudo-length of the pores. From the thickness, the T-plot area can be recalculated and agrees well with the measured T-plot surface area for the sample calcined at 500°C. Around 900°C, the walls become thicker and crystallizes into monoclinic zirconia without pore structure. In order to try to modify, the acidity of the mesoporous sulfated and oxo-phosphated zirconia, they were doped with aluminum. The sulfated zirconia only has a coating layer of amorphous alumina, while the phosphated zirconia has aluminum in the lattice and the alumina coat. A maximum ratio of Al/Zr ˜ 0.04 can be reached in the lattice. The introduction of aluminum into the lattice prevents the crystallization of the oxo-phosphate at 900°C, and helps to preserve the surface area and porosity of the sulfated

  5. Synthesis of mesoporous SAPO-34 zeolite from mesoporous silica materials for methanol to light olefins.

    PubMed

    Kang, Eun A; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Min; Jeong, Kwang-Eun; Kim, Joo-Wan; Kim, Chul-Ung; Jeong, Soon-Yong

    2013-11-01

    Mesoporous SAPO-34 zeolites were synthesized by using as-prepared mesoporous silica material as both silica source and mesopore tailor. The mesoporous SAPO-34 zeolite materials thus obtained are characterized by a series of different techniques, including poweder X-ray diffraction pattern, nitrogen physisorption analysis, scanning electron micrograph, temperature programmed desorption of ammonia, and inductively coupled plasma atomic emission spectrometry. The resultant mesoporous SAPO-34 crystals exhibit sphere-like particle with zeolite layer units. The mesopore size distribution and particle size can be changed by amounts of silica source and water. The methanol-to-olefins (MTO) reactions using these mesoporous SAPO-34 zeolites are carried out with a fixed-bed reactor. Catalytic tests exhibit that the mesoporous SAPO-34 zeolite materials show high catalytic activity compared with the conventional SAPO-34 for MTO reaction. The better catalytic activity and longer life time of the mesoporous SAPO-34 catalysts in MTO are mainly due to the existence of the mesoporosity of SAPO-34 with small particle size.

  6. Ecodesign of ordered mesoporous silica materials.

    PubMed

    Gérardin, Corine; Reboul, Julien; Bonne, Magali; Lebeau, Bénédicte

    2013-05-07

    Characterized by a regular porosity in terms of pore size and pore network arrangement, ordered mesoporous solids have attracted increasing interest in the last two decades. These materials have been identified as potential candidates for several applications. However, more environmentally friendly and economical synthesis routes of mesoporous silica materials were found to be necessary in order to develop these applications on an industrial scale. Consequently, ecodesign of ordered mesoporous silica has been considerably developed with the objective of optimizing the chemistry and the processing aspects of the material synthesis. In this review, the main strategies developed with this aim are presented and discussed.

  7. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGES

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

    2010-01-01

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

  8. Drug Loading of Mesoporous Silicon

    NASA Astrophysics Data System (ADS)

    Moffitt, Anne; Coffer, Jeff; Wang, Mengjia

    2011-03-01

    The nanostructuring of crystalline solids with low aqueous solubilities by their incorporation into mesoporous host materials is one route to improve the bioavailability of such solids. Earlier studies suggest that mesoporous Si (PSi), with pore widths in the range of 5-50 nm, is a candidate for such an approach. In this presentation, we describe efforts to load curcumin into free-standing microparticles of PSi. Curcumin is a compound extracted from turmeric root, which is an ingredient of curry. Curucmin has shown activity against selected cancer cell lines, bacteria, and other medical conditions. However, curcumin has a very low bioavailability due to its extremely low water solubility (0.6 μ g/mL). Incorporation of curcumin was achieved by straightforward loading of the molten solid at 185circ; C. Loading experiments were performed using PSi particles of two different size ranges, 45-75 μ m and 150-250 μ m. Longer loading times and ratio of curcumin to PSi leads to a higher percentage of loaded curcumin in both PSi particle sizes (as determined by weight difference). The extent of curcumin crystallinity was assessed by x-ray diffraction (XRD). The solubility and release kinetics of loaded curcumin from the PSi was determined by extraction into water at 37circ; C, with analysis using UV-VIS spectrometry. NSF-REU and TCU.

  9. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-09

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs.

  10. Active Fe-Containing Superoxide Dismutase and Abundant sodF mRNA in Nostoc commune (Cyanobacteria) after Years of Desiccation

    PubMed Central

    Shirkey, Breanne; Kovarcik, Don Paul; Wright, Deborah J.; Wilmoth, Gabriel; Prickett, Todd F.; Helm, Richard F.; Gregory, Eugene M.; Potts, Malcolm

    2000-01-01

    Active Fe-superoxide dismutase (SodF) was the third most abundant soluble protein in cells of Nostoc commune CHEN/1986 after prolonged (13 years) storage in the desiccated state. Upon rehydration, Fe-containing superoxide disumutase (Fe-SOD) was released and the activity was distributed between rehydrating cells and the extracellular fluid. The 21-kDa Fe-SOD polypeptide was purified, the N terminus was sequenced, and the data were used to isolate sodF from the clonal isolate N. commune DRH1. sodF encodes an open reading frame of 200 codons and is expressed as a monocistronic transcript (of approximately 750 bases) from a region of the genome which includes genes involved in nucleic acid synthesis and repair, including dipyrimidine photolyase (phr) and cytidylate monophosphate kinase (panC). sodF mRNA was abundant and stable in cells after long-term desiccation. Upon rehydration of desiccated cells, there was a turnover of sodF mRNA within 15 min and then a rise in the mRNA pool to control levels (quantity of sodF mRNA in cells in late logarithmic phase of growth) over approximately 24 h. The extensive extracellular polysaccharide (glycan) of N. commune DRH1 generated superoxide radicals upon exposure to UV-A or -B irradiation, and these were scavenged by SOD. Despite demonstrated roles for the glycan in the desiccation tolerance of N. commune, it may in fact be a significant source of damaging free radicals in vivo. It is proposed that the high levels of SodF in N. commune, and release of the enzyme from dried cells upon rehydration, counter the effects of oxidative stress imposed by multiple cycles of desiccation and rehydration during UV-A or -B irradiation in situ. PMID:10613879

  11. Active Fe-containing superoxide dismutase and abundant sodF mRNA in Nostoc commune (Cyanobacteria) after years of desiccation.

    PubMed

    Shirkey, B; Kovarcik, D P; Wright, D J; Wilmoth, G; Prickett, T F; Helm, R F; Gregory, E M; Potts, M

    2000-01-01

    Active Fe-superoxide dismutase (SodF) was the third most abundant soluble protein in cells of Nostoc commune CHEN/1986 after prolonged (13 years) storage in the desiccated state. Upon rehydration, Fe-containing superoxide disumutase (Fe-SOD) was released and the activity was distributed between rehydrating cells and the extracellular fluid. The 21-kDa Fe-SOD polypeptide was purified, the N terminus was sequenced, and the data were used to isolate sodF from the clonal isolate N. commune DRH1. sodF encodes an open reading frame of 200 codons and is expressed as a monocistronic transcript (of approximately 750 bases) from a region of the genome which includes genes involved in nucleic acid synthesis and repair, including dipyrimidine photolyase (phr) and cytidylate monophosphate kinase (panC). sodF mRNA was abundant and stable in cells after long-term desiccation. Upon rehydration of desiccated cells, there was a turnover of sodF mRNA within 15 min and then a rise in the mRNA pool to control levels (quantity of sodF mRNA in cells in late logarithmic phase of growth) over approximately 24 h. The extensive extracellular polysaccharide (glycan) of N. commune DRH1 generated superoxide radicals upon exposure to UV-A or -B irradiation, and these were scavenged by SOD. Despite demonstrated roles for the glycan in the desiccation tolerance of N. commune, it may in fact be a significant source of damaging free radicals in vivo. It is proposed that the high levels of SodF in N. commune, and release of the enzyme from dried cells upon rehydration, counter the effects of oxidative stress imposed by multiple cycles of desiccation and rehydration during UV-A or -B irradiation in situ.

  12. Sample Desorption/Onization From Mesoporous Silica

    DOEpatents

    Iyer, Srinivas; Dattelbaum, Andrew M.

    2005-10-25

    Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

  13. Complex Filling Dynamics in Mesoporous Thin Films.

    PubMed

    Mercuri, Magalí; Pierpauli, Karina; Bellino, Martín G; Berli, Claudio L A

    2017-01-10

    The fluid-front dynamics resulting from the coexisting infiltration and evaporation phenomena in nanofluidic systems has been investigated. More precisely, water infiltration in both titania and silica mesoporous films was studied through a simple experiment: a sessile drop was deposited over the film and the advancement of the fluid front into the porous structure was optically followed and recorded in time. In the case of titania mesoporous films, capillary infiltration was arrested at a given distance, and a steady annular region of the wetted material was formed. A simple model that combines Lucas-Washburn infiltration and surface evaporation was derived, which appropriately describes the observed filling dynamics and the annulus width in dissimilar mesoporous morphologies. In the case of wormlike mesoporous morphologies, a remarkable phenomenon was found: instead of reaching a steady infiltration-evaporation balance, the fluid front exhibits an oscillating behavior. This complex filling dynamics opens interesting possibilities to study the unusual nanofluidic phenomena and to discover novel applications.

  14. Ordered mesoporous metal oxides: synthesis and applications.

    PubMed

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

    2012-07-21

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

  15. Location of laccase in ordered mesoporous materials

    NASA Astrophysics Data System (ADS)

    Mayoral, Álvaro; Gascón, Victoria; Blanco, Rosa M.; Márquez-Álvarez, Carlos; Díaz, Isabel

    2014-11-01

    The functionalization with amine groups was developed on the SBA-15, and its effect in the laccase immobilization was compared with that of a Periodic Mesoporous Aminosilica. A method to encapsulate the laccase in situ has now been developed. In this work, spherical aberration (Cs) corrected scanning transmission electron microscopy combined with high angle annular dark field detector and electron energy loss spectroscopy were applied to identify the exact location of the enzyme in the matrix formed by the ordered mesoporous solids.

  16. Water repellent periodic mesoporous organosilicas.

    PubMed

    Wang, Wendong; Grozea, Daniel; Kohli, Sandeep; Perovic, Douglas D; Ozin, Geoffrey A

    2011-02-22

    This paper demonstrates for the first time thermally induced gradual hydrophobization, monitored quantitatively by ellipsometric porosimetry, of four prototypical periodic mesoporous organosilicas (PMOs) that are tailored through materials chemistry for use as low-dielectric-constant (low k) materials in microprocessors. Theoretical aspects of this quantification are briefly discussed. A comparison of structural, mechanical, dielectric, and hydrophobic properties of ethane, methane, ethene, and 3-ring PMOs is made. Particularly, ethane, methane, and 3-ring PMOs show impressive water repellency at post-treatment temperatures as low as 350 °C, with corresponding Young's modulus values greater than 10 GPa and k values smaller than 2, a figure of merit that satisfies the technological requirements of future generation microchips.

  17. Mesoporous silica templated zirconia nanoparticles

    NASA Astrophysics Data System (ADS)

    Ballem, Mohamed A.; Córdoba, José M.; Odén, Magnus

    2011-07-01

    Nanoparticles of zirconium oxide (ZrO2) were synthesized by infiltration of a zirconia precursor (ZrOCl2·8H2O) into a SBA-15 mesoporous silica mold using a wet-impregnation technique. X-ray diffractometry and high-resolution transmission electron microscopy show formation of stable ZrO2 nanoparticles inside the silica pores after a thermal treatment at 550 °C. Subsequent leaching out of the silica template by NaOH resulted in well-dispersed ZrO2 nanoparticles with an average diameter of 4 nm. The formed single crystal nanoparticles are faceted with 110 surfaces termination suggesting it to be the preferred growth orientation. A growth model of these nanoparticles is also suggested.

  18. Preparation of irregular mesoporous hydroxyapatite

    SciTech Connect

    Wang Hualin Zhai Linfeng; Li Yanhong; Shi Tiejun

    2008-06-03

    An irregular mesoporous hydroxyapatite (meso-HA), Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, is successfully prepared from Ca(NO{sub 3}){sub 2}.4H{sub 2}O and NH{sub 4}H{sub 2}PO{sub 4} using surfactant cetyltrimethyl ammonium bromide (CTAB) as template. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) results reveal that the positive head of CTAB is assembled on the surface precipitated HA and much NH{sub 4}{sup +} is enclosed in precipitated HA before calcination. Field scanning electron microscope (FSEM) reveals that there exist many interconnected pores throughout the HA reticular skeleton. Nitrogen adsorption-desorption experiment exhibits a mesoporous material type IV curve, and pore size distribution calculated from the desorption branch of the isotherms based on Barrett-Joyner-Halenda (BJH) model shows that most pores throughout the HA reticular skeleton are sized at about 40 nm, but the pores are not uniform on the whole, owning to decomposition of the 'organic' CTAB templating structures and ammonium salt enclosed in the precipitated HA. The specific surface area of irregular meso-HA is calculated to be 37.6 m{sup 2}/g according to the Brunauer-Emmett-Teller (BET) equation. Moreover, after polylactic acid/meso-HA (PLA/meso-HA) composites degraded 12 weeks in normal saline at 37 deg. C, the interconnected pores throughout the HA skeleton were enlarged and sized in micron degree, which resemble trabecular bone structure very much.

  19. Facile mesoporous template-assisted hydrothermal synthesis of ordered mesoporous magnesium silicate as an efficient adsorbent

    NASA Astrophysics Data System (ADS)

    Lu, Qingshan; Li, Qiang; Zhang, Jingjing; Li, Jingfeng; Lu, Jinhua

    2016-01-01

    Mesoporous materials with unique structure as well as special morphology have potential applications in pollutant adsorption. In this work, using mesoporous silica SBA-15 filled with carbon (C@SBA-15) as both silicon source and assisted template, the ordered mesoporous magnesium silicate (Mg3Si4O9(OH)4) has been fabricated at 140 °C by a novel and facile hydrothermal method. During the hydrothermal process, the magnesium silicate grew along the silica walls at the expense of consuming silica and deposited on the carbon surface of the C@SBA-15. Meanwhile, the rigid carbon inside the pores of the SBA-15 supported the magnesium silicate as mesoporous walls under hydrothermal condition. The obtained magnesium silicate possessed ordered mesoporous structure, high specific surface area of 446 m2/g, large pore volume of 0.84 cm3/g, and hierarchical structure assembled with ultrathin nanosheets of 15 nm in thickness. These characteristics endow the ordered mesoporous magnesium silicate with the fast adsorption rate and high adsorption capacity of 382 mg/g for methylene blue. In addition, this synthesis method opens a new approach to fabricate other ordered mesoporous silicates.

  20. Corrosion behavior of mesoporous transition metal nitrides

    SciTech Connect

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

    2013-09-15

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

  1. Ordered mesoporous materials as adsorbents.

    PubMed

    Wu, Zhangxiong; Zhao, Dongyuan

    2011-03-28

    Environmental pollution, energy consumption and biotechnology have induced more and more public concerns. Problems imposed by these issues will circulate in the 21st century. Adsorption-based processes may lead to one of the most efficient routes for removal of toxic substances, energy storage and bio-applications. The fundamental and great challenge is developing highly efficient adsorbents. In this regard, ordered mesoporous materials (OMMs) may be the answer in the future. They possess intrinsic high specific surface areas, regular and tunable pore sizes, large pore volumes, as well as stable and interconnected frameworks with active pore surfaces for modification or functionalization. Such features meet the requirements as excellent adsorbents, not only providing huge interface and large space capable of accommodating capacious guest species, but also enabling the possibility of specific binding, enrichment and separation. As a result, these materials have been extensively studied as advanced adsorbents and hundreds of papers have been published since the millennium. In this Highlight, we will mainly summarize and outlook the development in pollution control, gas storage and bioadsorption by using OMMs as adsorbents.

  2. Synthesis and characterization of mesoporous hydrocracking catalysts

    NASA Astrophysics Data System (ADS)

    Munir, D.; Usman, M. R.

    2016-08-01

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

  3. Drug release from ordered mesoporous silicas.

    PubMed

    Doadrio, Antonio L; Salinas, Antonio J; Sánchez-Montero, José M; Vallet-Regí, M

    2015-01-01

    The state-of-the-art in the investigation of drugs release from Silica-based ordered Mesoporous Materials (SMMs) is reviewed. First, the SMM systems used like host matrixes are described. Then, the model drugs studied until now, including their pharmacological action, structure and the mesoporous matrix employed for each drug, are comprehensively listed. Next, the factors influencing the release of drugs from SMMs and the strategies used to control the drug delivery, specially the chemical functionalization of the silica surface, are discussed. In addition, how all these factors were gathered in a kinetic equation that describes the drug release from the mesoporous matrixes is explained. The new application of molecular modeling and docking in the investigation of the drug delivery mechanisms from SMMs is also presented. Finally, the new approaches under investigation in this field are mentioned including the design of smart stimuli-responsive materials and other recent proposals for a future investigation.

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

    PubMed

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

    2017-09-11

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

  5. Orientation specific deposition of mesoporous particles

    NASA Astrophysics Data System (ADS)

    Kjellman, Tomas; Bodén, Niklas; Wennerström, Hâkan; Edler, Karen J.; Alfredsson, Viveka

    2014-11-01

    We present a protocol for a facile orientation specific deposition of plate-like mesoporous SBA-15 silica particles onto a surface (mesopores oriented normal to surface). A drop of an aqueous dispersion of particles is placed on the surface and water vaporizes under controlled relative humidity. Three requirements are essential for uniform coverage: particle dispersion should not contain aggregates, a weak attraction between particles and surface is needed, and evaporation rate should be low. Aggregates are removed by stirring/sonication. Weak attraction is realized by introducing cationic groups to the surface. Insight into the mechanisms of the so-called coffee stain effect is also provided.

  6. Location of laccase in ordered mesoporous materials

    SciTech Connect

    Mayoral, Álvaro; Gascón, Victoria; Blanco, Rosa M.; Márquez-Álvarez, Carlos; Díaz, Isabel

    2014-11-01

    The functionalization with amine groups was developed on the SBA-15, and its effect in the laccase immobilization was compared with that of a Periodic Mesoporous Aminosilica. A method to encapsulate the laccase in situ has now been developed. In this work, spherical aberration (C{sub s}) corrected scanning transmission electron microscopy combined with high angle annular dark field detector and electron energy loss spectroscopy were applied to identify the exact location of the enzyme in the matrix formed by the ordered mesoporous solids.

  7. Dehydration pathways of 1-propanol on HZSM-5 in the presence and absence of water

    SciTech Connect

    Zhi, Yuchun; Shi, Hui; Mu, Linyu; Liu, Yue; Mei, Donghai; Camaioni, Donald M.; Lercher, Johannes A.

    2015-12-23

    The Brønsted acid-catalyzed gas-phase dehydration of 1-propanol (0.075-4 kPa) was studied on zeolite H-MFI (Si/Al = 26, containing minimal amounts of extraframework Al moieties) in the absence and presence of co-fed water (0-2.5 kPa) at 413-443 K. It is shown that propene can be formed from monomeric and dimeric adsorbed 1-propanol. The stronger adsorption of 1-propanol relative to water indicates that the reduced dehydration rates in the presence of water are not a consequence of the competitive adsorption between 1-propanol and water. Instead, the deleterious effect is related to the different extents of stabilization of adsorbed intermediates and the relevant elimination/substitution transition states by water. Water stabilizes the adsorbed 1-propanol monomer significantly more than the elimination transition state, leading to a higher activation barrier and a greater entropy gain for the rate-limiting step, which eventually leads to propene. In a similar manner, an excess of 1-propanol stabilizes the adsorbed state of 1-propanol more than the elimination transition state. In comparison with the monomer-mediated pathway, adsorbed dimer and the relevant transition states for propene and ether formation are similarly, while less effectively, stabilized by intrazeolite water molecules. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and was performed in part using the Molecular Sciences Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located and the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE.

  8. H-ZSM5 Catalyzed co-pyrolysis of biomass and plastics

    USDA-ARS?s Scientific Manuscript database

    This study aims at addressing two important problems vital to agriculture, disposal of agricultural plastics and production of drop-in fuels from biomass via co-pyrolysis of both feedstocks. Mixtures of biomass (switchgrass, cellulose, xylan and lignin) and plastic (polyethylene terephthalate (PET),...

  9. Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

    USDA-ARS?s Scientific Manuscript database

    While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

  10. Effect of torrefaction temperature on lignin macromolecule and product distribution from HZSM-5 catalytic pyrolysis

    SciTech Connect

    Mahadevan, Ravishankar; Adhikari, Sushil; Shakya, Rajdeep; Wang, Kaige; Dayton, David C.; Li, Mi; Pu, Yunqiao; Ragauskas, Arthur J.

    2016-10-27

    Torrefaction is a low-temperature process considered as an effective pretreatment technique to improve the grindability of biomass as well as enhance the production of aromatic hydrocarbons from Catalytic Fast Pyrolysis (CFP). For this paper, this study was performed to understand the effect of torrefaction temperature on structural changes in the lignin macromolecule and its subsequent influence on in-situ CFP process. Lignin extracted from southern pine and switchgrass (via organosolv treatment) was torrefied at four different temperatures (150, 175, 200 and 225 °C) in a tubular reactor. Between the two biomass types studied, lignin from pine appeared to have greater thermal stability during torrefaction when compared with switchgrass lignin. The structural changes in lignin as a result of torrefaction were followed by using FTIR spectroscopy, solid state CP/MAS 13C NMR, 31P NMR spectroscopy and it was found that higher torrefaction temperature (200 and 225 °C) caused polycondensation and de-methoxylation of the aromatic units of lignin. Gel permeation chromatography analysis revealed that polycondensation during torrefaction resulted in an increase in the molecular weight and polydispersity of lignin. The torrefied lignin was subsequently used in CFP experiments using H+ZSM-5 catalyst in a micro-reactor (Py-GC/MS) to understand the effect of torrefaction on the product distribution from pyrolysis. It was observed that although the selectivity of benzene-toluene-xylene compounds from CFP of pine improved from 58.3% (torrefaction temp at 150 °C) to 69.0% (torrefaction temp at 225 °C), the severity of torrefaction resulted in a loss of overall aromatic hydrocarbon yield from 11.6% to 4.9% under same conditions. Torrefaction at higher temperatures also increased the yield of carbonaceous residues from 63.9% to 72.8%. Finally, overall, torrefying lignin caused structural transformations in both type of lignins (switchgrass and pine), which is ultimately detrimental to achieving a higher aromatic hydrocarbon yield from CFP.

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

    PubMed

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

    2008-11-01

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

  12. Mesoporous Transition Metal Oxides for Supercapacitors

    PubMed Central

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

    2015-01-01

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

  13. Preparation and characterization of multifunctional magnetic mesoporous calcium silicate materials

    PubMed Central

    Zhang, Jianhua; Zhu, Yufang; Li, Jie; Zhu, Min; Tao, Cuilian; Hanagata, Nobutaka

    2013-01-01

    We have prepared multifunctional magnetic mesoporous Fe–CaSiO3 materials using triblock copolymer (P123) as a structure-directing agent. The effects of Fe substitution on the mesoporous structure, in vitro bioactivity, magnetic heating ability and drug delivery property of mesoporous CaSiO3 materials were investigated. Mesoporous Fe–CaSiO3 materials had similar mesoporous channels (5–6 nm) with different Fe substitution. When 5 and 10% Fe were substituted for Ca in mesoporous CaSiO3 materials, mesoporous Fe–CaSiO3 materials still showed good apatite-formation ability and had no cytotoxic effect on osteoblast-like MC3T3-E1 cells evaluated by the elution cell culture assay. On the other hand, mesoporous Fe–CaSiO3 materials could generate heat to raise the temperature of the surrounding environment in an alternating magnetic field due to their superparamagnetic property. When we use gentamicin (GS) as a model drug, mesoporous Fe–CaSiO3 materials release GS in a sustained manner. Therefore, magnetic mesoporous Fe–CaSiO3 materials would be a promising multifunctional platform with bone regeneration, local drug delivery and magnetic hyperthermia. PMID:27877616

  14. Preparation and characterization of multifunctional magnetic mesoporous calcium silicate materials.

    PubMed

    Zhang, Jianhua; Zhu, Yufang; Li, Jie; Zhu, Min; Tao, Cuilian; Hanagata, Nobutaka

    2013-10-01

    We have prepared multifunctional magnetic mesoporous Fe-CaSiO3 materials using triblock copolymer (P123) as a structure-directing agent. The effects of Fe substitution on the mesoporous structure, in vitro bioactivity, magnetic heating ability and drug delivery property of mesoporous CaSiO3 materials were investigated. Mesoporous Fe-CaSiO3 materials had similar mesoporous channels (5-6 nm) with different Fe substitution. When 5 and 10% Fe were substituted for Ca in mesoporous CaSiO3 materials, mesoporous Fe-CaSiO3 materials still showed good apatite-formation ability and had no cytotoxic effect on osteoblast-like MC3T3-E1 cells evaluated by the elution cell culture assay. On the other hand, mesoporous Fe-CaSiO3 materials could generate heat to raise the temperature of the surrounding environment in an alternating magnetic field due to their superparamagnetic property. When we use gentamicin (GS) as a model drug, mesoporous Fe-CaSiO3 materials release GS in a sustained manner. Therefore, magnetic mesoporous Fe-CaSiO3 materials would be a promising multifunctional platform with bone regeneration, local drug delivery and magnetic hyperthermia.

  15. Preparation and characterization of multifunctional magnetic mesoporous calcium silicate materials

    NASA Astrophysics Data System (ADS)

    Zhang, Jianhua; Zhu, Yufang; Li, Jie; Zhu, Min; Tao, Cuilian; Hanagata, Nobutaka

    2013-10-01

    We have prepared multifunctional magnetic mesoporous Fe-CaSiO3 materials using triblock copolymer (P123) as a structure-directing agent. The effects of Fe substitution on the mesoporous structure, in vitro bioactivity, magnetic heating ability and drug delivery property of mesoporous CaSiO3 materials were investigated. Mesoporous Fe-CaSiO3 materials had similar mesoporous channels (5-6 nm) with different Fe substitution. When 5 and 10% Fe were substituted for Ca in mesoporous CaSiO3 materials, mesoporous Fe-CaSiO3 materials still showed good apatite-formation ability and had no cytotoxic effect on osteoblast-like MC3T3-E1 cells evaluated by the elution cell culture assay. On the other hand, mesoporous Fe-CaSiO3 materials could generate heat to raise the temperature of the surrounding environment in an alternating magnetic field due to their superparamagnetic property. When we use gentamicin (GS) as a model drug, mesoporous Fe-CaSiO3 materials release GS in a sustained manner. Therefore, magnetic mesoporous Fe-CaSiO3 materials would be a promising multifunctional platform with bone regeneration, local drug delivery and magnetic hyperthermia.

  16. Prototype of low thermal expansion materials: fabrication of mesoporous silica/polymer composites with densely filled polymer inside mesopore space.

    PubMed

    Kiba, Shosuke; Suzuki, Norihiro; Okawauchi, Yoshinori; Yamauchi, Yusuke

    2010-09-03

    A prototype of novel low thermal expansion materials using mesoporous silica particles is demonstrated. Mesoporous silica/polymer composites with densely filled polymer inside the mesopore space are fabricated by mechanically mixing both organically modified mesoporous silica and epoxy polymer. The mesopores are easily penetrated by polymers as a result of the capillary force during the mechanical composite processing. Furthermore, we propose a new model of polymer mobility restriction using mesoporous silica with a large pore space. The robust inorganic frameworks covering the polymer effectively restrict the polymer mobility against thermal energy. As a result, the degree of total thermal expansion of the composites is drastically decreased. From the mass-normalized thermal mechanical analysis (TMA) charts of various composites with different amounts of mesoporous silica particles, it is observed that the coefficient of thermal expansion (CTE) values gradually increase with an increase of the polymer amount outside the mesopores. It is proven that the CTE values in the range over the glass-transition temperatures (T(g)) are perfectly proportional to the outside polymer amounts. Importantly, the Y-intercept of the relation equation obtained by a least-square method is the CTE value and is almost zero. This means that thermal expansion does not occur if no polymers are outside the mesopores. Through such a quantative discussion, we clarify that only the outside polymer affects the thermal expansion of the composites, that is, the embedded polymers inside the mesopores do not expand at all during the thermal treatment.

  17. Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

    NASA Astrophysics Data System (ADS)

    Gao, Lin; Sun, Jihong; Li, Yuzhen

    2011-08-01

    The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N 2 adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation ft= ktn was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties.

  18. Synthesis of mesoporous silica nanoparticles by means of a hydrogel

    NASA Astrophysics Data System (ADS)

    Samadi-Maybodi, Abdolraouf; Vahid, Amir

    2013-05-01

    Synthesis and application of mesoporous silicate nanoparticles are important areas of research in many fields such as drug delivery, medicine, catalysis, and optic. The method of synthesis strongly affects the properties of a product. In this work, the mesoporous silica nanoparticles were synthesized by means of a hydrogel. The obtained product was characterized by X-ray diffraction, scanning electron microscopy, and nitrogen physisorption. The results show that highly ordered mesoporous silica nanoparticles were synthesized by means of a hydrogel.

  19. Synthesis and Characterization of Mesoporous Semiconductors

    NASA Astrophysics Data System (ADS)

    Kang, Chris Byung-hwa

    Widely studied mesoporous oxide materials have a range of potential applications, such as catalysis, absorption and separation. However, they are not generally considered for their optical and electronic properties. Elemental semiconductors with nano-sized pores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. This thesis describes two different routes to synthesize thin film mesoporous silicon and powder mesoporous germanium. Thin film of mesoporous silicon was produced from thin film of mesoporous silica at low temperature (<700°C) using magnesium as reducing agent. Excess magnesium risks the generation of volatile products and destruction of the bulk objects. In thin films, excess magnesium was convenient resulting in some structural loss. However, our X-ray diffraction data show that conversion to silicon and retention of order is possible even after exposure to HCl to remove magnesia and HF to remove remnant silica. Top-view SEM and low angle X-ray diffraction also proves retain in order and cross-section SEM shows retention of the surface features and pores in the bulk of the film. Nanoscale ordered germanium composite materials were produced from solution phase using surfactant as structural directing agents. Non-classic anionic germanium Zintl clusters, discrete Ge94- or polymeric (Ge92-)n, co-assemble with cationic surfactant molecules via electrostatic interactions. Depending upon size and overall charge of polymerized Zintl clusters, shape of the inorganic/organic hybrid micelle can be varied, and the periodical nano-structures of composites can be hexagonal, lamellar, or worm-like, as determined by low angle X-ray diffraction (XRD). The anionic germanium framework of the 2-D hexagonally ordered germanium cluster/surfactant composite is condensed via oxidative coupling between the germanium Zintl clusters. EXAFS

  20. Catalyst-free synthesis of transparent, mesoporous diamond monoliths from periodic mesoporous carbon CMK-8

    SciTech Connect

    Zhang, Li; Mohanty, Paritosh; Coombs, Neil; Fei, Yingwei; Mao, Ho-kwang; Landskrom, Kai

    2010-07-19

    We report on the synthesis of optically transparent, mesoporous, monolithic diamond from periodic mesoporous carbon CMK-8 at a pressure of 21 GPa. The phase transformation is already complete at a mild synthesis temperature of 1,300 °C without the need of a catalyst. Surprisingly, the diamond is obtained as a mesoporous material despite the extreme pressure. X-ray diffraction, SEM, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, and Z-contrast experiments suggest that the mesoporous diamond is composed of interconnected diamond nanocrystals having diameters around 5–10 nm. The Brunauer Emmett Teller surface area was determined to be 33 m2 g-1 according Kr sorption data. The mesostructure is diminished yet still detectable when the diamond is produced from CMK-8 at 1,600 °C and 21 GPa. The temperature dependence of the porosity indicates that the mesoporous diamond exists metastable and withstands transformation into a dense form at a significant rate due to its high kinetic inertness at the mild synthesis temperature. The findings point toward ultrahard porous materials with potential as mechanically highly stable membranes.

  1. Surface functionalized mesoporous material and method of making same

    DOEpatents

    Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA; Fryxell, Glen E [Kennewick, WA

    2001-12-04

    According to the present invention, an organized assembly of functional molecules with specific interfacial functionality (functional group(s)) is attached to available surfaces including within mesopores of a mesoporous material. The method of the present invention avoids the standard base soak that would digest the walls between the mesopores by boiling the mesoporous material in water for surface preparation then removing all but one or two layers of water molecules on the internal surface of a pore. Suitable functional molecule precursor is then applied to permeate the hydrated pores and the precursor then undergoes condensation to form the functional molecules on the interior surface(s) of the pore(s).

  2. Targeted mesoporous silica nanocarriers in oncology.

    PubMed

    Baeza, Alejandro; Vallet-Regí, Maria

    2016-06-02

    Cancer is one of the major leading causes of death worldwide and its prevalence will be higher in the coming years due to the progressive aging of the population. The development of nanocarriers in oncology has provided a new hope in the fight against this terrible disease. Among the different types of nanoparticles which have been described, mesoporous silica nanoparticles (MSNs) constitute a very promising material due to their inherent properties as high loading capacity of many different drugs, excellent biocompatibility and easiness functionalization. This review presents the current state of the art related with the development of mesoporous silica nanocarriers for antitumoral therapy paying special attention on targeted MSN able to selectively destroy tumoral cells reducing the side damage in healthy ones, and the basic principles of targeting tumoral tissues and cells.

  3. Inclusion chemistry in periodic mesoporous hosts

    SciTech Connect

    Moller, K.; Bein, T.

    1998-10-01

    This review provides an overview of different aspects of inclusion chemistry in ordered mesoporous host materials such as MCM-41 or MCM-48 (Mobil codes). A rich field of inclusion chemistry has been explored in this context, including sorption, ion exchange, inhibition followed by reduction, grafting of reactive metal alkoxides, halides, etc., grafting of silane coupling agents (sometimes followed by subsequent reactions), grafting of reactive metal complexes, and polymerization in the channels. Finally, co-condensation of reactive species during the mesopore synthesis is a method to incorporate functionality into the walls of the channel system. Important applications of these modified and functionalized systems are heterogeneous catalysis and photocatalysis involving bulky grated catalysts and/or the conversion of large substrates. Other potential applications include ion exchange and separations, removal of heavy metals, chromatography, stabilization of quantum wires, stabilization of dyes, and polymer composites.

  4. Synthesis of Mesoporous Supraparticles on Superamphiphobic Surfaces.

    PubMed

    Wooh, Sanghyuk; Huesmann, Hannah; Tahir, Muhammad Nawaz; Paven, Maxime; Wichmann, Kristina; Vollmer, Doris; Tremel, Wolfgang; Papadopoulos, Periklis; Butt, Hans-Jürgen

    2015-12-02

    A method for mesoporous supraparticle synthesis on superamphiphobic surfaces is designed. Therefore, supraparticles assembled with nanoparticles are synthesized by the evaporation of nanoparticle dispersion drops on the superamphiphobic surface. For synthesis, no further purification is required and no organic solvents are wasted. Moreover, by changing the conditions such as drop size and concentration, supraparticles of different sizes, compositions, and architectures are fabricated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Cubic mesoporous titanium phosphonates with multifunctionality.

    PubMed

    Ma, Tian-Yi; Lin, Xiu-Zhen; Yuan, Zhong-Yong

    2010-07-26

    Cubic mesoporous titanium phosphonate materials with bridged organic groups inside the framework were synthesized by means of a one-pot hydrothermal autoclaving process, with the assistance of cationic surfactant cetyltrimethylammonium bromide. 1-Hydroxyethylidene-1,1-diphosphonic acid was used as the coupling molecule. A typical cubic mesophase with surface area of 1052 m(2) g(-1) and pore size of 2.6 nm was confirmed by XRD, TEM, and N(2) sorption analysis. The organophosphonate groups were homogeneously incorporated in the network of the mesoporous solids, as revealed by FTIR and magic-angle spinning (MAS) NMR spectroscopy, and thermogravimetry and differential scanning calorimetry (TG-DSC) measurements. The synthesized hydroxyethylidene-bridged cubic mesoporous titanium phosphonates proved to be thermally stable up to 350 degrees C, with a well-preserved hybrid framework and cubic mesoporous architecture. The obtained cubic mesophase could be transformed into a hexagonal mesophase by simply adjusting the molar ratios of the added raw materials, namely, a Ti/P molar ratio of 1:4 and a CTAB/Ti molar ratio of 1.9-2.3 for the cubic phase and Ti/P molar ratio of 3:4 and CTAB/Ti molar ratio of 0.1-0.4 for the hexagonal phase. The cubic hybrid materials could be used as efficient photocatalysts for the photodegradation of rhodamine B. Moreover, they were also used for adsorption of CO(2) and heavy metal ions and exhibited a significant capture amount of around 1.0 mmol g(-1) for CO(2) molecules at 35 degrees C and high adsorption capacity of 28.5 micromol g(-1) for Cu(2+) ions with good reusability, which demonstrated their promising potential in environmental remediation.

  6. Polymer/mesoporous metal oxide composites

    NASA Astrophysics Data System (ADS)

    Ver Meer, Melissa Ann

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

  7. The Synthesis of Functional Mesoporous Materials

    SciTech Connect

    Fryxell, Glen E.

    2006-11-01

    The ability to decorate a silica surface with specific ligand fields and/or metal complexes creates powerful new capabilities for catalysis, chemical separations and sensor development. Integrating this with the ability to control the spacing of these complexes across the surface, as well as the symmetry and size of the pore structure, allows the synthetic chemist to hierarchically tailor these structured nanomaterials to specific needs. The next step up the “scale ladder” is provided by the ability to coat these mesoporous materials onto complex shapes, allowing for the intimate integration of these tailored materials into device interfaces. The ability to tailor the pore structure of these mesoporous supports is derived from the surfactant templated synthesis of mesoporous materials, an area which has seen an explosion of activity over the last decade.[1,2] The ability to decorate the surface with the desired functionality requires chemical modification of the oxide interface, most commonly achieved using organosilane self-assembly.[3-6] This manuscript describes recent results from the confluence of these two research areas, with a focus on synthetic manipulation of the morphology and chemistry of the interface, with the ultimate goal of binding metal centers in a chemically useful manner.

  8. Immobilization of Methyltrioxorhenium on Mesoporous Aluminosilicate Materials

    PubMed Central

    Stekrova, Martina; Zdenkova, Radka; Vesely, Martin; Vyskocilova, Eliska; Cerveny, Libor

    2014-01-01

    The presented report focuses on an in-depth detailed characterization of immobilized methyltrioxorhenium (MTO), giving catalysts with a wide spectra of utilization. The range of mesoporous materials with different SiO2/Al2O3 ratios, namely mesoporous alumina (MA), aluminosilicates type Siral (with Al content 60%–90%) and MCM-41, were used as supports for immobilization of MTO. The tested support materials (aluminous/siliceous) exhibited high surface area, well-defined regular structure and narrow pore size distribution of mesopores, and therefore represent excellent supports for the active components. Some of the supports were modified by zinc chloride in order to obtain catalysts with higher activities for instance in metathesis reactions. The immobilization of MTO was optimized using these supports and it was successful using all supports. The success of the immobilization of MTO and the properties of the prepared heterogeneous catalysts were characterized using X-ray Fluorescence (XRF), atomic absorption spectroscopy (AAS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), physical adsorption of N2, ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (FTIR), Fourier Transform Infrared Spectroscopy (FTIR) using pyridine as a probe molecule and X-ray photoelectron spectroscopy (XPS). Furthermore, the catalytic activity of the immobilized MTO on the tested supports was demonstrated on metathesis reactions of various substrates. PMID:28788588

  9. The Synthesis of Cadmium Doped Mesoporous TiO2

    SciTech Connect

    Li, Xiaohong S.; Fryxell, Glen E.; Engelhard, Mark H.; Wang, Chong M.

    2007-06-01

    Cd doped mesoporous titanium oxide was prepared using non-ionic surfactants and easily handled titanium precursors. The Cd doping was found to be able to significantly inhibit the growth of anatase crystal size, stabilize the mesoporous structure, and retard the densification of nanoporous TiO2 at elevated temperatures.

  10. Biodegradation-tunable mesoporous silica nanorods for controlled drug delivery.

    PubMed

    Park, Sung Bum; Joo, Young-Ho; Kim, Hyunryung; Ryu, WonHyoung; Park, Yong-il

    2015-05-01

    Mesoporous silica in the forms of micro- or nanoparticles showed great potentials in the field of controlled drug delivery. However, for precision control of drug release from mesoporous silica-based delivery systems, it is critical to control the rate of biodegradation. Thus, in this study, we demonstrate a simple and robust method to fabricate "biodegradation-tunable" mesoporous silica nanorods based on capillary wetting of anodic aluminum oxide (AAO) template with an aqueous alkoxide precursor solution. The porosity and nanostructure of silica nanorods were conveniently controlled by adjusting the water/alkoxide molar ratio of precursor solutions, heat-treatment temperature, and Na addition. The porosity and biodegradation kinetics of the fabricated mesoporous nanorods were analyzed using N2 adsorption/desorption isotherm, TGA, DTA, and XRD. Finally, the performance of the mesoporous silica nanorods as drug delivery carrier was demonstrated with initial burst and subsequent "zero-order" release of anti-cancer drug, doxorubicin.

  11. Iron oxide nanoparticles stabilized inside highly ordered mesoporous silica

    NASA Astrophysics Data System (ADS)

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

    2005-11-01

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

  12. 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

  13. Preparation of mesoporous zirconia microspheres as inert matrix

    NASA Astrophysics Data System (ADS)

    Guo, Ting; Wang, Chen; Lv, Jinlong; Liang, Tongxiang

    2016-12-01

    Mesoporous zirconia microspheres, with a diameter of 900 μm, were prepared as an inert accelerator driven system (ADS) transmutation element matrix by the sol-gel method. The purpose of mesopores is to improve the adsorption capacity of inert matrix fuel (IMF) for minor actinides. The study indicated that the mesoporous zirconia performance was improved after the microspheres were hydrothermally treated at 150 °C, the specific surface area increased from 28.29 m2/g to 61.28 m2/g, and hydrothermal treatment avoided the cracking of the microspheres. Pre-decomposition of the organics during the hydrothermal process stabilized the mesoporous structure. The average pore diameter of mesoporous microsphere was 14.3 nm.

  14. Comparison of mesoporous silicon and non-ordered mesoporous silica materials as drug carriers for itraconazole.

    PubMed

    Kinnari, Päivi; Mäkilä, Ermei; Heikkilä, Teemu; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A

    2011-07-29

    Mesoporous materials have an ability to enhance dissolution properties of poorly soluble drugs. In this study, different mesoporous silicon (thermally oxidized and thermally carbonized) and non-ordered mesoporous silica (Syloid AL-1 and 244) microparticles were compared as drug carriers for a hydrophobic drug, itraconazole (ITZ). Different surface chemistries pore volumes, surface areas, and particle sizes were selected to evaluate the structural effect of the particles on the drug loading degree and on the dissolution behavior of the drug at pH 1.2. The results showed that the loaded ITZ was apparently in amorphous form, and that the loading process did not change the chemical structure/morphology of the particles' surface. Incorporation of ITZ in both microparticles enhanced the solubility and dissolution rate of the drug, compared to the pure crystalline drug. Importantly, the physicochemical properties of the particles and the loading procedure were shown to have an effect on the drug loading efficiency and drug release kinetics. After storage under stressed conditions (3 months at 40 °C and 70% RH), the loaded silica gel particles showed practically similar dissolution profiles as before the storage. This was not the case with the loaded mesoporous silicon particles due to the almost complete chemical degradation of ITZ after storage.

  15. The development of chiral nematic mesoporous materials.

    PubMed

    Kelly, Joel A; Giese, Michael; Shopsowitz, Kevin E; Hamad, Wadood Y; MacLachlan, Mark J

    2014-04-15

    Cellulose nanocrystals (CNCs) are obtained from the sulfuric acid-catalyzed hydrolysis of bulk cellulose. The nanocrystals have diameters of ~5-15 nm and lengths of ~100-300 nm (depending on the cellulose source and hydrolysis conditions). This lightweight material has mostly been investigated to reinforce composites and polymers because it has remarkable strength that rivals carbon nanotubes. But CNCs have an additional, less explored property: they organize into a chiral nematic (historically referred to as cholesteric) liquid crystal in water. When dried into a thin solid film, the CNCs retain the helicoidal chiral nematic order and assemble into a layered structure where the CNCs have aligned orientation within each layer, and their orientation rotates through the stack with a characteristic pitch (repeating distance). The cholesteric ordering can act as a 1-D photonic structure, selectively reflecting circularly polarized light that has a wavelength nearly matching the pitch. During CNC self-assembly, it is possible to add sol-gel precursors, such as Si(OMe)4, that undergo hydrolysis and condensation as the solvent evaporates, leading to a chiral nematic silica/CNC composite material. Calcination of the material in air destroys the cellulose template, leaving a high surface area mesoporous silica film that has pore diameters of ~3-10 nm. Importantly, the silica is brilliantly iridescent because the pores in its interior replicate the chiral nematic structure. These films may be useful as optical filters, reflectors, and membranes. In this Account, we describe our recent research into mesoporous films with chiral nematic order. Taking advantage of the chiral nematic order and nanoscale of the CNC templates, new functional materials can be prepared. For example, heating the silica/CNC composites under an inert atmosphere followed by removal of the silica leaves highly ordered, mesoporous carbon films that can be used as supercapacitor electrodes. The composition

  16. Ordered mesoporous silica-based inorganic nanocomposites

    NASA Astrophysics Data System (ADS)

    Wang, Qingqing; Shantz, Daniel F.

    2008-07-01

    This article reviews the synthesis and characterization of nanoparticles and nanowires grown in ordered mesoporous silicas (OMS). Summarizing work performed over the last 4 years, this article highlights the material properties of the final nanocomposite in the context of the synthesis methodology employed. While certain metal-OMS systems (e.g. gold in MCM-41) have been extensively studied this article highlights that there is a rich set of chemistries that have yet to be explored. The article concludes with some thoughts on future developments and challenges in this area.

  17. Fluorescence properties of dye doped mesoporous silica

    SciTech Connect

    Carbonaro, Carlo M. Corpino, Riccardo Ricci, Pier Carlo Chiriu, Daniele; Cannas, Carla

    2014-10-21

    In this paper we present a review of the main results we obtained studying the emission properties of organic-inorganic hybrids obtained combining mesoporous silica and Xantene dyes, in particular the standard reference Rhodamine 6G. The purpose of the review is to show the possibility to efficiently 'dope' the transparent inorganic porous matrix to obtain promising systems for photonic and biomedical applications. The strategies to solve the concentration effect and the leaching phenomenon are discussed within the framework of the single exciton theory.

  18. Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

    SciTech Connect

    Gao Lin; Sun Jihong; Li Yuzhen

    2011-08-15

    The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N{sub 2} adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation f{sub t}=kt{sup n} was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties. - Graphical abstract: Loading (A) and release profiles (B) of aspirin in N-BMMs and N-MCM-41 indicated that BMMs have more drug loading capacity and faster release rate than that MCM-41. Highlights: > Bimodal mesoporous silicas (BMMs) and MCM-41 modified with amino group via post-treatment procedure. > Loading and release profiles of aspirin in modified BMMs and MCM-41. > Modified BMMs have more drug loading capacity and faster release rate than that modified MCM-41.

  19. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOEpatents

    Sachtler, W.M.H.; Huang, Y.Y.

    1998-07-28

    Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

  20. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOEpatents

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan

    1998-01-01

    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

  1. Mesoporous Trimetallic PtPdRu Spheres as Superior Electrocatalysts.

    PubMed

    Jiang, Bo; Ataee-Esfahani, Hamed; Li, Cuiling; Alshehri, Saad M; Ahamad, Tansir; Henzie, Joel; Yamauchi, Yusuke

    2016-05-17

    Mesoporous Trimetallic PtPdRu Spheres with well-defined spherical morphology and uniformly sized pores were synthesized in an aqueous solution using ascorbic acid as the reducing agent and triblock copolymer F127 as the pore directing agent. These mesoporous PtPdRu spheres exhibited enhanced electrocatalytic activity compared to commercial Pt black, resulting in a ∼4.9 times improvement in mass activity for the methanol oxidation reaction. The excellent electrocatalytic activity and stability are due to the unique mesoporous architecture and electronic landscape between different elements.

  2. Smart Mesoporous Silica Nanocarriers for Antitumoral Therapy.

    PubMed

    Baeza, Alejandro; Vallet-Regí, María

    2015-01-01

    The development of nanocarriers able transport and release therapeutic agents in a controlled manner has provided a promising alternative in the oncology field due to the lack of selectivity of the conventional treatments. The encapsulation of cytotoxic compounds within nanoparticles improves the pharmacokinetic profile of the trapped drugs and allows their selective accumulation into the tumoral tissue owing to the enhance permeation and retention effect (EPR. In addition, the selectivity of the nanocarrier can be enhanced attaching targeting agents on their surface able to be specifically recognized by cancer cells or by the tumor microenvironment. Among the different materials which can be employed, mesoporous silica nanoparticles (MCM-41 type constitutes a promising candidate due to their very interesting properties such as tuneable size, shape and porosity, high loading capacity, low toxicity, robustness and easiness fabrication and functionalization. This material presents a unique pore architecture which allows the synthesis of stimuliresponsive devices able to release the trapped drugs only in the presence of certain stimuli achieving a precise control on the drug dosage. This review presents some of the recent advances in the development of mesoporous silica nanocarriers for antitumoral therapy paying special attention on the stimuli-responsive systems able to release their load in response to external (light, magnetic field, temperature or ultrasounds or internal stimulus (enzymes, pH, redox, among others.

  3. Biodegradable mesoporous delivery system for biomineralization precursors.

    PubMed

    Yang, Hong-Ye; Niu, Li-Na; Sun, Jin-Long; Huang, Xue-Qing; Pei, Dan-Dan; Huang, Cui; Tay, Franklin R

    2017-01-01

    Scaffold supplements such as nanoparticles, components of the extracellular matrix, or growth factors have been incorporated in conventional scaffold materials to produce smart scaffolds for tissue engineering of damaged hard tissues. Due to increasing concerns on the clinical side effects of using large doses of recombinant bone-morphogenetic protein-2 in bone surgery, it is desirable to develop an alternative nanoscale scaffold supplement that is not only osteoinductive, but is also multifunctional in that it can perform other significant bone regenerative roles apart from stimulation of osteogenic differentiation. Because both amorphous calcium phosphate (ACP) and silica are osteoinductive, a biodegradable, nonfunctionalized, expanded-pore mesoporous silica nanoparticle carrier was developed for loading, storage, and sustained release of a novel, biosilicification-inspired, polyamine-stabilized liquid precursor phase of ACP for collagen biomineralization and for release of orthosilicic acid, both of which are conducive to bone growth. Positively charged poly(allylamine)-stabilized ACP (PAH-ACP) could be effectively loaded and released from nonfunctionalized expanded-pore mesoporous silica nanoparticles (pMSN). The PAH-ACP released from loaded pMSN still retained its ability to infiltrate and mineralize collagen fibrils. Complete degradation of pMSN occurred following unloading of their PAH-ACP cargo. Because PAH-ACP loaded pMSN possesses relatively low cytotoxicity to human bone marrow-derived mesenchymal stem cells, these nanoparticles may be blended with any osteoconductive scaffold with macro- and microporosities as a versatile scaffold supplement to enhance bone regeneration.

  4. Smart Mesoporous Nanomaterials for Antitumor Therapy

    PubMed Central

    Martínez-Carmona, Marina; Colilla, Montserrat; Vallet-Regí, Maria

    2015-01-01

    The use of nanomaterials for the treatment of solid tumours is receiving increasing attention by the scientific community. Among them, mesoporous silica nanoparticles (MSNs) exhibit unique features that make them suitable nanocarriers to host, transport and protect drug molecules until the target is reached. It is possible to incorporate different targeting ligands to the outermost surface of MSNs to selectively drive the drugs to the tumour tissues. To prevent the premature release of the cargo entrapped in the mesopores, it is feasible to cap the pore entrances using stimuli-responsive nanogates. Therefore, upon exposure to internal (pH, enzymes, glutathione, etc.) or external (temperature, light, magnetic field, etc.) stimuli, the pore opening takes place and the release of the entrapped cargo occurs. These smart MSNs are capable of selectively reaching and accumulating at the target tissue and releasing the entrapped drug in a specific and controlled fashion, constituting a promising alternative to conventional chemotherapy, which is typically associated with undesired side effects. In this review, we overview the recent advances reported by the scientific community in developing MSNs for antitumor therapy. We highlight the possibility to design multifunctional nanosystems using different therapeutic approaches aimed at increasing the efficacy of the antitumor treatment. PMID:28347103

  5. Continuous microwave flow synthesis of mesoporous hydroxyapatite.

    PubMed

    Akram, Muhammad; Alshemary, Ammar Z; Goh, Yi-Fan; Wan Ibrahim, Wan Aini; Lintang, Hendrik O; Hussain, Rafaqat

    2015-11-01

    We have successfully used continuous microwave flow synthesis (CMFS) technique for the template free synthesis of mesoporous hydroxyapatite. The continuous microwave flow reactor consisted of a modified 2.45GHz household microwave, peristaltic pumps and a Teflon coil. This cost effective and efficient system was exploited to produce semi-crystalline phase pure nano-sized hydroxyapatite. Effect of microwave power, retention time and the concentration of reactants on the phase purity, degree of crystallinity and surface area of the final product was studied in detail. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to study the phase purity and composition of the product, while transmission electron microscopy (TEM) was used to study the effect of process parameters on the morphology of hydroxyapatite. The TEM analysis confirmed the formation of spherical particles at low microwave power; however the morphology of the particles changed to mesoporous needle and rod-like structure upon exposing the reaction mixture to higher microwave power and longer retention time inside the microwave. The in-vitro ion dissolution behavior of the as synthesized hydroxyapatite was studied by determining the amount of Ca(2+) ion released in SBF solution. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Gated Silica Mesoporous Materials in Sensing Applications

    PubMed Central

    Sancenón, Félix; Pascual, Lluís; Oroval, Mar; Aznar, Elena; Martínez-Máñez, Ramón

    2015-01-01

    Silica mesoporous supports (SMSs) have a large specific surface area and volume and are particularly exciting vehicles for delivery applications. Such container-like structures can be loaded with numerous different chemical substances, such as drugs and reporters. Gated systems also contain addressable functions at openings of voids, and cargo delivery can be controlled on-command using chemical, biochemical or physical stimuli. Many of these gated SMSs have been applied for drug delivery. However, fewer examples of their use in sensing protocols have been reported. The approach of applying SMSs in sensing uses another concept—that of loading pores with a reporter and designing a capping mechanism that is selectively opened in the presence of a target analyte, which results in the delivery of the reporter. According to this concept, we provide herein a complete compilation of published examples of probes based on the use of capped SMSs for sensing. Examples for the detection of anions, cations, small molecules and biomolecules are provided. The diverse range of gated silica mesoporous materials presented here highlights their usefulness in recognition protocols. PMID:26491626

  7. Phosphoryl functionalized mesoporous silica for uranium adsorption

    NASA Astrophysics Data System (ADS)

    Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

    2017-04-01

    Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N2 adsorption-desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG0, ΔH0 and ΔS0) confirmed that the adsorption process was endothermic and spontaneous.

  8. Biocompatibility and levofloxacin delivery of mesoporous materials.

    PubMed

    Cicuéndez, Mónica; Izquierdo-Barba, Isabel; Portolés, María Teresa; Vallet-Regí, María

    2013-05-01

    A comparative study of mesoporous matrices designed for both drug-loading methods, impregnation (IP) and surfactant-assisted drug loading (also denoted as one-pot, OP), has been carried out evaluating their physicochemical characteristics, cell response, drug delivery profiles, and antibacterial activity. Surfactant-free (calcined) and surfactant-templated (non-calcined) mesoporous silica have been used as IP and OP starting matrices, respectively. Both non-calcined and calcined matrices do not exert any cytotoxic effect on osteoblasts. However, non-calcined matrices induce on fibroblasts a significant proliferation delay with morphological alterations and dose-dependent increases in fibroblast size, internal complexity, and intracellular calcium content but without cell lysis and apoptosis. Residual ethanol and the surface silanol groups in these non-calcined matrices are involved in the observed fibroblast changes. Finally, both IP and OP matrices have been loaded with levofloxacin to compare them as drug delivery systems. Both IP and OP matrices exhibit similar in vitro levofloxacin release profiles, showing an initial fast delivery followed by a sustained release during long time periods. These profiles and the antimicrobial activity results suggest the use of these IP and OP matrices as local drug delivery systems in the osteomyelitis and other bone infection treatments.

  9. Mesoporous titanium dioxide coating for metallic implants.

    PubMed

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

    2012-01-01

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

  10. Biodegradable mesoporous delivery system for biomineralization precursors

    PubMed Central

    Yang, Hong-ye; Niu, Li-na; Sun, Jin-long; Huang, Xue-qing; Pei, Dan-dan; Huang, Cui; Tay, Franklin R

    2017-01-01

    Scaffold supplements such as nanoparticles, components of the extracellular matrix, or growth factors have been incorporated in conventional scaffold materials to produce smart scaffolds for tissue engineering of damaged hard tissues. Due to increasing concerns on the clinical side effects of using large doses of recombinant bone-morphogenetic protein-2 in bone surgery, it is desirable to develop an alternative nanoscale scaffold supplement that is not only osteoinductive, but is also multifunctional in that it can perform other significant bone regenerative roles apart from stimulation of osteogenic differentiation. Because both amorphous calcium phosphate (ACP) and silica are osteoinductive, a biodegradable, nonfunctionalized, expanded-pore mesoporous silica nanoparticle carrier was developed for loading, storage, and sustained release of a novel, biosilicification-inspired, polyamine-stabilized liquid precursor phase of ACP for collagen biomineralization and for release of orthosilicic acid, both of which are conducive to bone growth. Positively charged poly(allylamine)-stabilized ACP (PAH-ACP) could be effectively loaded and released from nonfunctionalized expanded-pore mesoporous silica nanoparticles (pMSN). The PAH-ACP released from loaded pMSN still retained its ability to infiltrate and mineralize collagen fibrils. Complete degradation of pMSN occurred following unloading of their PAH-ACP cargo. Because PAH-ACP loaded pMSN possesses relatively low cytotoxicity to human bone marrow-derived mesenchymal stem cells, these nanoparticles may be blended with any osteoconductive scaffold with macro- and microporosities as a versatile scaffold supplement to enhance bone regeneration. PMID:28182119

  11. Synthesis of mesoporous nano-hydroxyapatite by using zwitterions surfactant

    EPA Science Inventory

    Mesoporous nano-hydroxyapatite (mn-HAP) was successfully synthesized via a novel micelle-templating method using lauryl dimethylaminoacetic acid as zwitterionic surfactant. The systematic use of such a surfactant in combination with microwave energy inputenables the precise contr...

  12. Enzyme catalytic membrane based on a hybrid mesoporous membrane.

    PubMed

    Fu, Wensheng; Yamaguchi, Akira; Kaneda, Hideaki; Teramae, Norio

    2008-02-21

    Immobilization of glucose oxidase (GOD) within a hybrid mesoporous membrane with 12 nm pore diameter was successfully achieved, resulting in catalytically high efficiency during flow of a glucose solution across the membrane.

  13. Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

    DOE PAGES

    Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...

    2017-09-05

    Here, we report a facile synthetic protocol to pre-pare mesoporous FeS2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeS2 is attributed to themore » exposed (210) facets. The mesoporous FeS2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

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

    SciTech Connect

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

    2015-01-27

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

  15. Synthesis of stishovite nanocrystals from periodic mesoporous silica.

    PubMed

    Mohanty, Paritosh; Li, Dong; Liu, Tianbo; Fei, Yingwei; Landskron, Kai

    2009-03-04

    Faceted stishovite nanocrystals with sizes of 200-400 nm were synthesized at a pressure of 12 GPa and a temperature of 400 degrees C in a multianvil apparatus using mesoporous silica SBA-16 as the precursor.

  16. Underpotential deposition and anodic stripping voltammetry at mesoporous microelectrodes.

    PubMed

    Sanchez, Pablo Lozano; Elliott, Joanne M

    2005-05-01

    Using the technique of liquid crystal templating a series of high surface area mesoporous platinum microelectrodes was fabricated. The underpotential deposition of metal ions at such electrodes was found to be similar to that at conventional platinum electrodes. The phenomena of underpotential deposition, in combination with the intrinsic properties of mesoporous microelectrodes (i.e. a high surface area and efficient mass transport) was exploited for the purpose of anodic stripping voltammetry. In particular the underpotential deposition of Ag(+), Pb(2+) and Cu(2+) ions was investigated and it was found that mesoporous microelectrodes were able to quantify the concentration of ions in solution down to the ppb range. The overall behaviour of the mesoporous electrodes was found to be superior to that of conventional microelectrodes and the effects of interference by surfactants were minimal.

  17. Synthesis of mesoporous nano-hydroxyapatite by using zwitterions surfactant

    EPA Science Inventory

    Mesoporous nano-hydroxyapatite (mn-HAP) was successfully synthesized via a novel micelle-templating method using lauryl dimethylaminoacetic acid as zwitterionic surfactant. The systematic use of such a surfactant in combination with microwave energy inputenables the precise contr...

  18. Mesoporous silicas with tunable morphology for the immobilization of laccase.

    PubMed

    Gascón, Victoria; Díaz, Isabel; Márquez-Álvarez, Carlos; Blanco, Rosa M

    2014-05-30

    Siliceous ordered mesoporous materials (OMM) are gaining interest as supports for enzyme immobilization due to their uniform pore size, large surface area, tunable pore network and the introduction of organic components to mesoporous structure. We used SBA-15 type silica materials, which exhibit a regular 2D hexagonal packing of cylindrical mesopores of uniform size, for non-covalent immobilization of laccase. Synthesis conditions were adjusted in order to obtain supports with different particle shape, where those with shorter channels had higher loading capacity. Despite the similar isoelectric points of silica and laccase and the close match between the size of laccase and the pore dimensions of these SBA-15 materials, immobilization was achieved with very low leaching. Surface modification of macro-/mesoporous amorphous silica by grafting of amine moieties was proved to significantly increase the isoelectric point of this support and improve the immobilization yield.

  19. Mesoporous silicates: Materials science and biological applications

    NASA Astrophysics Data System (ADS)

    Roggers, Robert Anthony

    This thesis dissertation presents the collective research into the advancement of mesoporous silicate particles as biointerface devices, the development of new materials and the application of these particles as solid supports for heterogeneous catalysis. Mesoporous silica has been utilized in the aforementioned applications due to several reasons; the first being the ability to achieve high surface areas (500 - 1000 m2 g-1) with controlled pore sizes and particle morphology. Another reason for their popularity is their robustness in applications of heterogeneous catalysis and the ability to functionalize the surface with a wide variety of organic functional groups. In the field of biointerface devices, mesoporous silica nanoparticles represent a class of materials that exhibit high biocompatibility. In addition, the ability to functionalize the surfaces (outer surface and pore interiors) allows the particles to be targeted to specific cell types as well as the ability to release many different therapeutic molecules under specific stimuli. A unique particle coating consisting of a chemically cleavable lipid bilayer that allows for the encapsulation of a fluorescent molecule and increases the biocompatibility of the particle has been developed. The lipid bilayer coated mesoporous silica nanoparticle (LB-MSN) was characterized using X-ray diffraction, transmission electron microscopy and nitrogen `sorption isotherms. The finished LB-MSN was then incubated with mammalian cells in order to prove their biocompatibility. Confocal micrographs demonstrate the endocytosis of the particles into the cells. In addition the micrographs also show that the LB-MSNs are separate from the endosomal compartments, however due to the lipophilic nature of the dye used to label the endosome there is some debate regarding this conclusion. The lipid bilayer coating was then applied to a large pore MSN (l-MSN) which had been previously shown to cause lysis of red blood cells (RBCs) at low

  20. Solar hydrogen and solar electricity using mesoporous materials

    NASA Astrophysics Data System (ADS)

    Mahoney, Luther

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

  1. Simple synthesis of mesoporous boron nitride with strong cathodoluminescence emission

    SciTech Connect

    Meng, Xiang-Lin; Lun, Ning; Qi, Yong-Xin; Zhu, Hui-Ling; Han, Fu-Dong; Yin, Long-Wei; Fan, Run-Hua; Bai, Yu-Jun; Bi, Jian-Qiang

    2011-04-15

    Mesoporous BN was prepared at 550 {sup o}C for 10 h or so via a simple reaction between NaBH{sub 4} and CO(NH{sub 2}){sub 2}. X-ray diffraction demonstrates the formation of t-BN with lattice constants a=2.46 and c=6.67 A. High-resolution transmission electron microscopy displays a lot of porous films in the product, which possesses a high surface area of 219 m{sup 2} g{sup -1} and a pore size primarily around 3.8 nm tested by nitrogen adsorption-desorption method. The mesoporous BN exhibits a strong luminescence emission around 3.41 eV in the cathodoluminescence spectra, a high stability in both morphology and structure, and good oxidation resistance up to 800 {sup o}C. The byproducts generated during the reaction are responsible for the formation of the mesoporous BN. -- Graphical abstract: The mesoporous BN with a high specific surface area of 219 m{sup 2} g{sup -1} exhibits a strong luminescence emission around 3.41 eV in the CL spectra, high thermal stability in both morphology and structure, and good oxidation resistance up to 800 {sup o}C. Display Omitted Research highlights: Mesoporous BN was prepared by a simple reaction between NaBH{sub 4} and CO(NH{sub 2}){sub 2} at 550 {sup o}C. The mesoporous BN possesses a high surface area of 219 m{sup 2} g{sup -1}. The mesoporous BN exhibits a strong luminescence emission around 3.41 eV. The mesoporous BN has high stability and good oxidation resistance up to 800 {sup o}C.

  2. Near-infrared emission from mesoporous crystalline germanium

    SciTech Connect

    Boucherif, Abderraouf; Aimez, Vincent; Arès, Richard; Korinek, Andreas

    2014-10-15

    Mesoporous crystalline germanium was fabricated by bipolar electrochemical etching of Ge wafer in HF-based electrolyte. It yields uniform mesoporous germanium layers composed of high density of crystallites with an average size 5-7 nm. Subsequent extended chemical etching allows tuning of crystallites size while preserving the same chemical composition. This highly controllable nanostructure exhibits photoluminescence emission above the bulk Ge bandgap, in the near-infrared range (1095-1360nm) with strong evidence of quantum confinement within the crystallites.

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

    SciTech Connect

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

    2010-02-15

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

  4. Near-infrared emission from mesoporous crystalline germanium

    NASA Astrophysics Data System (ADS)

    Boucherif, Abderraouf; Korinek, Andreas; Aimez, Vincent; Arès, Richard

    2014-10-01

    Mesoporous crystalline germanium was fabricated by bipolar electrochemical etching of Ge wafer in HF-based electrolyte. It yields uniform mesoporous germanium layers composed of high density of crystallites with an average size 5-7 nm. Subsequent extended chemical etching allows tuning of crystallites size while preserving the same chemical composition. This highly controllable nanostructure exhibits photoluminescence emission above the bulk Ge bandgap, in the near-infrared range (1095-1360nm) with strong evidence of quantum confinement within the crystallites.

  5. In-situ immobilization of enzymes in mesoporous silicas

    NASA Astrophysics Data System (ADS)

    Santalla, Esther; Serra, Elías; Mayoral, Alvaro; Losada, José; Blanco, Rosa M.; Díaz, Isabel

    2011-04-01

    Lipase from Candida antarctica B, horseradish peroxidase and laccase have been entrapped in silica cages rising mesoporous structures. Lipase and laccase yielded the highest structured mesoporous material whereas horseradish peroxidase may have altered the symmetry giving as a result mesocelullar foam (MCF) type of cages. The possible effect in the final structure of the material of the nature, size and surface structure of the proteins as well as the presence of various additives in the enzyme extracts is currently under investigations.

  6. Mesoporous VN prepared by solid-solid phase separation

    SciTech Connect

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

    2013-01-15

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

  7. Synthesis of high thermally-stable mesoporous alumina particles.

    PubMed

    Song, Lee-Hwa; Park, Seung Bin

    2010-01-01

    The mesoporous undoped and Si-doped alumina were prepared with an ultrasonic spray process, and found to have well-developed mesopore structures and large surface areas. The mesoporous Si-doped alumina has a high thermal stability up to 1473 K. Its surface area and pore volume were found to slowly decrease with increasing temperature. Mesoporous undoped alumina is transformed to gamma-alumina at 1073 K, whereas the amorphous nature of the pore walls of the Si-doped alumina is maintained up to 1073 K. When heat treatment was carried out at 1473 K for 2 h, the mesopore-networks of the undoped alumina collapsed, and then all the pore walls were converted into the alpha-alumina phase. In contrast, the mesoporosity of the Si-doped alumina persisted during heat treatment, and its pore walls were transformed to gamma-alumina. The decreases in the pore volume of the undoped alumina at 1073 K and 1473 K were found to be 36% and 99% respectively, but for the Si-doped alumina were only 24% and 36% respectively. The surface area of the undoped alumina at 1473 K was found to be 11 m2/g but that of the Si-doped samples at the same temperature is higher than 100 m2/g. Thus this mesoporous Si-doped alumina can be used as a catalytic support in reactions at high temperatures.

  8. Grafting Sulfated Zirconia on Mesoporous Silica

    SciTech Connect

    Wang, Yong; Lee, Kwan Young; Choi, Saemin; Liu, Jun; Wang, Li Q.; Peden, Charles HF

    2007-06-01

    Sulfated zirconia has received considerable attention as a potential solid acid catalyst in recent years. In this paper, the preparation and properties of acid catalysts obtained by grafting ziconia with atomic precision on MCM-41 mesoporous silica were studied. TEM and potential titration characterizations revealed that ZrO2/MCM-41 with monolayer coverage can be obtained using this grafting technique. Sulfated ZrO2/MCM-41 exhibits improved thermal stability than that of bulk sulfated zirconia, as evidenced by temperature programmed characterizations and XRD analysis. Temperature programmed reaction of isopropanol was used to evaluate the acidity of sulfated ZrO2/MCM-41. It was found that the acid strength of sulfated ZrO2/MCM-41 with monolayer coverage is weaker than bulk sulfated zirconia but stronger than SiO2-Al2O3, a common strong acid catalyst.

  9. C60-PMO: periodic mesoporous buckyballsilica.

    PubMed

    Whitnall, Wesley; Cademartiri, Ludovico; Ozin, Geoffrey A

    2007-12-19

    Here we report the first documented synthesis of a periodic mesoporous organosilica (PMO), that contains a multiply bonded C60 moiety integrated into the silica channel walls of the material, dubbed C60-PMO. This is accomplished through the acid-catalyzed co-assembly, of C60(NHCH2CH2CH2Si(OEt)3)x and tetraethylorthosilicate (TEOS) with a polyethyleneoxide-polylpropyleneoxide-polyethyleneoxide triblock copolymer template. The percentage of C60 in the final material was estimated to be a minimum of 63 vol %, but potentially as high as 91 vol %. The effects of the synthesis conditions on the mesostructure of the resulting materials are examined. In particular, we demonstrate that the C60 is uniformly distributed throughout the entire sample by the use of energy dispersive X-ray fluorescence (EDX) analysis and an OsO4 label bonded to the C60.

  10. Mesoporous organohydrogels from thermogelling photocrosslinkable nanoemulsions

    NASA Astrophysics Data System (ADS)

    Helgeson, Matthew E.; Moran, Shannon E.; An, Harry Z.; Doyle, Patrick S.

    2012-04-01

    We report the formation of mesoporous organohydrogels from oil-in-water nanoemulsions containing an end-functionalized oligomeric gelator in the aqueous phase. The nanoemulsions exhibit an abrupt thermoreversible transition from a low-viscosity liquid to a fractal-like colloidal gel of droplets with mesoscale porosity and solid-like viscoelasticity with moduli approaching 100 kPa, possibly the highest reported for an emulsion-based system. We hypothesize that gelation is brought about by temperature-induced interdroplet bridging of the gelator, as shown by its dependence on the gelator chemistry. The use of photocrosslinkable gelators enables the freezing of the nanoemulsion’s microstructure into a soft hydrogel nanocomposite containing a large fraction of dispersed liquid hydrophobic compartments, and we show its use in the encapsulation and release of lipophilic biomolecules. The tunable structural, mechanical and optical properties of these organohydrogels make them a robust material platform suitable for a wide range of applications.

  11. Mesoporous silica nanoparticles inhibit cellular respiration.

    PubMed

    Tao, Zhimin; Morrow, Matthew P; Asefa, Tewodros; Sharma, Krishna K; Duncan, Cole; Anan, Abhishek; Penefsky, Harvey S; Goodisman, Jerry; Souid, Abdul-Kader

    2008-05-01

    We studied the effect of two types of mesoporous silica nanoparticles, MCM-41 and SBA-15, on mitochondrial O 2 consumption (respiration) in HL-60 (myeloid) cells, Jurkat (lymphoid) cells, and isolated mitochondria. SBA-15 inhibited cellular respiration at 25-500 microg/mL; the inhibition was concentration-dependent and time-dependent. The cellular ATP profile paralleled that of respiration. MCM-41 had no noticeable effect on respiration rate. In cells depleted of metabolic fuels, 50 microg/mL SBA-15 delayed the onset of glucose-supported respiration by 12 min and 200 microg/mL SBA-15 by 34 min; MCM-41 also delayed the onset of glucose-supported respiration. Neither SBA-15 nor MCM-41 affected cellular glutathione. Both nanoparticles inhibited respiration of isolated mitochondria and submitochondrial particles.

  12. Preparation ways and photoluminescence of mesoporous alumina

    NASA Astrophysics Data System (ADS)

    Zhang, P.; Liu, J.; Zhao, X.; Wu, G.

    2010-12-01

    High specific surface area (SSA) mesoporous alumina (MA) is synthesized by a sol-gel method using pelagic clay as the raw material. The MA synthesized with a (1-hexadecyl) trimethylammonium bromide (CTAB): utea mixed template shows a SSA of 385.56 m2/g and a mean pore size of 3.6 nm. And the SSA of the MA synthesized with the mixed template is increased compared with the MA synthesized with a CTAB single template. Simultaneously, the MA exhibits a blue photoluminescence which come from the defect F+ and F centers, and the higher PL emission of the MA synthesized with a CTAB: utea mixed template is attributed to the high defect center density in the MA.

  13. (129)Xe NMR of Mesoporous Silicas

    SciTech Connect

    Anderson, M.T.; Asink, R.A.; Kneller, J.M.; Pietrass, T.

    1999-04-23

    The porosities of three mesoporous silica materials were characterized with {sup 129}Xe NMR spectroscopy. The materials were synthesized by a sol-gel process with r = 0, 25, and 70% methanol by weight in an aqueous cetyltrimethylammonium bromide solution. Temperature dependent chemical shifts and spin lattice relaxation times reveal that xenon does not penetrate the pores of the largely disordered (r= 70%) silica. For both r = 0 and 25%, temperature dependent resonances corresponding to physisorbed xenon were observed. An additional resonance for the r = 25% sample was attributed to xenon between the disordered cylindrical pores. 2D NMR exchange experiments corroborate the spin lattice relaxation data which show that xenon is in rapid exchange between the adsorbed and the gas phase.

  14. Enantioselective recognition at mesoporous chiral metal surfaces

    PubMed Central

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

    2014-01-01

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

  15. Enantioselective recognition at mesoporous chiral metal surfaces

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  16. Hierarchical Composites to Reduce N-Nitrosamines in Cigarette Smoke.

    PubMed

    Li, Yan Yan; Cao, Yi; Yue, Ming Bo; Yang, Jing; Zhu, Jian Hua

    2015-03-20

    In order to reduce the harmful constituents in cigarette smoke, two hierarchical composites were synthesized. Based on, zeolites HZSM-5 or NaY fragments were introduced into the synthetic system of mesoporous silica SBA-15 or MCM-41 and assembled with the mesoporous materials. These porous composites combine the advantages of micro- and mesoporous materials, and exhibit higher effects than activated carbon on reducing tobacco specific nitrosamines (TSNA) and some vapor phase compounds in smoke.

  17. Adsorption and release of biocides with mesoporous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Popat, Amirali; Liu, Jian; Hu, Qiuhong; Kennedy, Michael; Peters, Brenton; Lu, Gao Qing (Max); Qiao, Shi Zhang

    2012-01-01

    In this proof-of-concept study, an agricultural biocide (imidacloprid) was effectively loaded into the mesoporous silica nanoparticles (MSNs) with different pore sizes, morphologies and mesoporous structures for termite control. This resulted in nanoparticles with a large surface area, tunable pore diameter and small particle size, which are ideal carriers for adsorption and controlled release of imidacloprid. The effect of pore size, surface area and mesoporous structure on uptake and release of imidacloprid was systematically studied. It was found that the adsorption amount and release profile of imidacloprid were dependent on the type of mesoporous structure and surface area of particles. Specifically, MCM-48 type mesoporous silica nanoparticles with a three dimensional (3D) open network structure and high surface area displayed the highest adsorption capacity compared to other types of silica nanoparticles. Release of imidacloprid from these nanoparticles was found to be controlled over 48 hours. Finally, in vivo laboratory testing on termite control proved the efficacy of these nanoparticles as delivery carriers for biopesticides. We believe that the present study will contribute to the design of more effective controlled and targeted delivery for other biomolecules.In this proof-of-concept study, an agricultural biocide (imidacloprid) was effectively loaded into the mesoporous silica nanoparticles (MSNs) with different pore sizes, morphologies and mesoporous structures for termite control. This resulted in nanoparticles with a large surface area, tunable pore diameter and small particle size, which are ideal carriers for adsorption and controlled release of imidacloprid. The effect of pore size, surface area and mesoporous structure on uptake and release of imidacloprid was systematically studied. It was found that the adsorption amount and release profile of imidacloprid were dependent on the type of mesoporous structure and surface area of particles

  18. Enhanced retention of aqueous transition metals in mesoporous silica

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  19. Photoelectrochemical enzymatic biosensing of glucose using mesoporous TiO2

    NASA Astrophysics Data System (ADS)

    Chithralekha, P.; Kumar, V. T. Fidal; Chandra, T. S.; Roy, Somnath C.

    2017-05-01

    Mesoporous titania is prepared by sol-gel method. The enzymatic biosensing of glucose is done with mesoporous tiatania on ITO coated glass plates using photoelectrochemical method and mechanism of sensing is discussed.

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

    PubMed

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

    2001-10-21

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

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

    DOEpatents

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

    2017-04-11

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

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

    NASA Astrophysics Data System (ADS)

    Gomez, Sinue

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

  3. The Synthesis of Ag-Doped Mesoporous TiO2

    SciTech Connect

    Li, Xiaohong S.; Fryxell, Glen E.; Wang, Chong M.; Engelhard, Mark H.

    2008-04-15

    Ag-doped mesoporous titanium oxide was prepared using non-ionic surfactants and easily handled titanium precursors, under mild reaction conditions. In contrast to the stabilizing effect of Cd-doping on mesoporous TiO2, Ag-doping was found to significantly destabilize the mesoporous structure.

  4. Bioactive mesoporous wollastonite particles for bone tissue engineering

    PubMed Central

    Saravanan, S; Selvamurugan, Nagarajan

    2016-01-01

    The current investigation was aimed at identifying the role of mesoporous wollastonite particles on the healing of rat tibial bone defect. The bone defect was created with a 3-mm-diameter dental drill, and it was filled with mesoporous wollastonite particles. After second and fourth weeks of filling treatments, it was found that mesoporous wollastonite particles promoted bone formation as evidenced by X-ray, histological, scanning electron microscope, and energy-dispersive spectra studies. X-ray study showed the closure of drill hole as seen by high-dense radio-opacity image. Histological analysis depicted the deposition of collagen in the bone defect area in response to mesoporous wollastonite particles’ treatment. Scanning electron microscope–energy-dispersive spectra analyses of the sectioned implants also identified the deposition of apatite by these particles. Thus, our results suggested that mesoporous wollastonite particles have bioactive properties, and they can be used as a suitable filling material for promotion of bone formation in vivo. PMID:27928496

  5. Design and functionalization of photocatalytic systems within mesoporous silica.

    PubMed

    Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

    2014-06-01

    In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described.

  6. Mesoporous silica nanoparticles in target drug delivery system: A review

    PubMed Central

    Bharti, Charu; Nagaich, Upendra; Pal, Ashok Kumar; Gulati, Neha

    2015-01-01

    Due to lack of specification and solubility of drug molecules, patients have to take high doses of the drug to achieve the desired therapeutic effects for the treatment of diseases. To solve these problems, there are various drug carriers present in the pharmaceuticals, which can used to deliver therapeutic agents to the target site in the body. Mesoporous silica materials become known as a promising candidate that can overcome above problems and produce effects in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles (MSNs) are widely used as a delivery reagent because silica possesses favorable chemical properties, thermal stability, and biocompatibility. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release of the target site. The properties of mesoporous, including pore size, high drug loading, and porosity as well as the surface properties, can be altered depending on additives used to prepare MSNs. Active surface enables functionalization to changed surface properties and link therapeutic molecules. They are used as widely in the field of diagnosis, target drug delivery, bio-sensing, cellular uptake, etc., in the bio-medical field. This review aims to present the state of knowledge of silica containing mesoporous nanoparticles and specific application in various biomedical fields. PMID:26258053

  7. Organized thiol functional groups in mesoporous core shell colloids

    SciTech Connect

    Marchena, Martin H.; Granada, Mara; Bordoni, Andrea V.; Joselevich, Maria; Troiani, Horacio; Williams, Federico J.; Wolosiuk, Alejandro

    2012-03-15

    The co-condensation in situ of tetraethoxysilane (TEOS) and mercaptopropyltrimethoxysilane (MPTMS) using cetyltrimethylammonium bromide (CTAB) as a template results in the synthesis of multilayered mesoporous structured SiO{sub 2} colloids with 'onion-like' chemical environments. Thiol groups were anchored to an inner selected SiO{sub 2} porous layer in a bilayered core shell particle producing different chemical regions inside the colloidal layered structure. X-Ray Photoelectron Spectroscopy (XPS) shows a preferential anchoring of the -SH groups in the double layer shell system, while porosimetry and simple chemical modifications confirm that pores are accessible. We can envision the synthesis of interesting colloidal objects with defined chemical environments with highly controlled properties. - Graphical abstract: Mesoporous core shell SiO{sub 2} colloids with organized thiol groups. Highlights: Black-Right-Pointing-Pointer Double shell mesoporous silica colloids templated with CTAB. Black-Right-Pointing-Pointer Sequential deposition of mesoporous SiO{sub 2} layers with different chemistries. Black-Right-Pointing-Pointer XPS shows the selective functionalization of mesoporous layers with thiol groups.

  8. Formation of monodisperse mesoporous silica microparticles via spray-drying.

    PubMed

    Waldron, Kathryn; Wu, Winston Duo; Wu, Zhangxiong; Liu, Wenjie; Selomulya, Cordelia; Zhao, Dongyuan; Chen, Xiao Dong

    2014-03-15

    In this work, a protocol to synthesize monodisperse mesoporous silica microparticles via a unique microfluidic jet spray-drying route is reported for the first time. The microparticles demonstrated highly ordered hexagonal mesostructures with surface areas ranging from ~900 up to 1500 m(2)/g and pore volumes from ~0.6 to 0.8 cm(3)/g. The particle size could be easily controlled from ~50 to 100 μm from the same diameter nozzle via changing the initial solute content, or changing the drying temperature. The ratio of the surfactant (CTAB) and silica (TEOS), and the amount of water in the precursor were found to affect the degree of ordering of mesopores by promoting either the self-assembly of the surfactant-silica micelles or the condensation of the silica as two competing processes in evaporation induced self-assembly. The drying rate and the curvature of particles also affected the self-assembly of the mesostructure. The particle mesostructure is not influenced by the inlet drying temperature in the range of 92-160 °C, with even a relatively low temperature of 92 °C producing highly ordered mesoporous microparticles. The spray-drying derived mesoporous silica microparticles, while of larger sizes and more rapidly synthesized, showed a comparable performance with the conventional mesoporous silica MCM-41 in controlled release of a dye, Rhodamine B, indicating that these spray dried microparticles could be used for the immobilisation and controlled release of small molecules.

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

    PubMed

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

    2014-01-01

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

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

    PubMed Central

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

    2014-01-01

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

  11. Diamine Functionalized Cubic Mesoporous Silica for Ibuprofen Controlled Delivery.

    PubMed

    Sivaguru, J; Selvaraj, M; Ravi, S; Park, H; Song, C W; Chun, H H; Ha, C-S

    2015-07-01

    A diamine functionalized cubic mesostructured KIT-6 (N-KIT-6) has been prepared by post-synthetic method using calcined mesoporous KIT-6 with a diamine source, i.e., N-'[3-(tri methoxysilyl)- propyl]'ethylenediamine. The KIT-6 mesoporous silica used for N-KIT-6 was synthesized under weak acidic hydrothermal method using bitemplates, viz., Pluronic P123 and 1-butanol. The synthesized mesoporous materials, KIT-6 and N-KIT-6, have been characterized by the relevant instrumental techniques such as SAXS, N2 sorption isotherm, FT-IR, SEM, TEM and TGA to prove the standard mesoporous materials with the identification of diamine groups. The characterized mesoporous materials, KIT-6 and N-KIT-6, have been extensively used in the potential application of controlled drug delivery, where ibuprofen (IBU) employed as a model drug. The rate of IBU adsorption and release was monitored by UV vis-spectrometer. On the basis of the experimental results of controlled drug delivery system, the results of IBU adsorption and releasing rate in N-KIT-6 are higher than those of KIT-6 because of the higher hydrophobic nature as well as rich basic sites on the surface of inner pore wall silica.

  12. Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

    PubMed Central

    2012-01-01

    Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors. PMID:22643113

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  14. Nanostructured materials based on mesoporous silica and mesoporous silica/apatite as osteogenic growth peptide carriers.

    PubMed

    Mendes, L S; Saska, S; Martines, M A U; Marchetto, R

    2013-10-01

    The aim of this work was the preparation of inorganic mesoporous materials from silica, calcium phosphate and a nonionic surfactant and to evaluate the incorporation and release of different concentrations of osteogenic growth peptide (OGP) for application in bone regeneration. The adsorption and release of the labeled peptide with 5,6-carboxyfluorescein (OGP-CF) from the mesoporous matrix was monitored by fluorescence spectroscopy. The specific surface area was 880 and 484 m(2) g(-1) for pure silica (SiO) and silica/apatite (SiCaP), respectively; the area influenced the percentage of incorporation of the peptide. The release of OGP-CF from the materials in simulated body fluid (SBF) was dependent on the composition of the particles, the amount of incorporated peptide and the degradation of the material. The release of 50% of the peptide content occurred at around 4 and 30 h for SiCaP and SiO, respectively. In conclusion, the materials based on SiO and SiCaP showed in vitro bioactivity and degradation; thus, these materials should be considered as alternative biomaterials for bone regeneration.

  15. Zirconia-silica based mesoporous desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

    Palomino, Jessica M.; Tran, Dat T.; Kareh, Ana R.; Miller, Christopher A.; Gardner, Joshua M. V.; Dong, Hong; Oliver, Scott R. J.

    2015-03-01

    We report a series of mesoporous silicate sorbent materials templated by long-chain primary alkylamines that display record level of desulfurization of the jet fuel JP-8. Pure silica frameworks and those with a Si:Zr synthesis molar ratio ranging from 44:1 to 11:1 were investigated. The optimum sorbent was identified as dodecylamine-templated silica-zirconia synthesized from a gel with Si:Zr molar ratio of 15:1. With an optimized silver loading of 11 wt.%, a saturation adsorption capacity of 39.4 mgS g-1 and a silver efficiency of 1.21 molS mol Ag-1 were observed for JP-8. This sorbent displayed exceptional regenerability, maintaining 86% of its initial capacity in model fuel after solvent regeneration with diethyl ether. Low-cost, portable and reusable sorbents for the desulfurization of JP-8 jet fuel are needed to make solid oxide fuel cells (SOFCs) a reality for military power needs. SOFCs require ultra-low sulfur content fuel, which traditional desulfurization methods cannot achieve.

  16. Controlled drug release from bifunctionalized mesoporous silica

    SciTech Connect

    Xu Wujun; Gao Qiang; Xu Yao Wu Dong; Sun Yuhan; Shen Wanling; Deng Feng

    2008-10-15

    Serial of trimethylsilyl-carboxyl bifunctionalized SBA-15 (TMS/COOH/SBA-15) have been studied as carriers for controlled release of drug famotidine (Famo). To load Famo with large capacity, SBA-15 with high content of carboxyl groups was successfully synthesized by one-pot synthesis under the assistance of KCl. The mesostructure of carboxyl functionalized SBA-15 (COOH/SBA-15) could still be kept even though the content of carboxyl groups was up to 57.2%. Increasing carboxyl content could effectively enhance the loading capacity of Famo. Compared with pure SBA-15, into which Famo could be hardly adsorbed, the largest drug loading capacity of COOH/SBA-15 could achieve 396.9 mg/g. The release of Famo from mesoporous silica was studied in simulated intestine fluid (SIF, pH=7.4). For COOH/SBA-15, the release rate of Famo decreased with narrowing pore size. After grafting TMS groups on the surface of COOH/SBA-15 with hexamethyldisilazane, the release of Famo was greatly delayed with the increasing content of TMS groups. - Graphical abstract: Trimethylsilyl-carboxyl bifunctionalized SBA-15 has been studied as carrier for controlled release of drug famotidine. To load drug with large capacity, SBA-15 with high content of carboxyl groups was successfully synthesized. After grafting trimethylsilyl groups on the surface of carboxyl functionalized SBA-15, the release of Famo was greatly delayed with the increasing content of TMS groups.

  17. Mesoporous materials for clean energy technologies.

    PubMed

    Linares, Noemi; Silvestre-Albero, Ana M; Serrano, Elena; Silvestre-Albero, Joaquín; García-Martínez, Javier

    2014-11-21

    Alternative energy technologies are greatly hindered by significant limitations in materials science. From low activity to poor stability, and from mineral scarcity to high cost, the current materials are not able to cope with the significant challenges of clean energy technologies. However, recent advances in the preparation of nanomaterials, porous solids, and nanostructured solids are providing hope in the race for a better, cleaner energy production. The present contribution critically reviews the development and role of mesoporosity in a wide range of technologies, as this provides for critical improvements in accessibility, the dispersion of the active phase and a higher surface area. Relevant examples of the development of mesoporosity by a wide range of techniques are provided, including the preparation of hierarchical structures with pore systems in different scale ranges. Mesoporosity plays a significant role in catalysis, especially in the most challenging processes where bulky molecules, like those obtained from biomass or highly unreactive species, such as CO2 should be transformed into most valuable products. Furthermore, mesoporous materials also play a significant role as electrodes in fuel and solar cells and in thermoelectric devices, technologies which are benefiting from improved accessibility and a better dispersion of materials with controlled porosity.

  18. Nanostructured mesoporous silica matrices in nanomedicine.

    PubMed

    Vallet-Regí, M

    2010-01-01

    In the last few years the biomedical research field has shown a growing interest towards nanostructured mesoporous silica materials, whose chemical composition is silica and present nanometric pores. These bioceramics exhibit two important features: they can regenerate osseous tissues--the bond bioactivity of these materials has been confirmed by the formation of biological-like nanoapatites on their surface when in contact with physiological fluids--and they are able to act as controlled release systems. Drugs in the nanometre scale can be loaded on those matrices and then locally released in a controlled fashion. It is possible to chemically modify the silica walls to favour the adsorption of certain biomolecules such as peptides, proteins or growth factors. It is even possible to design smart biomaterials where the drug is released under an external stimulus. Thus, looking at all those properties, a question arises: Have these bioceramics good expectations to be used in clinical medical practice? Their biocompatibility, bioactivity, capacity to regenerate bone and ability to act as controlled release systems of biologically active species have been confirmed. In fact, their preliminary in vitro and in vivo essays have been positive. Now it is the time to adequate all these properties to the actual clinical problems, and to evaluate their efficiency in comparison with materials already known and currently employed such as bioglasses.

  19. Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents, whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. Details addressing the design, synthesis and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental clean-up necessary after 40 years of weapons grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  20. Mesoporous silica and organosilica films templated by nanocrystalline chitin.

    PubMed

    Nguyen, Thanh-Dinh; Shopsowitz, Kevin E; MacLachlan, Mark J

    2013-11-04

    Liquid crystalline phases can be used to impart order into inorganic solids, creating materials that mimic natural architectures. Herein, mesoporous silica and organosilica films with layered structures and high surface areas have been templated by nanocrystalline chitin. Aqueous suspensions of spindle-shaped chitin nanocrystals were prepared by sequential deacetylation and hydrolysis of chitin fibrils isolated from king crab shells. The nanocrystalline chitin self-assembles into a nematic liquid-crystalline phase that has been used to template silica and organosilica composites. Removal of the chitin template by either calcination or sulfuric-acid-catalyzed hydrolysis gave mesoporous silica and ethylene-bridged organosilica films. The large, crack-free mesoporous films have layered structures with features that originate from the nematic organization of the nanocrystalline chitin.

  1. Adsorption of vitamin E on mesoporous titania nanocrystals

    SciTech Connect

    Shih, C.J.; Lin, C.T.; Wu, S.M.

    2010-07-15

    Tri-block nonionic surfactant and titanium chloride were used as starting materials for the synthesis of mesoporous titania nanocrystallite powders. The main objective of the present study was to examine the synthesis of mesoporous titania nanocrystals and the adsorption of vitamin E on those nanocrystals using X-ray diffraction (XRD), transmission electron microscopy, and nitrogen adsorption and desorption isotherms. When the calcination temperature was increased to 300 {sup o}C, the reflection peaks in the XRD pattern indicated the presence of an anatase phase. The crystallinity of the nanocrystallites increased from 80% to 98.6% with increasing calcination temperature from 465 {sup o}C to 500 {sup o}C. The N{sub 2} adsorption data and XRD data taken after vitamin E adsorption revealed that the vitamin E molecules were adsorbed in the mesopores of the titania nanocrystals.

  2. Syntheses and applications of periodic mesoporous organosilica nanoparticles

    NASA Astrophysics Data System (ADS)

    Croissant, Jonas G.; Cattoën, Xavier; Wong Chi Man, Michel; Durand, Jean-Olivier; Khashab, Niveen M.

    2015-12-01

    Periodic Mesoporous Organosilica (PMO) nanomaterials are envisioned to be one of the most prolific subjects of research in the next decade. Similar to mesoporous silica nanoparticles (MSN), PMO nanoparticles (NPs) prepared from organo-bridged alkoxysilanes have tunable mesopores that could be utilized for many applications such as gas and molecule adsorption, catalysis, drug and gene delivery, electronics, and sensing; but unlike MSN, the diversity in chemical nature of the pore walls of such nanomaterials is theoretically unlimited. Thus, we expect that PMO NPs will attract considerable interest over the next decade. In this review, we will present a comprehensive overview of the synthetic strategies for the preparation of nanoscaled PMO materials, and then describe their applications in catalysis and nanomedicine. The remarkable assets of the PMO structure are also detailed, and insights are provided for the preparation of more complex PMO nanoplatforms.

  3. Syntheses and applications of periodic mesoporous organosilica nanoparticles.

    PubMed

    Croissant, Jonas G; Cattoën, Xavier; Wong, Michel Chi Man; Durand, Jean-Olivier; Khashab, Niveen M

    2015-12-28

    Periodic Mesoporous Organosilica (PMO) nanomaterials are envisioned to be one of the most prolific subjects of research in the next decade. Similar to mesoporous silica nanoparticles (MSN), PMO nanoparticles (NPs) prepared from organo-bridged alkoxysilanes have tunable mesopores that could be utilized for many applications such as gas and molecule adsorption, catalysis, drug and gene delivery, electronics, and sensing; but unlike MSN, the diversity in chemical nature of the pore walls of such nanomaterials is theoretically unlimited. Thus, we expect that PMO NPs will attract considerable interest over the next decade. In this review, we will present a comprehensive overview of the synthetic strategies for the preparation of nanoscaled PMO materials, and then describe their applications in catalysis and nanomedicine. The remarkable assets of the PMO structure are also detailed, and insights are provided for the preparation of more complex PMO nanoplatforms.

  4. Mesoporous materials for energy conversion and storage devices

    NASA Astrophysics Data System (ADS)

    Li, Wei; Liu, Jun; Zhao, Dongyuan

    2016-06-01

    To meet the growing energy demands in a low-carbon economy, the development of new materials that improve the efficiency of energy conversion and storage systems is essential. Mesoporous materials offer opportunities in energy conversion and storage applications owing to their extraordinarily high surface areas and large pore volumes. These properties may improve the performance of materials in terms of energy and power density, lifetime and stability. In this Review, we summarize the primary methods for preparing mesoporous materials and discuss their applications as electrodes and/or catalysts in solar cells, solar fuel production, rechargeable batteries, supercapacitors and fuel cells. Finally, we outline the research and development challenges of mesoporous materials that need to be overcome to increase their contribution in renewable energy applications.

  5. Ordered mesoporous materials based on interfacial assembly and engineering.

    PubMed

    Li, Wei; Yue, Qin; Deng, Yonghui; Zhao, Dongyuan

    2013-10-04

    Ordered mesoporous materials have inspired prominent research interest due to their unique properties and functionalities and potential applications in adsorption, separation, catalysis, sensors, drug delivery, energy conversion and storage, and so on. Thanks to continuous efforts over the past two decades, great achievements have been made in the synthesis and structural characterization of mesoporous materials. In this review, we summarize recent progresses in preparing ordered mesoporous materials from the viewpoint of interfacial assembly and engineering. Five interfacial assembly and synthesis are comprehensively highlighted, including liquid-solid interfacial assembly, gas-liquid interfacial assembly, liquid-liquid interfacial assembly, gas-solid interfacial synthesis, and solid-solid interfacial synthesis, basics about their synthesis pathways, princples and interface engineering strategies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

  7. Highly Aminated Mesoporous Silica Nanoparticles with Cubic Pore Structure

    PubMed Central

    Suteewong, Teeraporn; Sai, Hiroaki; Cohen, Roy; Wang, Suntao; Bradbury, Michelle; Baird, Barbara; Gruner, Sol M.; Wiesner, Ulrich

    2010-01-01

    Mesoporous silica with cubic symmetry has attracted interest from researchers for some times. Here we present the room temperature synthesis of mesoporous silica nanoparticles possessing cubic Pm3̄n symmetry with very high molar ratios (>50%) of 3-aminopropyl triethoxysilane. The synthesis is robust allowing, e.g. for co-condensation of organic dyes without loss of structure. By means of pore expander molecules, the pore size can be enlarged from 2.7 to 5 nm, while particle size decreases. Adding pore expander and co-condensing fluorescent dyes in the same synthesis reduces average particle size further down to 100 nm. After PEGylation, such fluorescent aminated mesoporous silica nanoparticles are spontaneously uptaken by cells as demonstrated by fluorescence microscopy. PMID:21158438

  8. Plutonium complexation by phosphonate-functionalized mesoporous silica

    SciTech Connect

    Parsons-Moss, T; Schwaiger, L K; Hubaud, A; Hu, Y J; Tuysuz, H; Yang, P; Balasubramanian, K; Nitsche, H

    2010-10-27

    MCM-41-type mesoporous silica functionalized with the CMPO-based 'Ac-Phos' silane has been reported in the literature (1) to show good capacity as an acftinide sorbent material, with potential applications in environmental sequestration, aqueous waste separation and/or vitrification, and chemical sensing of actinides in solution. The study explores the complexation of Pu(IV and VI) and other selected actinides and lanthanides by SBA-15 type mesoporous silica functionalized with Ac-Phos. The Pu binding kinetics and binding capacity were determined for both the Ac-Phos functionalized and unmodified SBA-15. They analyzed the binding geometry and redox behavior of Pu(VI) by X-ray absorption spectroscopy (XAS). They discuss the synthesis and characterization of the functionalized mesoporous material, batch sorption experiments, and the detailed analyses of the actinide complexes that are formed. Structural measurements are paired with high-level quantum mechanical modeling to elucidate the binding mechanisms.

  9. Bare and Effective Charge of Mesoporous Silica Particles.

    PubMed

    Valetti, Sabrina; Feiler, Adam; Trulsson, Martin

    2017-07-25

    We develop and combine a novel numerical model, within the Poisson-Boltzmann framework, with classical experimental titration techniques for mesoporous silica particles to study the charging behavior as both pH and the amount of monovalent salt are varied. One key finding is that these particles can be considered to have an effectively or apparent electroneutral inner core with an effectively charged rim. As a consequence, the total apparent charge of the particle is several orders of magnitude smaller than that of the bare silica charge, which accounts only for the charged silanol groups of the mesoporous silica particles and which has its major contribution from the interior. Hence, the interior dictates the mesoporous silicas' bare charge while the rim its effective charge. We furthermore report density, charge, and accumulated charge profiles across the particle's interface.

  10. Ultrahigh porosity in mesoporous MOFs: promises and limitations.

    PubMed

    Senkovska, Irena; Kaskel, Stefan

    2014-07-11

    Mesoporous MOFs are currently record holders in terms of the specific surface area with values exceeding 7000 m(2) g(-1), a textural feature unattained by traditional porous solids such as zeolites, carbons and even by graphene. They are promising candidates for high pressure gas storage and also for conversion or separation of larger molecules, whose size exceeds the pore size of zeolites. The rational strategies for synthesis of mesoporous MOF are outlined and the unambiguous consistent assessment of the surface area of such ultrahighly porous materials, as well as present challenges in the exciting research field, of mesoporous MOFs are discussed. The crystallinity, dynamic properties, functional groups, and wide range tunability render these materials as exceptional solids, but for the implementation in functional devices and even in industrial processes several aspects and effective characteristics (such as volumetric storage capacities, recyclability, mechanical and chemical stability, activation) should be addressed.

  11. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    PubMed

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

  12. Mesoporous Silica Molecular Sieve based Nanocarriers: Transpiring Drug Dissolution Research.

    PubMed

    Pattnaik, Satyanarayan; Pathak, Kamla

    2017-01-01

    Improvement of oral bioavailability through enhancement of dissolution for poorly soluble drugs has been a very promising approach. Recently, mesoporous silica based molecular sieves have demonstrated excellent properties to enhance the dissolution velocity of poorly water-soluble drugs. Current research in this area is focused on investigating the factors influencing the drug release from these carriers, the kinetics of drug release and manufacturing approaches to scale-up production for commercial manufacture. This comprehensive review provides an overview of different methods adopted for synthesis of mesoporous materials, influence of processing factors on properties of these materials and drug loading methods. The drug release kinetics from mesoporous silica systems, the manufacturability and stability of these formulations are reviewed. Finally, the safety and biocompatibility issues related to these silica based materials are discussed. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  13. Ordered mesoporous silica (OMS) as an adsorbent and membrane for separation of carbon dioxide (CO2).

    PubMed

    Chew, Thiam-Leng; Ahmad, Abdul L; Bhatia, Subhash

    2010-01-15

    Separation of carbon dioxide (CO(2)) from gaseous mixture is an important issue for the removal of CO(2) in natural gas processing and power plants. The ordered mesoporous silicas (OMS) with uniform pore structure and high density of silanol groups, have attracted the interest of researchers for separation of carbon dioxide (CO(2)) using adsorption process. These mesoporous silicas after functionalization with amino groups have been studied for the removal of CO(2). The potential of functionalized ordered mesoporous silica membrane for separation of CO(2) is also recognized. The present paper reviews the synthesis of mesoporous silicas and important issues related to the development of mesoporous silicas. Recent studies on the CO(2) separation using ordered mesoporous silicas (OMS) as adsorbent and membrane are highlighted. The future prospectives of mesoporous silica membrane for CO(2) adsorption and separation are also presented and discussed. Copyright 2009 Elsevier B.V. All rights reserved.

  14. Structure and infrared emissivity of polyimide/mesoporous silica composite films

    SciTech Connect

    Lin Baoping . E-mail: lbp@seu.edu.cn; Tang Jinan; Liu Hongjian; Sun Yueming; Yuan Chunwei

    2005-03-15

    Polyimide/mesoporous silica composite films were prepared by direct mixing of polyamic acid solution and silylated mesoporous silica particles, or by condensation polymerization of dianhydride and diamine with silylated mesoporous silica particles in N,N-dimethylacetamide, followed with thermal imidization. Structure and glass transition temperatures of the composite films were measured with FTIR, SEM, EDX, XPS and DMTA. The results show that the silylated mesoporous silica particles in the composites tend to form the aggregation with a strip shape due to phase separation. The composite films exhibit higher glass transition temperature as comparing with that of pure polyimide. It is found that the composite films present lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value is related to the content of silylated mesoporous silica in the composite films. Inhibiting actions of silylated mesoporous silica on infrared emission of the composite films may be owing to presence of nanometer-scale pores in silylated mesoporous silica.

  15. Mesoporous bioactive glass scaffolds for efficient delivery of vascular endothelial growth factor.

    PubMed

    Wu, Chengtie; Fan, Wei; Chang, Jiang; Xiao, Yin

    2013-09-01

    In this article, we, for the first time, investigated mesoporous bioactive glass scaffolds for the delivery of vascular endothelial growth factor. We have found that mesoporous bioactive glass scaffolds have significantly higher loading efficiency and more sustained release of vascular endothelial growth factor than non-mesoporous bioactive glass scaffolds. In addition, vascular endothelial growth factor delivery from mesoporous bioactive glass scaffolds has improved the viability of endothelial cells. The study has suggested that mesopore structures in mesoporous bioactive glass scaffolds play an important role in improving the loading efficiency, decreasing the burst release, and maintaining the bioactivity of vascular endothelial growth factor, indicating that mesoporous bioactive glass scaffolds are an excellent carrier of vascular endothelial growth factor for potential bone tissue engineering applications.

  16. The synthesis and application of two mesoporous silica nanoparticles as drug delivery system with different shape

    NASA Astrophysics Data System (ADS)

    Wang, Jiayi; Wang, Zhuyuan; Chen, Hui; Zong, Shenfei; Cui, Yiping

    2015-05-01

    Mesoporous silica nanospheres(MSNSs) have been obtained utilizing the conventional reverse micelles synthesis method while the mesoporous silica nanorods(MSNRs) have been acquired by means of changing certain parameters. Afterwards, the prepared mesoporous silica nanospheres and nanorods were used as drug carriers to load and release the classical cancer therapeutic drug—DOX. According to the absorption spectra, the encapsulation efficiency of the mesoporous silica nanospheres is almost as high as that of the nanospheres. Different from the familiar encapsulation efficiency, the release characteristic curves of the mesoporous silica nanospheres and nanorods possessed certain differences during the release process. Finally incellular fluorescence imaging was achieved to observe the endocytosis of the mesoporous silica materials. Our results show that although both of the two kinds of nanoparticles possess favourable properties for loading and releasing drugs, the mesoporous silica nanospheres perform better in dispersity and controlled release than the nanorods, which probably endow them the potential as incellular drug delivery system.

  17. Biological mineral range effects on biomass conversion to aromatic hydrocarbons via catalytic fast pyrolysis over HZSM-5

    USDA-ARS?s Scientific Manuscript database

    A set of 20 biomass samples, comprising 10 genotypes of switchgrass, sorghum and miscanthus grown in two different soils with high and low poultry manure input conditions, and having a wide biological range of mineral content, were subjected to catalytic fast pyrolysis (CFP) over HZMS-5 using py-G...

  18. Hypercrosslinked phenolic polymers with well developed mesoporous frameworks

    DOE PAGES

    Zhang, Jinshui; Qiao, Zhenan -An; Mahurin, Shannon Mark; ...

    2015-02-12

    A soft chemistry synthetic strategy based on a Friedel Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro-mesoporous architecture with well-preserved organic functional groups, which is effective for carbon capture. Furthermore, this soft chemistry synthetic protocol can be further extended to nanotexture other aromatic-based polymers with robust frameworks.

  19. Optical and electronic loss analysis of mesoporous solar cells

    NASA Astrophysics Data System (ADS)

    Kovalsky, Anton; Burda, Clemens

    2016-07-01

    We review the art of complete optical and electronic characterization of the popular mesoporous solar cell motif. An overview is given of how the mesoporous paradigm is applied to solar cell technology, followed by a discussion on the variety of techniques available for thoroughly probing efficiency leaching mechanisms at every stage of the energy transfer pathway. Some attention is dedicated to the rising importance of computational results to augment loss analysis due to the complexity of solar cell devices, which have emergent properties that are important to account for, but difficult to measure, such as parasitic absorption.

  20. A Review of Recent Developments of Mesoporous Materials.

    PubMed

    Suib, Steven L

    2017-06-29

    This personal account concerns novel recent discoveries in the area of mesoporous materials. Most of the papers discussed have been published within the last two to three years. A major emphasis of most of these papers is the synthesis of unique mesoporous materials by a variety of synthetic methods. Many of these articles focus on the control of the pore sizes and shapes of mesoporous materials. Synthetic methods of various types have been used for such control of porosity including soft templating, hard templating, nano-casting, electrochemical methods, surface functionalization, and trapping of species in pores. The types of mesoporous materials range from carbon materials, metal oxides, metal sulfides, metal nitrides, carbonitriles, metal organic frameworks (MOFs), and composite materials. The vast majority of recent publications have centered around biological applications with a majority dealing with drug delivery systems. Several other bio-based articles on mesoporous systems concern biomass conversion and biofuels, magnetic resonance imaging (MRI) studies, ultrasound therapy, enzyme immobilization, antigen targeting, biodegradation of inorganic materials, applications for improved digestion, and antitumor activity. Numerous nonbiological applications of mesoporous materials have been pursued recently. Some specific examples are photocatalysis, photo-electrocatalysis, lithium ion batteries, heterogeneous catalysis, extraction of metals, extraction of lanthanide and actinide species, chiral separations and catalysis, capturing and the mode of binding of carbon dioxide (CO2 ), optical devices, and magneto-optical devices. Of this latter class of applications, heterogeneous catalysis is predominant. Some of the types of catalytic reactions being pursued include hydrogen generation, selective oxidations, aminolysis, Suzuki coupling and other coupling reactions, oxygen reduction reactions (ORR), oxygen evolution reactions (OER), and bifunctional catalysis. For

  1. Monolithic Gyroidal Mesoporous Mixed Titanium–Niobium Nitrides

    PubMed Central

    2015-01-01

    Mesoporous transition metal nitrides are interesting materials for energy conversion and storage applications due to their conductivity and durability. We present ordered mixed titanium–niobium (8:2, 1:1) nitrides with gyroidal network structures synthesized from triblock terpolymer structure-directed mixed oxides. The materials retain both macroscopic integrity and mesoscale ordering despite heat treatment up to 600 °C, without a rigid carbon framework as a support. Furthermore, the gyroidal lattice parameters were varied by changing polymer molar mass. This synthesis strategy may prove useful in generating a variety of monolithic ordered mesoporous mixed oxides and nitrides for electrode and catalyst materials. PMID:25122534

  2. Nanoindentation studies of nickel zinc ferrite embedded mesoporous silica template

    NASA Astrophysics Data System (ADS)

    Banerjee, S.; Hajra, P.; Mada, M. R.; Bandopadhyay, S.; Chakravorty, D.

    2013-02-01

    Nickel zinc ferrite (NZF) embedded mesoporous silica KIT-6 nanocomposite (NZFMS) was synthesized via impregnation method. The microstructure of the samples was characterized by transmission electron microscopy (TEM). Nanoindentation (NI) studies were carried out on both mesoporous silica (MS) and the nanocomposite NZFMS. It was found that the young's modulus (E) and hardness (H) of the NZFMS were higher than that of the MS. From creep measurement it was observed that the creep-strain rate was greater for NZFMS compared to MS. This arose due to diffusion of Fe3+ ions from nickel zinc ferrite to the silica glass. The results indicate that the NZFMS material shows superplastic behaviour at room temperature.

  3. Monolithic gyroidal mesoporous mixed titanium-niobium nitrides.

    PubMed

    Robbins, Spencer W; Sai, Hiroaki; DiSalvo, Francis J; Gruner, Sol M; Wiesner, Ulrich

    2014-08-26

    Mesoporous transition metal nitrides are interesting materials for energy conversion and storage applications due to their conductivity and durability. We present ordered mixed titanium-niobium (8:2, 1:1) nitrides with gyroidal network structures synthesized from triblock terpolymer structure-directed mixed oxides. The materials retain both macroscopic integrity and mesoscale ordering despite heat treatment up to 600 °C, without a rigid carbon framework as a support. Furthermore, the gyroidal lattice parameters were varied by changing polymer molar mass. This synthesis strategy may prove useful in generating a variety of monolithic ordered mesoporous mixed oxides and nitrides for electrode and catalyst materials.

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-05-10

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

  6. Mesoporous silicates prepared using preorganized templates in supercritical fluids.

    PubMed

    Pai, Rajaram A; Humayun, Raashina; Schulberg, Michelle T; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J

    2004-01-23

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

  7. Mesoporous Silicates Prepared Using Preorganized Templates in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Pai, Rajaram A.; Humayun, Raashina; Schulberg, Michelle T.; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J.

    2004-01-01

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

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

    PubMed

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

    2011-09-21

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

  9. Electric Field-Responsive Mesoporous Suspensions: A Review

    PubMed Central

    Kwon, Seung Hyuk; Piao, Shang Hao; Choi, Hyoung Jin

    2015-01-01

    This paper briefly reviews the fabrication and electrorheological (ER) characteristics of mesoporous materials and their nanocomposites with conducting polymers under an applied electric field when dispersed in an insulating liquid. Smart fluids of electrically-polarizable particles exhibit a reversible and tunable phase transition from a liquid-like to solid-like state in response to an external electric field of various strengths, and have potential applications in a variety of active control systems. The ER properties of these mesoporous suspensions are explained further according to their dielectric spectra in terms of the flow curve, dynamic moduli, and yield stress. PMID:28347119

  10. Host–guest chemistry of mesoporous silicas: precise design of location, density and orientation of molecular guests in mesopores

    PubMed Central

    Sohmiya, Minoru; Saito, Kanji; Ogawa, Makoto

    2015-01-01

    Mesoporous solids, which were prepared from inorganic-surfactant mesostructured materials, have been investigated due to their very large surface area and high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification. Morphosyntheses from macroscopic morphologies such as bulk monolith and films, to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. This class of materials has been studied for such applications as adsorbents and catalysts, and later on, for optical, electronic, environmental and bio-related ones. This review summarizes the studies on the chemistry of mesoporous silica and functional guest species (host–guest chemistry) to highlight the present status and future applications of the host–guest hybrids. PMID:27877830

  11. Bifunctional mesoporous silicas with clearly distinguished localization of grafted groups

    NASA Astrophysics Data System (ADS)

    Roik, N. V.; Belyakova, L. A.

    2013-12-01

    Bifunctional mesoporous silicas with clearly distinguished localization of grafted groups on the surface of particles and inside their pores were obtained by means of sol-gel synthesis with postsynthetic vapor-phase treatment in vacuum. It was found that the synthesized materials have the hexagonally ordered porous structure typical of MCM-41 type silica.

  12. Contamination-resistant silica antireflective coating with closed ordered mesopores.

    PubMed

    Sun, Jinghua; Zhang, Qinghua; Ding, Ruimin; Lv, Haibing; Yan, Hongwei; Yuan, Xiaodong; Xu, Yao

    2014-08-21

    Porous silica optical antireflective (AR) coatings prepared by traditional sol-gel method have been extensively used for high power laser systems, but a serious drawback is that contamination existing in the high vacuum is easily absorbed by the disordered open pore structure, resulting in a fast decrease in transmittance. To improve the stability of transmittance in vacuum, a contamination-resistant silica AR coating with ordered mesopores completely closed by hydrophobic-oleophobic groups was successfully developed on a fused quartz substrate. The ordered mesopores in the coating were controlled under the direction of surfactant F127 via an evaporation-induced-self-assembling process and then were closed by post-grafting long chain fluoroalkylsilane. The grazing incidence small angle X-ray scattering (GISAXS) and the X-ray reflectivity (XRR) results indicated that the mesopores in the coating constructed a Fmmm orthorhombic symmetry structure with a (010) plane parallel to the substrate. Cage-like mesopores were confirmed by nitrogen adsorption-desorption analysis. The obtained coatings showed low surface roughness, excellent abrase-resistance and high transmittance of 100% on quartz substrate. Especially, the decrease of transmittance tested with polydimethylsiloxane pollution in vacuum within one-month was as small as 0.02%. The laser induced damage threshold was up to 59.8 J cm(-2) at a 12 ns laser pulse of 1053 nm wavelength. This work provides an alternative way to fabricate AR coatings with high stability.

  13. Mesoporous hybrid thin films: the physics and chemistry beneath.

    PubMed

    Soler-Illia, G J A A; Innocenzi, P

    2006-06-02

    Mesoporous films containing organic or biological functions within an organised array of cavities are produced by combining sol-gel, self-assembly of supramolecular templates and surface chemistry. This paper reviews the essential physics and chemical concepts behind the synthesis of these complex multifunctional materials.

  14. Antibacterial performance of nanocrystallined titania confined in mesoporous silica nanotubes.

    PubMed

    Cendrowski, Krzysztof; Peruzynska, Magdalena; Markowska-Szczupak, Agata; Chen, Xuecheng; Wajda, Anna; Lapczuk, Joanna; Kurzawski, Mateusz; Kalenczuk, Ryszard J; Drozdzik, Marek; Mijowska, Ewa

    2014-06-01

    In this paper, we study synthesis and characteristics of mesoporous silica nanotubes modified by titanium dioxide, as well as their antimicrobial properties and influence on mitochondrial activity of mouse fibroblast L929. Nanocrystalized titania is confined in mesopores of silica nanotubes and its light activated antibacterial response is revealed. The analysis of the antibacterial effect on Escherichia coli. (ATCC 25922) shows strong enhancement during irradiation with the artificial visible and ultraviolet light in respect to the commercial catalyst and control sample free from the nanomaterials. In darkness, the mesoporous silica/titania nanostructures exhibited antibacterial activity dependent on the stirring speed of the suspension containing nanomaterials. Obtained micrograph proved internalization of the sample into the microorganism trough the cell membrane. The analysis of the mitochondrial activity and amount of lactate dehydrogenase released from mouse fibroblast cells L929 in the presence of the sample were determined with LDH and WST1 assays, respectively. The synthesized silica/titania antibacterial agent also exhibits pronounced photoinduced inactivation of the bacterial growth under the artificial visible and UV light irritation in respect to the commercial catalyst. Additionally, mesoporous silica/titania nanotubes were characterized in details by means of high resolution transmission electron microscopy (HR-TEM), XRD and BET Isotherm.

  15. Enhanced photocatalytic properties in well-ordered mesoporous WO3.

    PubMed

    Li, Li; Krissanasaeranee, Methira; Pattinson, Sebastian W; Stefik, Morgan; Wiesner, Ulrich; Steiner, Ullrich; Eder, Dominik

    2010-10-28

    We used polyisoprene-block-ethyleneoxide copolymers as structure-directing agents to synthesise well-ordered and highly-crystalline mesoporous WO(3) architectures that possess improved photocatalytic properties due to enhanced dye-adsorption in absence of diffusion limitation.

  16. Regeneration of mesoporous silica aerogel for hydrocarbon adsorption and recovery.

    PubMed

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

    2017-09-15

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

  17. Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

    NASA Astrophysics Data System (ADS)

    Ho, Li-Ngee; Ikegawa, Tasuku; Nishiguchi, Hiroyasu; Nagaoka, Katsutoshi; Takita, Yusaku

    2006-07-01

    A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of 27Al and 31P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m 2/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo 4+ and Mo 6+ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.

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

    PubMed

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

    2010-03-11

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

  19. Incorporation of anti-inflammatory agent into mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rodrigues Braz, Wilson; Lamec Rocha, Natállia; de Faria, Emerson H.; Silva, Márcio L. A. e.; Ciuffi, Katia J.; Tavares, Denise C.; Furtado, Ricardo Andrade; Rocha, Lucas A.; Nassar, Eduardo J.

    2016-09-01

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol-gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol-gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  20. Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Milina, Maria; Mitchell, Sharon; Crivelli, Paolo; Cooke, David; Pérez-Ramírez, Javier

    2014-05-01

    Deactivation due to coking limits the lifetime of zeolite catalysts in the production of chemicals and fuels. Superior performance can be achieved through hierarchically structuring the zeolite porosity, yet no relation has been established between the mesopore architecture and the catalyst lifetime. Here we introduce a top-down demetallation strategy to locate mesopores in different regions of MFI-type crystals with identical bulk porous and acidic properties. In contrast, well-established bottom-up strategies as carbon templating and seed silanization fail to yield materials with matching characteristics. Advanced characterization tools capable of accurately discriminating the mesopore size, distribution and connectivity are applied to corroborate the concept of mesopore quality. Positron annihilation lifetime spectroscopy proves powerful to quantify the global connectivity of the intracrystalline pore network, which, as demonstrated in the conversions of methanol or of propanal to hydrocarbons, is closely linked to the lifetime of zeolite catalysts. The findings emphasize the need to aptly tailor hierarchical materials for maximal catalytic advantage.

  1. Preparation of mesoporous titania solid superacid and its catalytic property.

    PubMed

    Jiang, Tingshun; Zhao, Qian; Li, Mei; Yin, Hengbo

    2008-11-30

    Mesoporous titania (TiO(2)) was synthesized by hydrothermal method using cetyltrimethyl ammonium bromide (CTAB) as a template and using anhydrous ethanol and tetra-n-butyl titanate (TBOT) as raw materials. Mesoporous titania solid superacid and nanosized titania solid superacid catalysts were prepared by wet impregnation method. The structure and property of as-prepared samples were characterized by means of XRD, FT-IR and N(2) physical adsorption. The esterification of salicylic acid with isoamyl alcohol and the condensation of cyclohexanone with ethylene were used as model reactions to test the catalytic activities of the catalysts. On the other hand, the comparison of catalytic activities of the prepared solid superacid catalysts and the conventional liquid acid H(2)SO(4) was also carried out under the same experimental conditions. The results show that the catalytic activities of the prepared solid superacid catalysts were higher than that of the conventional liquid acid H(2)SO(4), and that the catalytic activity of mesoporous TiO(2) solid superacid is the highest among the three catalysts. Mesoporous TiO(2) solid superacid is a good catalyst for the synthesis of isoamyl salicylate or cyclohexanone ethylene ketal.

  2. Functionalized mesoporous silica nanoparticles for stimuli-responsive and targeted

    SciTech Connect

    Knezevic, Nikola

    2009-12-15

    Construction of functional supramolecular nanoassemblies has attracted great deal of attention in recent years for their wide spectrum of practical applications. Mesoporous silica nanoparticles (MSN) in particular were shown to be effective scaffolds for the construction of drug carriers, sensors and catalysts. Herein, we describe the synthesis and characterization of stimuli-responsive, controlled release MSN-based assemblies for drug delivery.

  3. Incorporation of anti-inflammatory agent into mesoporous silica.

    PubMed

    Braz, Wilson Rodrigues; Rocha, Natállia Lamec; de Faria, Emerson H; Silva, Márcio L A E; Ciuffi, Katia J; Tavares, Denise C; Furtado, Ricardo Andrade; Rocha, Lucas A; Nassar, Eduardo J

    2016-09-23

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol-gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol-gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  4. Adsorption of mycotoxins in beverages onto functionalized mesoporous silicas

    USDA-ARS?s Scientific Manuscript database

    Mycotoxins, natural toxins produced by fungi, are a global concern as contaminates of agricultural commodities. Exposure to these toxins can be reduced by the use of binding materials. Templated mesoporous silicas are promising materials with favorable adsorptive properties for dyes, ions, and toxin...

  5. Fabrication of mesoporous silica/polymer composites through solvent evaporation process and investigation of their excellent low thermal expansion property.

    PubMed

    Suzuki, Norihiro; Kiba, Shosuke; Yamauchi, Yusuke

    2011-03-21

    We fabricate mesoporous silica/epoxy polymer composites through a solvent evaporation process. The easy penetration of the epoxy polymers into mesopores is achieved by using a diluted polymer solution including a volatile organic solvent. After the complete solvent evaporation, around 90% of the mesopores are estimated to be filled with the epoxy polymer chains. Here we carefully investigate the thermal expansion behavior of the obtained mesoporous silica/polymer composites. Thermal mechanical analysis (TMA) charts revealed that coefficient of linear thermal expansion (CTE) gradually decreases, as the amount of the doped mesoporous silica increases. Compared with spherical silica particle without mesopores, mesoporous silica particles show a greater effect on lowering the CTE values. Interestingly, it is found that the CTE values are proportionally decreased with the decrease of the total amount of the polymers outside the mesopores. These data demonstrate that polymers embedded inside the mesopores become thermally stable, and do not greatly contribute to the thermal expansion behavior of the composites.

  6. Rapid synthesis of ordered hexagonal mesoporous silica and their incorporation with Ag nanoparticles by solution plasma

    SciTech Connect

    Pootawang, Panuphong; Saito, Nagahiro; Takai, Osamu; Lee, Sang Yul

    2012-10-15

    Graphical abstract: Overall reactions of mesoporous silica and AgNPs-incorporated mesoporous silica syntheses by solution plasma process (SPP). Highlights: ► SPP for rapid synthesis of mesoporous silica. ► SPP for rapid synthesis of mesoporous silica and AgNPs incorporation. ► Higher surface area and larger pore diameter of mesoporous silica synthesized by SPP. -- Abstract: Rapid synthesis of silica with ordered hexagonal mesopore arrangement was obtained using solution plasma process (SPP) by discharging the mixture of P123 triblock copolymer/TEOS in acid solution. SPP, moreover, was utilized for Ag nanoparticles (AgNPs) incorporation in silica framework as one-batch process using silver nitrate (AgNO{sub 3}) solution as precursor. The turbid silicate gel was clearly observed after discharge for 1 min and the white precipitate formed at 3 min. The mesopore with hexagonal arrangement and AgNPs were observed in mesoporous silica. Two regions of X-ray diffraction patterns (2θ < 2° and 2θ = 35–90°) corresponded to the mesoporous silica and Ag nanocrystal characteristics. Comparing with mesoporous silica prepared by a conventional sol–gel route, surface area and pore diameter of mesoporous silica prepared by solution plasma were observed to be larger. In addition, the increase in Ag loading resulted in the decrease in surface area with insignificant variation in the pore diameter of mesoporous silica. SPP could be successfully utilized not only to enhance gelation time but also to increase surface area and pore diameter of mesoporous silica.

  7. A magnetic mesoporous silica nanoparticle-based drug delivery system for photosensitive cooperative treatment of cancer with a mesopore-capping agent and mesopore-loaded drug

    NASA Astrophysics Data System (ADS)

    Knežević, Nikola Ž.; Lin, Victor S.-Y.

    2013-01-01

    Lately, there has been a growing interest in anticancer therapy with a combination of different drugs that work by different mechanisms of action, which decreases the possibility that resistant cancer cells will develop. Herein we report on the development of a drug delivery system for photosensitive delivery of a known anticancer drug camptothecin along with cytotoxic cadmium sulfide nanoparticles from a magnetic drug nanocarrier. Core-shell nanoparticles consisting of magnetic iron-oxide-cores and mesoporous silica shells are synthesized with a high surface area (859 m2 g-1) and hexagonal packing of mesopores, which are 2.6 nm in diameter. The mesopores are loaded with anticancer drug camptothecin while entrances of the mesopores are blocked with 2-nitro-5-mercaptobenzyl alcohol functionalized CdS nanoparticles through a photocleavable carbamate linkage. Camptothecin release from this magnetic drug delivery system is successfully triggered upon irradiation with UV light, as measured by fluorescence spectroscopy. Photosensitive anticancer activity of the drug delivery system is monitored by viability studies on Chinese hamster ovarian cells. The treatment of cancer cells with drug loaded magnetic material leads to a decrease in viability of the cells due to the activity of capping CdS nanoparticles. Upon exposure to low power UV light (365 nm) the loaded camptothecin is released which induces additional decrease in viability of CHO cells. Hence, the capping CdS nanoparticles and loaded camptothecin exert a cooperative anticancer activity. Responsiveness to light irradiation and magnetic activity of the nanocarrier enable its potential application for selective targeted treatment of cancer.

  8. Hollow-structured mesoporous materials: chemical synthesis, functionalization and applications.

    PubMed

    Li, Yongsheng; Shi, Jianlin

    2014-05-28

    Hollow-structured mesoporous materials (HMMs), as a kind of mesoporous material with unique morphology, have been of great interest in the past decade because of the subtle combination of the hollow architecture with the mesoporous nanostructure. Benefitting from the merits of low density, large void space, large specific surface area, and, especially, the good biocompatibility, HMMs present promising application prospects in various fields, such as adsorption and storage, confined catalysis when catalytically active species are incorporated in the core and/or shell, controlled drug release, targeted drug delivery, and simultaneous diagnosis and therapy of cancers when the surface and/or core of the HMMs are functionalized with functional ligands and/or nanoparticles, and so on. In this review, recent progress in the design, synthesis, functionalization, and applications of hollow mesoporous materials are discussed. Two main synthetic strategies, soft-templating and hard-templating routes, are broadly sorted and described in detail. Progress in the main application aspects of HMMs, such as adsorption and storage, catalysis, and biomedicine, are also discussed in detail in this article, in terms of the unique features of the combined large void space in the core and the mesoporous network in the shell. Functionalization of the core and pore/outer surfaces with functional organic groups and/or nanoparticles, and their performance, are summarized in this article. Finally, an outlook of their prospects and challenges in terms of their controlled synthesis and scaled application is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. Magnetic mesoporous materials for removal of environmental wastes

    SciTech Connect

    Kim, Byoung Chan; Lee, Jinwoo; Um, Wooyong; Kim, Jaeyun; Joo, Jin; Lee, Jin Hyung; Kwak, Ja Hun; Kim, Jae Hyun; Lee, Changha; Lee, Hongshin; Addleman, Raymond S.; Hyeon, Taeghwan; Gu, Man Bock; Kim, Jungbae

    2011-09-15

    We have synthesized two different magnetic mesoporous materials that can be easily separated from aqueous solutions by applying a magnetic field. Synthesized magnetic mesoporous materials, Mag-SBA-15 (magnetic ordered mesoporous silica) and Mag-OMC (magnetic ordered mesoporous carbon), have a high loading capacity of contaminants due to high surface area of the supports and high magnetic activity due to the embedded iron oxide particles. Application of surface-modified Mag-SBA-15 was investigated for the collection of mercury from water. The mercury adsorption using Mag-SBA-15 was rapid during the initial contact time and reached a steady-state condition, with an uptake of approximately 97% after 7 hours. Application of Mag-OMC for collection of organics from water, using fluorescein as an easily trackable model analyte, was explored. The fluorescein was absorbed into Mag-OMC within minutes and the fluorescent intensity of solution was completely disappeared after an hour. In another application, Mag-SBA-15 was used as a host of tyrosinase, and employed as recyclable catalytic scaffolds for tyrosinase-catalyzed biodegradation of catechol. Tyrosinase aggregates in Mag-SBA-15, prepared in a two step process of tyrosinase adsorption and crosslinking, could be used repeatedly for catechol degradation with no serious loss of enzyme activity. Considering these results of cleaning up water from toxic inorganic, organic and biochemical contaminants, magnetic mesoporous materials have a great potential to be employed for the removal of environmental contaminants and potentially for the application in large-scale wastewater treatment plants.

  11. Structurally stabilized organosilane-templated thermostable mesoporous titania.

    PubMed

    Amoli, Vipin; Tiwari, Rashmi; Dutta, Arghya; Bhaumik, Asim; Sinha, Anil Kumar

    2014-01-13

    Structurally thermostable mesoporous anatase TiO2 (m-TiO2) nanoparticles, uniquely decorated with atomically dispersed SiO2, is reported for the first time. The inorganic Si portion of the novel organosilane template, used as a mesopores-directing agent, is found to be incorporated in the pore walls of the titania aggregates, mainly as isolated sites. This is evident by transmission electron microscopy and high-angle annular dark field scanning transmission electron microscopy, combined with electron dispersive X-ray spectroscopy. This type of unique structure provides exceptional stability to this new material against thermal collapse of the mesoporous structure, which is reflected in its high surface area (the highest known for anatase titania), even after high-temperature (550 °C) calcination. Control of crystallite size, pore diameter, and surface area is achieved by varying the molar ratios of the titanium precursor and the template during synthesis. These mesoporous materials retain their porosity and high surface area after template removal and further NaOH/HCl treatment to remove silica. We investigate their performance for dye-sensitized solar cells (DSSCs) with bilayer TiO2 electrodes, which are prepared by applying a coating of m-TiO2 onto a commercial titania (P25) film. The high surface area of the upper mesoporous layer in the P25-m-TiO2 DSSC significantly increases the dye loading ability of the photoanode. The photocurrent and fill factor for the DSSC with the bilayer TiO2 electrode are greatly improved. The large increase in photocurrent current (ca. 56%) in the P25-m-TiO2 DSSC is believed to play a significant role in achieving a remarkable increase in the photovoltaic efficiency (60%) of the device, compared to DSSCs with a monolayer of P25 as the electrode. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Near-field radiative heat transfer in mesoporous alumina

    NASA Astrophysics Data System (ADS)

    Jing, Li; Yan-Hui, Feng; Xin-Xin, Zhang; Cong-Liang, Huang; Ge, Wang

    2015-01-01

    The thermal conductivity of mesoporous material has aroused the great interest of scholars due to its wide applications such as insulation, catalyst, etc. Mesoporous alumina substrate consists of uniformly distributed, unconnected cylindrical pores. Near-field radiative heat transfer cannot be ignored, when the diameters of the pores are less than the characteristic wavelength of thermal radiation. In this paper, near-field radiation across a cylindrical pore is simulated by employing the fluctuation dissipation theorem and Green function. Such factors as the diameter of the pore, and the temperature of the material are further analyzed. The research results show that the radiative heat transfer on a mesoscale is 2˜4 orders higher than on a macroscale. The heat flux and equivalent thermal conductivity of radiation across a cylindrical pore decrease exponentially with pore diameter increasing, while increase with temperature increasing. The calculated equivalent thermal conductivity of radiation is further developed to modify the thermal conductivity of the mesoporous alumina. The combined thermal conductivity of the mesoporous alumina is obtained by using porosity weighted dilute medium and compared with the measurement. The combined thermal conductivity of mesoporous silica decreases gradually with pore diameter increasing, while increases smoothly with temperature increasing, which is in good agreement with the experimental data. The larger the porosity, the more significant the near-field effect is, which cannot be ignored. Project supported by the National Natural Science Foundation of China (Grant No. 51422601), the National Basic Research Program of China (Grant No. 2012CB720404), and the National Key Technology Research and Development Program of China (Grant No. 2013BAJ01B03).

  13. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

    2008-05-06

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

  14. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

    1999-01-01

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

  15. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, P.J.; Baskaran, S.; Bontha, J.R.; Liu, J.

    1999-07-13

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s). 24 figs.

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

    PubMed

    Sun, Junming; Bao, Xinhe

    2008-01-01

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

  17. Biocompatibility, degradability, bioactivity and osteogenesis of mesoporous/macroporous scaffolds of mesoporous diopside/poly(l-lactide) composite

    PubMed Central

    Liu, Zhulin; Ji, Jiajin; Tang, Songchao; Qian, Jun; Yan, Yonggang; Yu, Baoqing; Su, Jiacan; Wei, Jie

    2015-01-01

    Bioactive mesoporous diopside (m-DP) and poly(l-lactide) (PLLA) composite scaffolds with mesoporous/macroporous structure were prepared by the solution-casting and particulate-leaching method. The results demonstrated that the degradability and bioactivity of the mesoporous/macroporous scaffolds were significantly improved by incorporating m-DP into PLLA, and that the improvement was m-DP content-dependent. In addition, the scaffolds containing m-DP showed the ability to neutralize acidic degradation products and prevent the pH from dropping in the solution during the soaking period. Moreover, the scaffolds containing m-DP enhanced attachment, proliferation and alkaline phosphatase activity of MC3T3-E1 cells, which were also m-DP content-dependent. Furthermore, the histological and immunohistochemical analysis results showed that the scaffolds with m-DP significantly promoted new bone formation and improved the materials degraded in vivo, indicating good biocompatibility. The results suggested that the mesoporous/macroporous scaffolds of the m-DP/PLLA composite with osteogenesis had a potential for bone regeneration. PMID:26378120

  18. Interactions of Plutonium and Lanthanides with Ordered Mesoporous Materials

    NASA Astrophysics Data System (ADS)

    Parsons-Moss, Tashi

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

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

    NASA Astrophysics Data System (ADS)

    Jin, Zhao

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

  20. Multitasking mesoporous nanomaterials for biorefinery applications

    SciTech Connect

    Kandel, Kapil

    2013-01-01

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

  1. Multitasking mesoporous nanomaterials for biorefinery applications

    NASA Astrophysics Data System (ADS)

    Kandel, Kapil

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

  2. Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

    NASA Astrophysics Data System (ADS)

    Vivero-Escoto, Juan L.; Chiang, Ya-Dong; C-W Wu, Kevin; Yamauchi, Yusuke

    2012-02-01

    This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.

  3. Recent progress in mesoporous titania materials: adjusting morphology for innovative applications.

    PubMed

    Vivero-Escoto, Juan L; Chiang, Ya-Dong; Wu, Kevin; Yamauchi, Yusuke

    2012-02-01

    This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.

  4. Synthesis, characterization and catalytic activity of a novel mesoporous ZSM-5 zeolite

    SciTech Connect

    Ma, Yuanyuan; Hu, Jing; Jia, Lihua; Li, Zhifang; Kan, Qiubin; Wu, Shujie

    2013-05-15

    Highlights: ► Mesoporous ZSM-5 zeolites. ► The strong acidic intensity. ► High activity for the alkylation of phenol and tert-butyl alcohol. ► Remarkable hydrothermal stability. - Abstract: A novel mesoporous ZSM-5 zeolite was hydrothermally synthesized using glucose as a template. Characterizations by XRD, TEM and nitrogen isotherms indicated that ZSM-5 possessed worm-like mesoporous. {sup 27}Al-MAS-NMR and NH{sub 3}-TPD showed that the mesoporous ZSM-5 preserved tetrahedral coordination aluminum and stronger acidity than conventional mesoporous material. As-prepared mesoporous ZSM-5 was successfully used in alkylation reaction of phenol with tert-butanol and exhibited significantly high phenol conversion and 2,4-DTBP selectivity. In addition, the hydrothermal stability was also studied by boiling in water for 7 days and displayed good results.

  5. First Synthesis of Continuous Mesoporous Copper Films with Uniformly Sized Pores by Electrochemical Soft Templating.

    PubMed

    Li, Cuiling; Jiang, Bo; Wang, Zhongli; Li, Yunqi; Hossain, Md Shahriar A; Kim, Jung Ho; Takei, Toshiaki; Henzie, Joel; Dag, Ömer; Bando, Yoshio; Yamauchi, Yusuke

    2016-10-04

    Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.

  6. Sunlight-Catalyzed Conversion of Cyclic Organics with Novel Mesoporous Organosilicas

    DTIC Science & Technology

    2006-10-17

    www.elsevier.com/locate/catcom Catalysis Communications 8 (2007) 1052–1056Sunlight-catalyzed conversion of cyclic organics with novel mesoporous...2006Abstract Porphyrin-embedded periodic mesoporous organosilica (PMO) materials were developed for sunlight-stimulated degradation of cyclic organics . The...Periodic mesoporous organosilicas (PMOs) provide organic functionality in a silica matrix through the combi- nation of covalently linked organic and silica

  7. Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Kong, Jiangrong; Liu, Yaru; Liu, Qicheng; Zhu, Hongze

    2015-03-01

    Mesoporous carbon is constructed by monolithic polyaromatic mesophase deriving from the hexane insoluble of coal-tar pitch. This carbon material exhibits spherical morphology and layered crystallite, and thereby can be graphitized at 900 °C without destroying the mesoporous structure. Electrochemical measurements indicate that graphitic mesoporous carbon (GMC) support not only improves the activity of Pt electrocatalyst to oxygen reduction reaction (ORR), but also shows higher corrosion resistance than commercial XC-72 carbon black in the acid cathode environment.

  8. Using Silica Sol as a Nanoglue to Prepare Nanoscale Mesoporous Composite Gel and Aerogels

    DTIC Science & Technology

    2000-03-31

    entitled: "USING SILICA SOL AS A NANOGLUE TO PREPARE NANOSCALE MESOPOROUS COMPOSITE GEL AND AEROGELS" Request for release for publication. REF...L. Anderson, Karen E. Swider Lyons, Ceha I. Merzbacher, Joseph V. Ryan and Veronica M. Cepak 3 MESOPOROUS COMPOSITE GELS AND AEROGELS 4 5 6 1...to mesoporous composite gels and aerogels and their various uses. 9 10 2. Description of the Background Art 11 Xerogels and aerogels

  9. Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications

    SciTech Connect

    Huh, Seong

    2004-12-19

    I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu2+ adsorption capacity tests, The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu2+ adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst

  10. Morphological control of multifunctionalized mesoporous silica nanomaterials for catalysis applications

    NASA Astrophysics Data System (ADS)

    Huh, Seong

    I found an efficient method to control the morphology of the organically monofunctionalized mesoporous silica materials by introducing different types of organoalkoxysilanes in a base-catalyzed co-condensation reaction. The monofunctionalized materials exhibit different particle morphologies relative to the pure MCM-41 material. The concentration dependence of the morphology is a critical factor to determine the final particle shape. A proposed mechanism of the shape evolution is also offered. After understanding the role of organoalkoxysilanes in producing various well-shaped nanomaterials, I also obtained a series of bifunctional mesoporous silica materials with certain particle morphology. A series of bifunctional mesoporous silica nanospheres (MSNs) whose physicochemical properties was investigated via solid state NMR techniques and Cu 2+ adsorption capacity tests. The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu2+ adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst system that is capable of

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

    PubMed

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

    2009-01-01

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

  12. Aromatization of Ethanol Over Desilicated ZSM-5 Zeolites: Effect of Pore Size in the Mesoporous Region.

    PubMed

    Jun, Jong Won; Hasan, Zubair; Kim, Chul-Ung; Jeong, Soon-Yong; Jhung, Sung Hwa

    2016-05-01

    Mesoporous ZSM-5 zeolites were obtained from microporous ZSM-5 by desilication using aqueous NaOH solutions, and their catalytic activity in the aromatization of ethanol was investigated in order to understand the effects of pore size, in the mesoporous region, on the product distribution and stability of the catalysts. Mesopores generally enhanced the selectivities towards aromatics and stability for aromatization. Mesopores with a maximum pore diameter of around 13 nm were the most effective in the aromatization process (especially for benzene and toluene), suggesting that pore-diameter optimization is necessary for efficient catalysis such as aromatization.

  13. Effect of mesoporous silica under Neisseria meningitidis transformation process: environmental effects under meningococci transformation

    PubMed Central

    2011-01-01

    Background This study aimed the use of mesoporous silica under the naturally transformable Neisseria meningitidis, an important pathogen implicated in the genetic horizontal transfer of DNA causing a escape of the principal vaccination measures worldwide by the capsular switching process. This study verified the effects of mesoporous silica under N. meningitidis transformation specifically under the capsular replacement. Methods we used three different mesoporous silica particles to verify their action in N. meningitis transformation frequency. Results we verified the increase in the capsular gene replacement of this bacterium with the three mesoporous silica nanoparticles. Conclusion the mesouporous silica particles were capable of increasing the capsule replacement frequency in N. meningitidis. PMID:21787408

  14. Introduction of bridging and pendant organic groups into mesoporous alumina materials.

    PubMed

    Grant, Stacy M; Woods, Stephan M; Gericke, Arne; Jaroniec, Mietek

    2011-11-01

    Incorporation of organic functionalities into soft-templated mesoporous alumina was performed via organosilane-assisted evaporation induced self-assembly using aluminum alkoxide precursors and block copolymer templates. This strategy permits one to obtain mesoporous alumina-based materials with tailorable adsorption, surface and structural properties. Isocyanurate, ethane, mercaptopropyl, and ureidopropyl-functionalized mesoporous alumina materials were synthesized with relatively high surface area and large pore volume with uniform and wormhole-like mesopores. The presence of organosilyl groups within these hybrid materials was confirmed by IR or Raman spectroscopy and their concentration was determined by elemental analysis.

  15. Effects of catalyst pore structure and acid properties on the dehydration of glycerol.

    PubMed

    Choi, Youngbo; Park, Hongseok; Yun, Yang Sik; Yi, Jongheop

    2015-03-01

    Hierarchical porous catalysts have recently attracted increasing interest because of the enhanced accessibility to active sites on such materials. In this context, previously reported hierarchically mesoporous ASN and ASPN materials are evaluated by applying them to the dehydration of glycerol, and demonstrate excellent catalytic performance. In addition, a comprehensive understanding of the effects of pore structures and the acid properties on the reaction through comparative studies with microporous HZSM-5 and mesoporous AlMCM-41 is provided.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-01-01

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

  19. Surface properties of mesoporous carbon-silica gel adsorbents

    SciTech Connect

    Leboda, R.; Turov, V.V.; Charmas, B.; Skubiszewska-Zieba, J.; Gun'ko, V.M.

    2000-03-01

    Carbon/silica (carbosil) samples prepared utilizing mesoporous silica gel (Si-60) modified by methylene chloride pyrolysis were studied by nitrogen adsorption, quasi-isothermal thermogravimetry, p-nitrophenol adsorption from aqueous solution, and {sup 1}H NMR methods. The structural characteristics and other properties of carbosils depend markedly on the synthetic conditions and the amount of carbon deposited. The changes in the pore size distribution with increasing carbon concentration suggest grafting of carbon mainly in pores, leading to diminution of the mesopore radii. However, heating pure silica gel at the pyrolysis temperature of 550 C leads to an increase in the pore radii. The quasi-isothermal thermogravimetry and {sup 1}H NMR spectroscopy methods used to investigate the water layers on carbosils showed a significant capability of carbosils to adsorb water despite a relatively large content of the hydrophobic carbon deposit, which represents a nonuniform layer incompletely covering the oxide surface.

  20. Graphitic mesoporous carbon as a durable fuel cell catalyst support

    SciTech Connect

    Dai, Sheng; Liang, Chengdu; Shanahan, Paul; Xu, Lianbin; Waje, Mahesh; Yan, Y.S.

    2008-01-01

    Highly stable graphitic mesoporous carbons (GMPCs) are synthesized by heat-treating polymer-templated mesoporous carbon (MPC) at 2600 C. The electrochemical durability of GMPC as Pt catalyst support (Pt/GMPC) is compared with that of carbon black (Pt/XC-72). Comparisons are made using potentiostatic and cyclic voltammetric techniques on the respective specimens under conditions simulating the cathode environment of PEMFC (proton exchange membrane fuel cell). The results indicate that the Pt/GMPC is much more stable than Pt/XC-72, with 96% lower corrosion current. The Pt/GMPC also exhibits a greatly reduced loss of catalytic surface area: 14% for Pt/GMPC vs. 39% for Pt/XC-72.

  1. Measurement of the orthopositronium confinement energy in mesoporous thin films

    SciTech Connect

    Crivelli, Paolo; Gendotti, Ulisse; Rubbia, Andre; Liszkay, Laszlo; Perez, Patrice; Corbel, Catherine

    2010-05-15

    In this paper, we present measurements of the ortho-positronium (ortho-Ps) emission energy in vacuum from mesoporous films using the time-of-flight technique. We show evidence of quantum mechanical confinement in the mesopores that defines the minimal energy of the emitted Ps. Two samples with different effective pore sizes, measured with positron annihilation lifetime spectroscopy, are compared for the data collected in the temperature range 50-400 K. The sample with smaller pore size exhibits a higher minimal energy (73{+-}5 meV), compared to the sample with bigger pores (48{+-}5 meV), due to the stronger confinement. The dependence of the emission energy with the temperature of the target is modeled as ortho-Ps being confined in rectangular boxes in thermodynamic equilibrium with the sample. We also measured that the yield of positronium emitted in vacuum is not affected by the temperature of the target.

  2. Chemoradiotherapeutic wrinkled mesoporous silica nanoparticles for use in cancer therapy

    SciTech Connect

    Munaweera, Imalka; Balkus, Kenneth J. Jr. E-mail: Anthony.DiPasqua@unthsc.edu; Koneru, Bhuvaneswari; Shi, Yi; Di Pasqua, Anthony J. E-mail: Anthony.DiPasqua@unthsc.edu

    2014-11-01

    Over the last decade, the development and application of nanotechnology in cancer detection, diagnosis, and therapy have been widely reported. Engineering of vehicles for the simultaneous delivery of chemo- and radiotherapeutics increases the effectiveness of the therapy and reduces the dosage of each individual drug required to produce an observable therapeutic response. We here developed a novel chemoradiotherapeutic 1,2-dioleoyl-sn-glycero-3-phosphocholine lipid coated/uncoated platinum drug loaded, holmium-containing, wrinkled mesoporous silica nanoparticle. The materials were characterized with TEM, FTIR, {sup 1}H NMR, energy dispersive x-ray, inductively coupled plasma-mass spectrometry, and zeta potential measurements. In vitro platinum drug release from both lipid coated and uncoated chemoradiotherapeutic wrinkled mesoporous silica are reported. Various kinetic models were used to analyze the release kinetics. The radioactivity of the chemoradiotherapeutic nanocarriers was measured after neutron-activation.

  3. Mesoporous Silica Nanoparticles and Films for Cargo Delivery

    NASA Astrophysics Data System (ADS)

    Guardado Alvarez, Tania Maria

    Mesoporous silica materials are well known materials that can range from films to nanoparticles. Mesoporous silica nanoparticles (MSNs) and mesoporous silica films have been of increasing interest among the scientific community for its use in cargo delivery. Silica provides ease of functionalization, a robust support and biocompatibility. Several methods have been used in order to give the mesoporous silica nanomaterials different qualities that render them a useful material with different characteristics. Among these methods is surface modification by taking advantage of the OH groups on the surface. When a molecule attached to the surface can act as a molecular machine it transforms the nanomaterial to act as delivery system that can be activated upon command. The work covered in this thesis focuses on the development and synthesis of different mesoporous silica materials for the purpose of trapping and releasing cargo molecules. Chapter 2 focuses in the photoactivation of "snap-top" stoppers over the pore openings of mesoporous silica nanoparticles that releases intact cargo molecules from the pores. The on-command release can be stimulated by either one UV photon or two coherent near-IR photons. Two-photon activation is particularly desirable for use in biological systems because it enables good tissue penetration and precise spatial control. Chapter 3 focuses on the design and synthesis of a nano-container consisting of mesoporous silica nanoparticles with the pore openings covered by "snap-top" caps that are opened by near-IR light. A photo transducer molecule that is a reducing agent in an excited electronic state is covalently attached to the system. Near IR two-photon excitation causes intermolecular electron transfer that reduces a disulfide bond holding the cap in place, thus allowing the cargo molecules to escape. The operation of the "snap-top" release mechanism by both one- and two photon is described. This system presents a proof of concept of a near

  4. Preparation and photoluminescence study of mesoporous indium hydroxide nanorods

    SciTech Connect

    Li, Changyu; Lian, Suoyuan; Liu, Yang; Liu, Shouxin; Kang, Zhenhui

    2010-02-15

    Mesoporous indium hydroxide nanorods were successfully synthesized by a mild one-step one-pot method. The obtained samples were characterized by X-ray diffraction, transmission electron microscopy with selected area electron diffraction, N{sub 2} adsorption, ultraviolet-visible absorption and photoluminescence, respectively. Transmission electron microscopy showed that there were some pores in the samples, which were mainly composed of rod-like shapes with length of 300 nm and diameter of 90 nm. N{sub 2} adsorption/desorption measurements confirmed that the prepared powder was mesoporous with average pore diameter of 3.1 nm. The ultraviolet-visible absorption spectroscopy analysis indicated that the band gap energy of the samples was 5.15 eV. Photoluminescence spectrum showed that there were two strong emissions under ultraviolet light irradiation. The growth mechanism of indium hydroxide nanorods and the role of cetyltrimethyl ammonium bromide were also discussed.

  5. Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon.

    PubMed

    Wang, Gang; Dou, Baojuan; Zhang, Zhongshen; Wang, Junhui; Liu, Haier; Hao, Zhengping

    2015-04-01

    Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.

  6. Chemoradiotherapeutic wrinkled mesoporous silica nanoparticles for use in cancer therapy

    NASA Astrophysics Data System (ADS)

    Munaweera, Imalka; Koneru, Bhuvaneswari; Shi, Yi; Di Pasqua, Anthony J.; Balkus, Kenneth J., Jr.

    2014-11-01

    Over the last decade, the development and application of nanotechnology in cancer detection, diagnosis, and therapy have been widely reported. Engineering of vehicles for the simultaneous delivery of chemo- and radiotherapeutics increases the effectiveness of the therapy and reduces the dosage of each individual drug required to produce an observable therapeutic response. We here developed a novel chemoradiotherapeutic 1,2-dioleoyl-sn-glycero-3-phosphocholine lipid coated/uncoated platinum drug loaded, holmium-containing, wrinkled mesoporous silica nanoparticle. The materials were characterized with TEM, FTIR, 1H NMR, energy dispersive x-ray, inductively coupled plasma-mass spectrometry, and zeta potential measurements. In vitro platinum drug release from both lipid coated and uncoated chemoradiotherapeutic wrinkled mesoporous silica are reported. Various kinetic models were used to analyze the release kinetics. The radioactivity of the chemoradiotherapeutic nanocarriers was measured after neutron-activation.

  7. Fluorescent Functionalized Mesoporous Silica for Radioactive Material Extraction

    SciTech Connect

    Li, Juan; Zhu, Kake; Shang, Jianying; Wang, Donghai; Nie, Zimin; Guo, Ruisong; Liu, Chongxuan; Wang, Zheming; Li, Xiaolin; Liu, Jun

    2012-08-01

    Mesoporous silica with covalently bound salicylic acid molecules incorporated in the structure was synthesized with a one-pot, co-condensation reaction at room temperature. The as-synthesized material has a large surface area, uniform particle size, and an ordered pore structure as determined by characterization with transmission electron microscopy, thermal gravimetric analysis, and infrared spectra, etc. Using the strong fluorescence and metal coordination capability of salicylic acid, functionalized mesoporous silica (FMS) was developed to track and extract radionuclide contaminants, such as uranyl [U(VI)] ions encountered in subsurface environments. Adsorption measurements showed a strong affinity of the FMS toward U(VI) with a Kd value of 105 mL/g, which is four orders of magnitude higher than the adsorption of U(VI) onto most of the sediments in natural environments. The new materials have a potential for synergistic environmental monitoring and remediation of the radionuclide U(VI) from contaminated subsurface environments.

  8. Tunable thermal conductivity in mesoporous silicon by slight porosity change

    NASA Astrophysics Data System (ADS)

    Seol, Jae Hun; Barth, David S.; Zhu, Jia; Ćoso, Dušan; Hippalgaonkar, Kedar; Lim, Jongwoo; Han, Junkyu; Zhang, Xiang; Majumdar, Arun

    2017-08-01

    We report the thermal conductivity of photoelectrochemically synthesized mesoporous silicon (MPS), with ˜20-nm diameter pores and 52%-58% porosity. The thermal conductivity of MPS samples with a thickness of a few microns was measured using the three omega (3 ω ) differential technique. We experimentally demonstrated that the thermal conductivity of MPS varies between 3 and 7 W/m K at room temperature and is dependent on the photoelectrochemical etching times used during the MPS synthesis, which induces a slight change in the MPS porosity. Calculations were conducted using the Boltzmann transport equation in the relaxation time approximation, with the results suggesting that the large thermal conductivity reduction in the MPSs was not entirely explained by the pore boundary scattering. Our findings indicate that elastic softening in the mesoporous structure may be responsible for the reduction in the thermal conductivity.

  9. Incorporation of terbium(III) ion into mesoporous silica particles

    NASA Astrophysics Data System (ADS)

    Kataoka, Takuya; Wang, Liyin; Kobayashi, Kouhei; Nishikawa, Masami; Tagaya, Motohiro

    2016-10-01

    Terbium(III)-doped mesoporous silicas were synthesized, and the states of terbium ions in the silica frameworks were investigated. The mesopores were preserved upon doping at terbium ion molar concentrations relative to (Si+Tb) up to 15 mol %, indicating the interaction of terbium ions with Si-O bonds. Significant morphological changes of the particles were observed with increasing the doping concentration. The shapes of the photoluminescence spectra due to the transitions of 5D4 → 7F6 and 5D4 → 7F5 were indicative of the presence of terbium ions in the silica matrix, and the quantum efficiency (2.1-2.8%) and lifetime (1.6-1.9 ms) decreased with increasing the doping concentration up to 15 mol %. Therefore, the terbium ions are considered to be located inside the amorphous silica frameworks, where they electrostatically interact with the O atoms of silanol and siloxane groups.

  10. Antibiofilm effect of supramolecularly templated mesoporous silica coatings.

    PubMed

    Pezzoni, Magdalena; Catalano, Paolo N; Pizarro, Ramón A; Desimone, Martín F; Soler-Illia, Galo J A A; Bellino, Martín G; Costa, Cristina S

    2017-08-01

    Bacteria attached to solid surfaces and encased in a self-synthesized matrix, so-called biofilms, are highly difficult to eradicate and present negative impact on industry and human health. The ability of supramolecularly templated mesoporous silica coatings to inhibit biofilm formation in Pseudomonas aeruginosa is shown here. Assays employing submerged and air-liquid interface biofilms demonstrated that mesoporous coatings with tuned pore size significantly reduce the number of attached bacteria and matrix production. Given its versatility, scalability, robustness and low cost, our proposal is attractive for the production of transparent, inert and permanent antibiofilm coatings that could be applied on multiple surfaces. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Catalytic Mesoporous Janus Nanomotors for Active Cargo Delivery

    PubMed Central

    2015-01-01

    We report on the synergy between catalytic propulsion and mesoporous silica nanoparticles (MSNPs) for the design of Janus nanomotors as active cargo delivery systems with sizes <100 nm (40, 65, and 90 nm). The Janus asymmetry of the nanomotors is given by electron beam (e-beam) deposition of a very thin platinum (2 nm) layer on MSNPs. The chemically powered Janus nanomotors present active diffusion at low H2O2 fuel concentration (i.e., <3 wt %). Their apparent diffusion coefficient is enhanced up to 100% compared to their Brownian motion. Due to their mesoporous architecture and small dimensions, they can load cargo molecules in large quantity and serve as active nanocarriers for directed cargo delivery on a chip. PMID:25844893

  12. Positronium lifetime measurements in micro- and mesoporous ferrisilicates

    NASA Astrophysics Data System (ADS)

    Dũng, Trần Quốc; Lázár, Károly

    2017-10-01

    Positron annihilation lifetime, Doppler broadening measurements have been used to study microporous FER and MFI structures containing framework subtituted iron in different amounts. Mesoporous SBA-15 samples without and with iron introduced to the pore walls were also investigated by these methods. Mössbauer measurements have been accompanied to prove the extent of isomorphous incorporation of iron into the different structures. The results reveal a certain dependence of lifetimes on the various pore and channel sizes. Addition of iron does not influence significantly the observed lifetimes in FER microporous systems. However a slight decrease of lifetimes can be observed in the MFI samples. The effect of addition of iron in mesoporous SBA-15 system is more expressed. Supplement of iron also has an influence on the S parameter of Doppler broadening spectra.

  13. Modeling the abnormally slow infiltration rate in mesoporous films.

    PubMed

    Berli, Claudio L A; Mercuri, Magalí; Bellino, Martín G

    2017-01-18

    Mesoporous films have been shown to exhibit striking behaviors in capillary-driven infiltration experiments. The process has been shown to follow classical Lucas-Washburn dynamics, but the effective pore radius has been calculated from hydrodynamic resistance considerations to be orders of magnitude lower than measured pore dimensions. In addition, the infiltration rate has been observed to decrease with increasing pore diameter, in contrast to the expected trend for capillary-like pores. Here, we present a simple model accounting for the mechanism behind these anomalous effects. We found the infiltration rate to be inversely proportional to the cubed ratio of pore to neck size. This physical scaling correctly modeled both the magnitude of the infiltration rate and its variation with pore diameters, for a wide range of experimental data. The model established a connection between capillary filling dynamics and nanoscale pore structure, which is of practical interest for the design and characterization of mesoporous films.

  14. Novel nanofluids based on mesoporous silica for enhanced heat transfer

    NASA Astrophysics Data System (ADS)

    Nikkam, N.; Saleemi, M.; Toprak, M. S.; Li, S.; Muhammed, M.; Haghighi, E. B.; Khodabandeh, R.; Palm, B.

    2011-11-01

    Nanofluids, which are liquids with engineered nanometer-sized particles suspensions, have drawn remarkable attraction from the researchers because of their enormous potential to enhance the efficiency in heat-transfer fluids. In the present study, water-based calcined mesoporous silica nanofluids were prepared and characterized. The commercial mesoporous silica (MPSiO2) nanoparticles were dispersed in deionized water by means of pH adjustment and ultrasonic agitation. MPSiO2 nanoparticles were observed to have an average particle size of 350 ± 100 nm by SEM analysis. The concentration of MPSiO2 was varied between 1 and 6 wt%. The physicochemical properties of nanofluids were characterized using various techniques, such as particle size analyzer, zeta-potential meter, TEM, and FT-IR. The thermal conductivity was measured by Transient Plane Source (TPS) method, and nanofluids showed a higher thermal conductivity than the base liquid for all the tested concentrations.

  15. Mesoporous silica nanoparticles for bioadsorption, enzyme immobilisation, and delivery carriers

    NASA Astrophysics Data System (ADS)

    Popat, Amirali; Hartono, Sandy Budi; Stahr, Frances; Liu, Jian; Qiao, Shi Zhang; Qing (Max) Lu, Gao

    2011-07-01

    Mesoporous silica nanoparticles (MSNs) provide a non-invasive and biocompatible delivery platform for a broad range of applications in therapeutics, pharmaceuticals and diagnosis. The creation of smart, stimuli-responsive systems that respond to subtle changes in the local cellular environment are likely to yield long term solutions to many of the current drug/gene/DNA/RNA delivery problems. In addition, MSNs have proven to be promising supports for enzyme immobilisation, enabling the enzymes to retain their activity, affording them greater potential for wide applications in biocatalysis and energy. This review provides a comprehensive summary of the advances made in the last decade and a future outlook on possible applications of MSNs as nanocontainers for storage and delivery of biomolecules. We discuss some of the important factors affecting the adsorption and release of biomolecules in MSNs and review of the cytotoxicity aspects of such nanomaterials. The review also highlights some promising work on enzyme immobilisation using mesoporous silica nanoparticles.

  16. Mesoporous silica nanoparticles for bioadsorption, enzyme immobilisation, and delivery carriers.

    PubMed

    Popat, Amirali; Hartono, Sandy Budi; Stahr, Frances; Liu, Jian; Qiao, Shi Zhang; Qing Max Lu, Gao

    2011-07-01

    Mesoporous silica nanoparticles (MSNs) provide a non-invasive and biocompatible delivery platform for a broad range of applications in therapeutics, pharmaceuticals and diagnosis. The creation of smart, stimuli-responsive systems that respond to subtle changes in the local cellular environment are likely to yield long term solutions to many of the current drug/gene/DNA/RNA delivery problems. In addition, MSNs have proven to be promising supports for enzyme immobilisation, enabling the enzymes to retain their activity, affording them greater potential for wide applications in biocatalysis and energy. This review provides a comprehensive summary of the advances made in the last decade and a future outlook on possible applications of MSNs as nanocontainers for storage and delivery of biomolecules. We discuss some of the important factors affecting the adsorption and release of biomolecules in MSNs and review of the cytotoxicity aspects of such nanomaterials. The review also highlights some promising work on enzyme immobilisation using mesoporous silica nanoparticles.

  17. Synthesis and characterization of acidic mesoporous borosilicate thin films.

    PubMed

    Xiu, Tongping; Liu, Qian; Wang, Jiacheng

    2009-02-01

    Work on the synthesis and characterization of acidic wormhole-like ordered mesoporous borosilicate thin films (MBSTFs) on silicon wafers is described in this paper. The MBSTFs coated by the dip-coating method were prepared through an evaporation-induced self-assembly (EISA) process using nonionic block copolymers as structure-directing agents. Fourier transform infrared (FT-IR) spectroscopy confirmed the formation of borosiloxane bonds (Si-O-B). High-resolution transmission electron microscopy (HRTEM) and N2 sorption evidenced a wormhole-like mesoporous structure in the MBSTFs obtained. Scanning electron microscopy (SEM) images of the cross sections and surfaces of the samples showed that MBSTFs on silicon wafers were continuous, homogeneous and did not crack. The acidic properties of the MBSTFs were characterized by FT-IR spectra of chemisorbed pyridine. The MBSTFs thus prepared may find their future applications in many fields including chemical sensors, catalysis, optical coating, molecule separation, etc.

  18. Natural dye -sensitized mesoporous ZnO solar cell

    NASA Astrophysics Data System (ADS)

    Wu, Qishuang; Shen, Yue; Wu, Guizhi; Li, Linyu; Cao, Meng; Gu, Feng

    2011-02-01

    Natural dye-sensitized solar cells (N-DSSCs) were assembled using chlorophyll sensitized mesoporous ZnO (based on FTO) as the photoanode and platinum plate as the cathode. The natural dyes (chlorophyll) were extracted from spinach by simple procedure. The absorption spectrum and fluorescence spectrum of chlorophyll were studied. Mesoporous ZnO (m-ZnO) applied to the N-DSSCs was synthesized through hydrothermal method. The structures and morphologies were characterized by X-ray Diffraction (XRD) and diffuse reflection. The results indicated that the samples had an average pore size of 17 nm and the m-ZnO was hexagonal wurtzite structure. The performances of the N-DSSCs were investigated under AM 1.5G illumination. The Voc of the N-DSSCs was about 480mv, and the Isc was about 470μA. The performance of the N-DSSCs could be further improved by adjusting its structure.

  19. Natural dye -sensitized mesoporous ZnO solar cell

    NASA Astrophysics Data System (ADS)

    Wu, Qishuang; Shen, Yue; Wu, Guizhi; Li, Linyu; Cao, Meng; Gu, Feng

    2010-10-01

    Natural dye-sensitized solar cells (N-DSSCs) were assembled using chlorophyll sensitized mesoporous ZnO (based on FTO) as the photoanode and platinum plate as the cathode. The natural dyes (chlorophyll) were extracted from spinach by simple procedure. The absorption spectrum and fluorescence spectrum of chlorophyll were studied. Mesoporous ZnO (m-ZnO) applied to the N-DSSCs was synthesized through hydrothermal method. The structures and morphologies were characterized by X-ray Diffraction (XRD) and diffuse reflection. The results indicated that the samples had an average pore size of 17 nm and the m-ZnO was hexagonal wurtzite structure. The performances of the N-DSSCs were investigated under AM 1.5G illumination. The Voc of the N-DSSCs was about 480mv, and the Isc was about 470μA. The performance of the N-DSSCs could be further improved by adjusting its structure.

  20. Purification of Sewage Contaminated by Oil Products Using Mesoporous Coal

    NASA Astrophysics Data System (ADS)

    Gvazava, Elene; Maisuradze, Nino; Samkharadze, Irma

    2016-10-01

    The sorption properties of mesoporous coals (pore size of ∼⃒ 4 nm, the specific surface area of 25 to 150 m2/g) of Georgian hard coal deposit have been studied and the efficacy of their usage for the treatment of sewage water polluted by oil products has been established. Purification rate depends on coal mass loaded in filter, grain size, initial concentration of oil products, the water acidity, etc.

  1. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    SciTech Connect

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  2. Magnetic Properties of ni Nanowires Grown in Mesoporous Silicon Templates

    NASA Astrophysics Data System (ADS)

    Dolgiy, A. L.; Redko, S. V.; Yanushkevich, K. I.

    2013-05-01

    Magnetic properties of Ni nanowires electrochemically deposited into pores of mesoporous silicon template under the stationary galvanostatic regime were investigated by measuring the temperature dependence (77-700 K) of the specific magnetization σ. The measured σ values were lower with respect to that of bulk Ni. The Curie temperature, TC, derived from σ(T) for low deposition times of Ni was less (575 K) than that for bulk Ni (630 K). This is caused by dimensional effects of Ni nanoparticles.

  3. Tailoring the mesoporous texture of graphitic carbon nitride.

    PubMed

    Yang, Jae-Hun; Kim, Gain; Domen, Kazunari; Choy, Jin-Ho

    2013-11-01

    Recently, graphitic carbon nitride (g-C3N4) materials have received a great attention from many researchers due to their various roles as a visible light harvesting photocatalyst, metal-free catalyst, reactive template, nitrogen source of nitridation reaction, etc. g-C3N4 could be prepared by temperature-induced polymerization of cyanamide or melamine. In this study, we report a preparation of mesoporous graphitic carbon nitrides with tailored porous texture including pore size, and specific surface area from cyanamide and colloidal silica nanoparticles (Ludox). At first, cyanamide-silica nanocomposites were prepared by mixing colloidal silica with different size in the range of 7-22 nm and cyanamide, followed by evaporating the solvent in the resulting mixture. Mesoporous g-C3N4 samples were prepared by calcining cyanamide-silica nanocomposite at 550 degrees C for 4 hrs and removing the silica nanoparticles by using ammonium hydrogen fluoride. The formation of g-C3N4 was confirmed by the sharp (002) peak (d = 3.25 A) of graphitic interlayer stacking, and the broad (100) peak (d = 6.86 A) of in-plane repeating unit in the X-ray diffraction patterns. According to N2 adsorption-desorption analysis, the pore size of mesoporous carbon nitrides was similar to the size of colloidal silica used as hard template (7-22 nm). The specific surface area of mesoporous g-C3N4 could be tailored in the range of 189 m2/g-288 m2/g.

  4. Substitutions of strontium in mesoporous calcium silicate and their physicochemical and biological properties.

    PubMed

    Zhu, Yufang; Zhu, Min; He, Xing; Zhang, Jianhua; Tao, Cuilian

    2013-05-01

    Calcium silicate (Ca-Si) based bioceramics have been regarded as a potential bioactive materials for bone tissue regeneration. In this study, we have successfully prepared ordered mesoporous strontium (Sr)-substituted CaSiO3 (Sr-CaSiO3) materials by using a triblock copolymer (P123) as a structure-directing agent. The microstructure and porosity of mesoporous Sr-CaSiO3 materials were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and the N2 adsorption-desorption technique. The substitution of Sr for Ca in mesoporous CaSiO3 did not change the mesoporous structure, but the surface area and pore volume decreased with increasing Sr substitution. The effects of the Sr substitution on the physiochemical and biological properties of mesoporous CaSiO3 materials were evaluated by the ion dissolution, apatite-forming ability, proliferation and alkaline phosphatase (ALP) activity of osteoblast-like MC3T3-E1 cells. The results showed that the increasing Sr substitution decreased the dissolution rate of Ca and Si ions from mesoporous CaSiO3 materials and enhanced the ability to stabilize the pH environment. Mesoporous Sr-CaSiO3 materials have a similar apatite-forming ability to mesoporous CaSiO3 material, and stimulated the proliferation and ALP activity of MC3T3-E1 cells. Furthermore, using gentamicin as a model drug, mesoporous Sr-CaSiO3 materials exhibited a sustained drug release property which could be used in local drug delivery therapy. Furthermore, the drug release rate decreased to some extent with increasing Sr substitution in mesoporous CaSiO3 materials. Therefore, mesoporous Sr-CaSiO3 materials have more potential for application in bone tissue regeneration. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  5. Soft-Template-Synthesized Mesoporous Carbon for Oral Drug Delivery

    SciTech Connect

    Saha, Dipendu; Warren, Kaitlyn E; Naskar, Amit K

    2014-01-01

    Template-synthesized mesoporous carbons were successfully used in in vitro investigations of controlled delivery of three model drugs, captopril, furosemide, and ranitidine hydrochloride. Captopril and furosemide exhibited desorption kinetics over 30 40 h, and ranitidine HCl had a complete release time of 5 10 h. As evident from the slow release kinetics, we contend that our mesoporous carbon is an improved drug-delivery medium compared to state-of-the-art porous silica-based substrates. The mesoporous carbons, synthesized from phloroglucinol and lignin, a synthetic and a sustainable precursor, respectively, exhibit BET surface area of 200 400 m2 g-1 and pore volume of 0.2 0.6 cm3 g-1. The phloroglucinol-based carbon has narrower pore widths and higher pore volume than the lignin-derived counterpart and maintains a longer release time. Numerical modeling of the release kinetics data reveals that the diffusivities of all the drugs from lignin-based carbon media are of equivalent magnitude (10-22 to 10-24 m2 s-1). However, a tailored reduction of pore width in the sorbent reduces the diffusivity of smaller drug molecules (captopril) by an order of magnitude. Thus, engineered pore morphology in our synthesized carbon sorbent, along with its potential to tailor the chemistry of its interaction with sorbet, can be exploited for optimal delivery system of a preferred drug within its therapeutic level and below the level of toxicity.

  6. Carbon dioxide capture using polyethylenimine-loaded mesoporous carbons.

    PubMed

    Wang, Jitong; Chen, Huichao; Zhou, Huanhuan; Liu, Xiaojun; Qiao, Wenming; Long, Donghui; Ling, Licheng

    2013-01-01

    A high efficiency sorbent for CO2 capture was developed by loading polyethylenimine (PEI) on mesoporous carbons which possessed well-developed mesoporous structures and large pore volume. The physicochemical properties of the sorbent were characterized by N2 adsorption/desorption, scanning electron microscopy (SEM), thermal gravimetric analysis (TG) and Fourier transform infrared spectroscopy (FT-IR) techniques followed by testing for CO2 capture. Factors that affected the sorption capacity of the sorbent were studied. The sorbent exhibited extraordinary capture capacity with CO2 concentration ranging from 5% to 80%. The optimal PEI loading was determined to be 65 wt.% with a CO2 sorption capacity of 4.82 mmol-CO2/g-sorbent in 15% CO2/N2 at 75 degrees C, owing to low mass-transfer resistance and a high utilization ratio of the amine compound (63%). Moisture had a promoting effect on the sorption separation of CO2. In addition, the developed sorbent could be regenerated easily at 100 degrees C, and it exhibited excellent regenerability and stability. These results indicate that this PEI-loaded mesoporous carbon sorbent should have a good potential for CO2 capture in the future.

  7. Morphology control in mesoporous carbon films using solvent vapor annealing.

    PubMed

    Qiang, Zhe; Xue, Jiachen; Cavicchi, Kevin A; Vogt, Bryan D

    2013-03-12

    Ordered mesoporous (2-50 nm) carbon films were fabricated using cooperative self-assembly of a phenolic resin oligomer with a novel block copolymer template (poly(styrene-block-N,N-dimethyl-n-octadecylamine p-styrenesulfonate), (PS-b-PSS-DMODA)) synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Due to the high Tg of the PS segment and the strong interactions between the phenolic resin and the PSS-DMODA, the segmental rearrangement is kinetically hindered relative to the cross-linking rate of the phenolic resin, which inhibits long-range ordering and yields a poorly ordered mesoporous carbon with a broad pore size distribution. However, relatively short exposure (2 h) to controlled vapor pressures of methyl ethyl ketone (MEK) yields significant improvements in the long-range ordering and narrows the pore size distribution. The average pore size increases as the solvent vapor pressure during annealing increases, but an upper limit of p/p0 = 0.85 exists above which the films dewet rapidly during solvent vapor annealing. This approach can be extended using mesityl oxide, which has similar solvent qualities to MEK, but is not easily removed by ambient air drying after solvent annealing. This residual solvent can impact the morphology that develops during cross-linking of the films. These results illustrate the ability to fine-tune the mesostructure of ordered mesoporous carbon films through simple changes in the processing without any compositional changes in the initial cast film.

  8. Thermally Stable Mesoporous Silica Spheres synthesized under Mild Conditions

    NASA Astrophysics Data System (ADS)

    Ziegler, Christopher; You, Eunyoung; Watkins, James

    2009-03-01

    Thermally stable, mesoporous silica spheres were synthesized using a one-pot technique under mild conditions. As-calcined silica spheres were shown to be highly porous with surface areas greater than 1000 m^2/g and pore volumes on the order of 1 cc/g. Pore walls were found to be highly resistant to collapse as a consequence of thermal treatment at temperatures exceeding 750 C or hydrothermal treatment in boiling water at temperatures exceeding 100 C for over 100 hours. ^29Si-^1H cross polarization NMR data indicate that the silica is highly condensed at the surface providing rationale for the exceptional pore wall stability observed. The mesoporous silica spheres were synthesized from tetraethyl orthosilicate (TEOS) at room temperature and near-neutral pH using cysteamine and cetyltrimethylammonium bromide (CTAB) in a mixed water and ethanol system. Sphere size was shown to be tunable by altering the relative amounts of ethanol, CTAB, or TEOS. Sphere diameters ranging from 30 nm to 560 nm were observed. The preparation method and characterization of these highly condensed, thermally stable, mesoporous silica spheres for applications including sensing, catalysis, purification, and payload encapsulation is presented.

  9. Sustained release of fungicide metalaxyl by mesoporous silica nanospheres

    NASA Astrophysics Data System (ADS)

    Wanyika, Harrison

    2013-08-01

    The use of nanomaterials for the controlled delivery of pesticides is nascent technology that has the potential to increase the efficiency of food production and decrease pollution. In this work, the prospect of mesoporous silica nanoparticles (MSN) for storage and controlled release of metalaxyl fungicide has been investigated. Mesoporous silica nanospheres with average particle diameters of 162 nm and average pore sizes of 3.2 nm were prepared by a sol-gel process. Metalaxyl molecules were loaded into MSN pores from an aqueous solution by a rotary evaporation method. The loaded amount of metalaxyl as evaluated by thermogravimetric analysis was about 14 wt%. Release of the fungicide entrapped in the MSN matrix revealed sustained release behavior. About 76 % of the free metalaxyl was released in soil within a period of 30 days while only 11.5 and 47 % of the metalaxyl contained in the MSN carrier was released in soil and water, respectively, within the same period. The study showed that MSN can be used to successfully store metalaxyl molecules in its mesoporous framework and significantly delay their release in soil.

  10. Catalytic upgrading of xylan over mesoporous Y catalyst.

    PubMed

    Kim, Seong-Soo; Jun, Bo Ram; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Kim, Tae-Wan; Park, Young-Kwon

    2014-04-01

    In-situ catalytic cracking of xylan, a model compound of hemicellulose, was carried out using pyrolysis-gas chromatography/mass spectrometry over mesoporous Y for the first time. Experiments were conducted at three different temperatures, 400 degrees C, 450 degrees C, and 500 degrees C, to investigate the effect of reaction temperature. Three different biomass-to-catalyst ratios, 1:1, 1:2, and 1:3, were tested at 500 degrees C to examine the effect of catalyst dose. In addition, the catalytic activity of mesoporous Y was compared with that of Al-MCM-41. The catalysts used were characterized by N2 adsorption-desorption, temperature programmed desorption of NH3, and X-ray diffraction. The main pyrolysis products of xylan were acids, hydrocarbons, phenolics, oxygenates, aromatics, and polycyclic aromatic hydrocarbons. Mesoporous Y, which has acid sites with larger quantity and stronger acidity than those of Al-MCM-41, was shown to enhance the quality of bio-oil to a larger extent, producing a larger quantity of high-value-added products, such as aromatics and furans.

  11. Functionalized mesoporous silica nanoparticles for oral delivery of budesonide

    SciTech Connect

    Yoncheva, K.; Popova, M.; Szegedi, A.; Mihaly, J.; Tzankov, B.; Lambov, N.; Konstantinov, S.; Tzankova, V.; Pessina, F.; Valoti, M.

    2014-03-15

    Non-functionalized and amino-functionalized mesoporous silica nanoparticle were loaded with anti-inflammatory drug budesonide and additionally post-coated with bioadhesive polymer (carbopol). TEM images showed spherical shape of the nanoparticles and slightly higher polydispersity after coating with carbopol. Nitrogen physisorption and thermogravimetic analysis revealed that more efficient loading and incorporation into the pores of nanoparticles was achieved with the amino-functionalized silica carrier. Infrared spectra indicated that the post-coating of these nanoparticles with carbopol led to the formation of bond between amino groups of the functionalized carrier and carboxyl groups of carbopol. The combination of amino-functionalization of the carrier with the post-coating of the nanoparticles sustained budesonide release. Further, an in vitro model of inflammatory bowel disease showed that the cytoprotective effect of budesonide loaded in the post-coated silica nanoparticles on damaged HT-29 cells was more pronounced compared to the cytoprotection obtained with pure budesonide. -- Graphical abstract: Silica mesoporous MCM-41 particles were amino-functionalized, loaded with budesonide and post-coated with bioadhesive polymer (carbopol) in order to achieve prolonged residence of anti-inflammatory drug in GIT. Highlights: • Higher drug loading in amino-functionalized mesoporous silica. • Amino-functionalization and post-coating of the nanoparticles sustained drug release. • Achievement of higher cytoprotective effect with drug loaded into the nanoparticles.

  12. Adsorption behavior of natural anthocyanin dye on mesoporous silica

    NASA Astrophysics Data System (ADS)

    Kohno, Yoshiumi; Haga, Eriko; Yoda, Keiko; Shibata, Masashi; Fukuhara, Choji; Tomita, Yasumasa; Maeda, Yasuhisa; Kobayashi, Kenkichiro

    2014-01-01

    Because of its non-toxicity, naturally occurring anthocyanin is potentially suitable as a colorant for foods and cosmetics. To the wider use of the anthocyanin, the immobilization on the inorganic host for an easy handling as well as the improvement of the stability is required. This study is focused on the adsorption of significant amount of the natural anthocyanin dye onto mesoporous silica, and on the stability enhancement of the anthocyanin by the complexation. The anthocyanin has successfully been adsorbed on the HMS type mesoporous silica containing small amount of aluminum. The amount of the adsorbed anthocyanin has been increased by modifying the pore wall with n-propyl group to make the silica surface hydrophobic. The light fastness of the adsorbed anthocyanin has been improved by making the composite with the HMS samples containing aluminum, although the degree of the improvement is not so large. It has been proposed that incorporation of the anthocyanin molecule deep inside the mesopore is required for the further enhancement of the stability.

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

    PubMed Central

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

    2015-01-01

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

  14. Immobilization of mesoporous silica particles on stainless steel plates

    NASA Astrophysics Data System (ADS)

    Pasqua, Luigi; Morra, Marco

    2017-03-01

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

  15. Parameters affecting morphologies and efficiencies of mesoporous perovskite solars cells

    NASA Astrophysics Data System (ADS)

    Abdoul-latif, M. M.; Xu, J.; Yao, J.; Dai, S.

    2017-07-01

    The mesoporous perovskite morphologies and optical and electronic properties are influenced by many parameters with which the device performance could be affected. Firstly, the working temperature can be mentioned. Secondly the substrate temperature which combined with spin coated speed could permit to load perovskite inside the mesoporous independent to working temperature. And other factor as the methyl ammonium iodide (CH3NH3I) solution concentration could be temperature dependent on the lead iodide, means the reaction is most probable done when the concentration increase with the increasing temperature, whereas the reaction between lead iodide and methyl ammonium can be decrease with lead iodide thickness. It is most probable that the solution concentration also has a significant effect on the morphology of the perovskite that is confined in the pores of the mesoporous TiO2. It is most probable also the spin coating speed has added at this decreasing, meaning the large size of crystal decreased the transformation lead iodide to Perovskite. Andhere it will try to explain thickness of capping layer can improve the short-circuit photocurrent (Jsc) but this enhancement decrease with high working temperature.

  16. A Review: Fundamental Aspects of Silicate Mesoporous Materials

    PubMed Central

    ALOthman, Zeid A.

    2012-01-01

    Silicate mesoporous materials have received widespread interest because of their potential applications as supports for catalysis, separation, selective adsorption, novel functional materials, and use as hosts to confine guest molecules, due to their extremely high surface areas combined with large and uniform pore sizes. Over time a constant demand has developed for larger pores with well-defined pore structures. Silicate materials, with well-defined pore sizes of about 2.0–10.0 nm, surpass the pore-size constraint (<2.0 nm) of microporous zeolites. They also possess extremely high surface areas (>700 m2 g−1) and narrow pore size distributions. Instead of using small organic molecules as templating compounds, as in the case of zeolites, long chain surfactant molecules were employed as the structure-directing agent during the synthesis of these highly ordered materials. The structure, composition, and pore size of these materials can be tailored during synthesis by variation of the reactant stoichiometry, the nature of the surfactant molecule, the auxiliary chemicals, the reaction conditions, or by post-synthesis functionalization techniques. This review focuses mainly on a concise overview of silicate mesoporous materials together with their applications. Perusal of the review will enable researchers to obtain succinct information about microporous and mesoporous materials.

  17. Nucleation Pathways of CO2 Condensation under Mesoporous Templated Glass

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Byran, Matthew S.; Warren, Garfield T.; Sokol, Paul E.; Indiana University Team; NIST Collaboration

    2015-03-01

    Carbon capture and storage (CCS) are important elements in reducing greenhouse gas emission and combating global warming. The adsorption behavior of CO2 under mesoporous confinement at room temperature is particularly relevant. , Small Angle Scattering of X-ray (SAXS) and Neutron (SANS) were used to probe the adsorption process of CO2 under such mesoporous confinement MCM-41 and details of nucleation pathways were mapped out by fitting the scattering intensities with adsorption models. From both experiments, the nucleation of CO2 on the inner pore surface of MCM-41 is found to be a two-step process; high density liquid phase CO2 first forms uniform layers following the long range translational symmetry of the porous matrix, above one CO2 filling, determined by the pore size and temperature, capillary condensation initiates. The nucleation sites formed during capillary condensation start to separate the long range symmetry from the one at uniform layers. Finally, SAXS and SANS techniques are compared and they both showed their unique properties of probing the filling-dependent structures of adsorbed CO2 under such mesoporous system.

  18. Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

    SciTech Connect

    Yu Changlin; Yu, Jimmy C.; Chan Mui

    2009-05-15

    A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO{sub 2} microspheres was developed. Formation of mesoporous TiO{sub 2} and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO{sub 2} microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO{sub 2} microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide. - Graphical abstract: A novel method for preparing fluorinated mesoporous TiO{sub 2} microspheres was developed by a combined ultrasonic and hydrothermal treatment. The fluorinated TiO{sub 2} microspheres show high crystallinity, stability and enhanced photocatalytic activity.

  19. Packaging biological cargoes in mesoporous materials: opportunities for drug delivery.

    PubMed

    Siefker, Justin; Karande, Pankaj; Coppens, Marc-Olivier

    2014-11-01

    Confinement of biomolecules in structured nanoporous materials offers several desirable features ranging from chemical and thermal stability, to resistance to degradation from the external environment. A new generation of mesoporous materials presents exciting new possibilities for the formulation and controlled release of biological agents. Such materials address niche applications in enteral and parenteral delivery of biologics, such as peptides, polypeptides, enzymes and proteins for use as therapeutics, imaging agents, biosensors, and adjuvants. Mesoporous silica Santa Barbara Amorphous-15 (SBA-15), with its unique, tunable pore diameter, and easily functionalized surface, provides a representative example of this new generation of materials. Here, we review recent advances in the design and synthesis of nanostructured mesoporous materials, focusing on SBA-15, and highlight opportunities for the delivery of biological agents to various organ and tissue compartments. The SBA-15 platform provides a delivery carrier that is inherently separated from the active biologic due to distinct intra and extra-particle environments. This permits the SBA-15 platform to not require direct modification of the active biological therapeutic. Additionally, this makes the platform universal and allows for its application independent of the desired methods of discovery and development. The SBA-15 platform also directly addresses issues of targeted delivery and controlled release, although future challenges in the implementation of this platform reside in particle design, biocompatibility, and the tunability of the internal and external material properties. Examples illustrating the flexibility in the application of the SBA-15 platform are also discussed.

  20. Three dimensional mesoporous silica strucutres with templated macropores

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    A novel approach to fabricate three dimensional macroporous structures comprised of mesoporous silica is demonstrated. Well-ordered mesoporous silica structures with macroporosity were obtained by using humidified supercritical carbon dioxide as a carrier medium to infuse and domain selectively condense silica alkoxide precursor in a microphase separated block copolymer/small molecule additive blend solution casted on macroporous supports such as cellulose filter paper and sponge. Subsequent calcination was used to remove both the block copolymer template and the macroporous support. Transition electron microscopy (TEM) and small angle x-ray diffraction (SAXD) confirmed the presence of well-ordered mesopores. Scanning electron microscopy confirmed faithful replication of the features of the macroporous supports. Physisorption showed BET surface areas as high as 400m2/g and the BJH pore size distributions obtained are in close agreement with the TEM and SAXD results. This dual scale porosity within the silica template will enhance overall transport and diffusion, which is appropriate for many applications including catalysis and sensing.

  1. Capacity of mesoporous bioactive glass nanoparticles to deliver therapeutic molecules

    NASA Astrophysics Data System (ADS)

    El-Fiqi, Ahmed; Kim, Tae-Hyun; Kim, Meeju; Eltohamy, Mohamed; Won, Jong-Eun; Lee, Eun-Jung; Kim, Hae-Won

    2012-11-01

    Inorganic bioactive nanomaterials are attractive for hard tissue regeneration, including nanocomponents for bone replacement composites and nanovehicles for delivering therapeutics. Bioactive glass nanoparticles (BGn) have recently gained potential usefulness as bone and tooth regeneratives. Here we demonstrate the capacity of the BGn with mesopores to load and deliver therapeutic molecules (drugs and particularly genes). Spherical BGn with sizes of 80-90 nm were produced to obtain 3-5 nm sized mesopores through a sono-reacted sol-gel process. A simulated body fluid test of the mesoporous BGn confirmed their excellent apatite forming ability and the cellular toxicity study demonstrated their good cell viability up to 100 μg ml-1. Small molecules like chemical drug (Na-ampicillin) and gene (small interfering RNA; siRNA) were introduced as model drugs considering the mesopore size of the nanoparticles. Moreover, amine-functionalization allowed switchable surface charge property of the BGn (from -20-30 mV to +20-30 mV). Loading of ampicillin or siRNA saturated within a few hours (~2 h) and reflected the mesopore structure. While the ampicillin released relatively rapidly (~12 h), the siRNA continued to release up to 3 days with almost zero-order kinetics. The siRNA-nanoparticles were easily taken up by the cells, with a transfection efficiency as high as ~80%. The silencing effect of siRNA delivered from the BGn, as examined by using bcl-2 model gene, showed dramatic down-regulation (~15% of control), suggesting the potential use of BGn as a new class of nanovehicles for genes. This, in conjunction with other attractive properties, including size- and mesopore-related high surface area and pore volume, tunable surface chemistry, apatite-forming ability, good cell viability and the possible ion-related stimulatory effects, will potentiate the usefulness of the BGn in hard tissue regeneration.Inorganic bioactive nanomaterials are attractive for hard tissue regeneration

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

    PubMed

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

    2015-04-21

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

  3. Mesoporous Calcium Silicate Nanoparticles with Drug Delivery and Odontogenesis Properties.

    PubMed

    Huang, Ching-Yuang; Huang, Tsui-Hsien; Kao, Chia-Tze; Wu, Yuan-Haw; Chen, Wan-Chen; Shie, Ming-You

    2017-01-01

    Calcium silicate (CS) -based materials play an important role in the development of endodontic materials that induce bone/cementum tissue regeneration and inhibit bacterial viability. The aim of this study was to prepare novel mesoporous CS (MesoCS) nanoparticles that have osteogenic, drug delivery, and antibacterial characteristics for endodontic materials and also have an excellent ability to develop apatite mineralization. The MesoCS nanoparticles were prepared using sol-gel methods. In addition, the mesoporous structure, specific surface area, pore volume, and morphology of the MesoCS nanoparticles were analyzed. The apatite mineralization ability, in vitro odontogenic differentiation, drug delivery, and antibacterial properties of the MesoCS nanoparticles were further investigated. The results indicate that the 200-nm-sized MesoCS nanoparticles synthesized using a facile template method exhibited a high specific surface area and pore volume with internal mesopores (average pore size = 3.05 nm). Furthermore, the MesoCS nanoparticles can be used as drug carriers to maintain sustained release of gentamicin and fibroblast growth factor-2 (FGF-2). The MesoCS-loaded FGF-2 might stimulate more odontogenic-related protein than CS because of the FGF-2 release. Based on this work, it can be inferred that MesoCS nanoparticles are potentially useful endodontic materials for biocompatible and osteogenic dental pulp tissue regenerative materials. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  4. Facile preparation of mesoporous carbon-silica-coated graphene for the selective enrichment of endogenous peptides.

    PubMed

    Zhang, Quanqing; Zhang, Qinghe; Xiong, Zhichao; Wan, Hao; Chen, Xiaoting; Li, Hongmei; Zou, Hanfa

    2016-01-01

    A sandwich-like composite composed of ordered mesoporous carbon-silica shell-coated graphene (denoted as graphene@mSiO2-C) was prepared by an in-situ carbonation strategy. A mesoporous silica shell was synthesized by a sol-gel method, and cetyltrimethyl ammonium bromide inside the mesopores were in-situ carbonized as a carbon source to obtain a carbon-silica shell. The resulting mesoporous carbon-silica material with a sandwich structure possesses a high surface area (600 m(2) g(-1)), large pore volume (0.587 cm(3) g(-1)), highly ordered mesoporous pore (3 nm), and high carbon content (30%). This material shows not only high hydrophobicity of graphene and mesoporous carbon but also a hydrophilic silica framework that ensures excellent dispersibility in aqueous solution. The material can capture many more peptides from bovine serum albumin tryptic digests than mesoporous silica shell-coated graphene, demonstrating great enrichment efficiency for peptides. Furthermore, the prepared composite was applied to the enrichment of low-abundance endogenous peptides in human serum. Based on Matrix-Assisted Laser Desorption/ Ionization Time of Flight Mass Spectrometry identification, the graphene@mSiO2-C could efficiently size-exclude proteins and enriches the low-abundant peptides on the graphene and mesoporous carbon. And based on the LC-MS/MS results, 892 endogenous peptides were obtained by graphene@mSiO2-C, hinting at its great potential in peptides analysis.

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

    SciTech Connect

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

    2015-01-15

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

  6. Hierarchical mesoporous silica nanofibers as multifunctional scaffolds for bone tissue regeneration.

    PubMed

    Ravichandran, Ranjithkumar; Gandhi, Sakthivel; Sundaramurthi, Dhakshinamoorthy; Sethuraman, Swaminathan; Krishnan, Uma Maheswari

    2013-01-01

    Mesoporous materials with pore sizes between 2 and 50 nm have elicited widespread interest in catalysis, separation, adsorption, sensors, and drug delivery applications due to its highly ordered pore size along with high hydrothermal stability and easily modifiable surface functionalities. Fabricating these mesoporous materials as continuous fibers offers exciting vistas for biomedical applications especially in tissue engineering. The aim of the present study was to fabricate, characterize, and evaluate the cellular and gene expression of mesoporous silica with a long ordered fibrous morphology to support regeneration of bone tissue. Tetraethyl orthosilicate, polyvinyl pyrrolidone, and the tri-block copolymer P-123 were subjected to electrospinning to fabricate continuous ordered mesoporous silica nanofibers by optimizing solution and operation parameters. Mesoporous silica fibers with an average diameter of 470 nm and mesopores of dimension 5.97 nm were obtained. The combination of micropores, mesopores, macropores, and the nanofibrous morphology imparted excellent bioactivity to the mesoporous silica fibrous scaffolds as demonstrated by the proliferation of human osteoblast-like cells (MG63) and by the maintenance of its phenotype. The upregulation of collagen I, alkaline phosphatase, osteocalcin, osteopontin, and bone sialoprotein signifies the maturation of MG63 cells on the silica scaffold. Hence, these novel scaffolds are promising new biomaterials for orthopaedic applications.

  7. Novel pitch-based carbons with bimodal distribution of uniform mesopores.

    PubMed

    Gierszal, Kamil P; Jaroniec, Mietek

    2004-11-21

    A new method is proposed for the synthesis of pitch-based carbons with bimodal distribution of uniform mesopores formed by co-imprinting of spherical silica colloids and hexagonally ordered mesoporous particles of SBA-15 into mesophase pitch particles and subsequent silica dissolution.

  8. Nitrogen enriched mesoporous carbon as a high capacity cathode in lithium-oxygen batteries.

    PubMed

    Nie, Hongjiao; Zhang, Huamin; Zhang, Yining; Liu, Tao; Li, Jing; Lai, Qinzhi

    2013-09-21

    Nitrogen enriched mesoporous carbon (N-MCS) with extremely high mesopore volume and nitrogen content is prepared through a one-step hard template method. The N-MCS cathode shows excellent discharge performance in lithium-oxygen batteries. The pore space is better utilized due to its optimized pore structure and uniformly incorporated N.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  10. Studies on Supercapacitor Electrode Material from Activated Lignin-Derived Mesoporous Carbon

    SciTech Connect

    Saha, Dipendu; Li, Yunchao; Bi, Zhonghe; Chen, Jihua; Keum, Jong Kahk; Hensley, Dale K; Grappe, Hippolyte A.; Meyer III, Harry M; Dai, Sheng; Paranthaman, Mariappan Parans; Naskar, Amit K

    2014-01-01

    We synthesized mesoporous carbon from pre-cross-linked lignin gel impregnated with a surfactant as the pore-forming agent, and then activated the carbon through physical and chemical methods to obtain activated mesoporous carbon. The activated mesoporous carbons exhibited 1.5- to 6-fold increases in porosity with a maximum BET specific surface area of 1148 m2/g and a pore volume of 1.0 cm3/g. Slow physical activation helped retain dominant mesoporosity; however, aggressive chemical activation caused some loss of the mesopore volume fraction. Plots of cyclic voltammetric data with the capacitor electrode made from these carbons showed an almost rectangular curve depicting the behavior of ideal double-layer capacitance. Although the pristine mesoporous carbon exhibited the same range of surface-area-based capacitance as that of other known carbon-based supercapacitors, activation decreased the surface-area-based specific capacitance and increased the gravimetric-specific capacitance of the mesoporous carbons. Surface activation lowered bulk density and electrical conductivity. Warburg impedance as a vertical tail in the lower frequency domain of Nyquist plots supported good supercapacitor behavior for the activated mesoporous carbons. Our work demonstrated that biomass-derived mesoporous carbon materials continue to show potential for use in specific electrochemical applications.

  11. A reconstruction strategy to synthesize mesoporous SAPO molecular sieve single crystals with high MTO catalytic activity.

    PubMed

    Wang, Chan; Yang, Miao; Li, Mingrun; Xu, Shutao; Yang, Yue; Tian, Peng; Liu, Zhongmin

    2016-05-11

    Mesoporous SAPO-34 single crystals with tunable porosity and Si content have been fast synthesized within 4 hours by a reconstruction strategy, which show excellent hydrothermal stability and MTO catalytic activity. This new strategy is further proven to be applicable to prepare other mesoporous SAPO molecular sieve single crystals.

  12. Effect of Nickel Contents on the Microstructure of Mesoporous Nickel Gadolinium-Doped Ceria

    NASA Astrophysics Data System (ADS)

    Ahn, Seunghyun; Koo, Hyun; Bae, Sung-Hwan; Park, Chan; Cho, Guyoung; Chang, Ikwhang; Cha, Suk-Won; Yoo, Young-Sung

    2013-08-01

    The effect of NiO contents on the microstructure of mesoporous NiO-Gd0.25Ce0.75O2-x (NiO-GDC) composite for intermediate temperature solid oxide fuel cells (IT-SOFC) was investigated. Mesoporous NiO-GDC powders with different NiO contents were synthesized by self-assembly hydrothermal method using tri-block copolymer, Pluronic F127, as a structure directing agent. Grain growth/agglomeration behaviors of NiO particles and changes of mesoporous structure of GDC particles were characterized by microstructural analyses. NiO-GDC powders were composed of GDC nano particles with ordered mesopore inside the particles and octahedral NiO grains with truncated-edges. As the amount of NiO increases, specific area value of mesoporous NiO-GDC was decreased, and the agglomeration/growth behavior of NiO grains was accelerated.

  13. Micro-mesoporous materials obtained by zeolite recrystallization: synthesis, characterization and catalytic applications.

    PubMed

    Ivanova, Irina I; Knyazeva, Elena E

    2013-05-07

    The review covers the recent developments in the field of novel micro-mesoporous materials obtained by zeolite recrystallization. The materials are classified into three distinctly different groups depending on the degree of recrystallization: (i) coated mesoporous zeolites (RZEO-1); (ii) micro-mesoporous nanocomposites (RZEO-2); and (iii) mesoporous materials with zeolitic fragments in the walls (RZEO-3). The first part of the review is focused on the analysis of the synthetic strategies leading to different types of recrystallized materials. In the second part, a comprehensive view on their structure, texture and porosity in connection with acidic and diffusion properties is given. The last part is devoted to the catalytic applications of recrystallized materials. The advantages and disadvantages with respect to pure micro- and mesoporous molecular sieves and other hierarchical zeolites are critically analyzed and the future opportunities and perspectives are discussed.

  14. Diffusion of single dye molecules in hydrated TiO2 mesoporous films.

    PubMed

    Angiolini, Juan F; Stortz, Martín; Steinberg, Paula Y; Mocskos, Esteban; Bruno, Luciana; Soler-Illia, Galo; Angelomé, Paula C; Wolosiuk, Alejandro; Levi, Valeria

    2017-09-26

    Mesoporous oxide films are attractive frameworks in technological areas such as catalysis, sensing, environmental protection, and photovoltaics. Herein, we used fluorescence correlation spectroscopy to explore how the pore dimensions of hydrated TiO2 mesoporous calcined films modulate the molecular diffusion. Rhodamine B molecules in mesoporous films follow a Fickian process 2-3 orders slower compared to the probe in water. The mobility increases with the pore and neck radii reaching an approximately constant value for a neck radius >2.8 nm. However, the pore size does not control the dye diffusion at low ionic strength emphasizing the relevance of the probe interactions with the pore walls on dye mobility. In conclusion, our results show that the thermal conditioning of TiO2 mesoporous films provides an exceptional tool for controlling the pore and neck radii on the nanometer scale and has a major impact on molecular diffusion within the mesoporous network.

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

    DOEpatents

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

    2016-12-06

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

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

    DOEpatents

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

    2014-12-16

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

  17. Mesoporous hybrids containing Eu 3+ complexes covalently bonded to SBA-15 functionalized: Assembly, characterization and photoluminescence

    NASA Astrophysics Data System (ADS)

    Li Kong, Li; Yan, Bing; Li, Ying

    2009-07-01

    A novel series of luminescent mesoporous organic-inorganic hybrid materials has been prepared by linking Eu 3+ complexes to the functionalized ordered mesoporous SBA-15 which was synthesis by a co-condensation process of 1,3-diphenyl-1,3-propanepione (DBM) modified by the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC), tetraethoxysilane (TEOS), Pluronic P123 surfactant as a template. It was demonstrated that the efficient intramolecular energy transfer in the mesoporous material Eu(DBMSi-SBA-15) 3phen mainly occurred between the modified DBM (named as DBM-Si) and the central Eu 3+ ion. So the Eu(DBMSi-SBA-15) 3phen showed characteristic emission of Eu 3+ ion under UV irradiation with higher luminescence quantum efficiency. Moreover, the mesoporous hybrid materials exhibited excellent thermal stability as the lanthanide complex was covalently bonded to the mesoporous matrix.

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

    PubMed Central

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

    2010-01-01

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

  19. Fabrication of continuous highly ordered mesoporous silica nanofibre with core/sheath structure and its application as catalyst carrier

    NASA Astrophysics Data System (ADS)

    Wang, Haiyan; Wu, Dayong; Li, Dongzhou; Niu, Zhongwei; Chen, Yuzhe; Tang, Daihua; Wu, Min; Cao, Jianhua; Huang, Yong

    2011-09-01

    A core/sheath structured mesoporous silica nanofibre was prepared by coaxial electrospinning combined with the solvent evaporation induced surfactant assembly process. The characterization has given convincing evidence for the continuous highly ordered mesoporous structures, and its catalyst application was tested.A core/sheath structured mesoporous silica nanofibre was prepared by coaxial electrospinning combined with the solvent evaporation induced surfactant assembly process. The characterization has given convincing evidence for the continuous highly ordered mesoporous structures, and its catalyst application was tested. Electronic supplementary information (ESI) available: Synthesis of highly ordered mesoporous silica nanofibres and immobilized catalysts, characterization, and photosensitized oxidation. See DOI: 10.1039/c1nr10547g

  20. Enhanced performance of {0 0 1} facets dominated mesoporous TiO2 photocatalyst composed of high-reactive nanocrystals and mesoporous spheres

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Lu, Chunhua; Ni, Yaru; Peng, Fengping; Xu, Zhongzi

    2013-01-01

    {0 0 1} facets dominated mesoporous anatase TiO2 sheets composed of mesoporous spheres and high reactive nanocrystals with exposed {0 0 1} facets were synthesized successfully with NH4F as the capping agent by the hydrothermal and heat treatment method. The photocatalyst exhibits a high specific surface area and a higher photocatalytic activity than Degussa P25 and pure TiO2 nanosheets in the degradation of organic dyes under UV irradiation.

  1. Dual-mesoporous ZSM-5 zeolite with highly b-axis-oriented large mesopore channels for the production of benzoin ethyl ether.

    PubMed

    Zhou, Xiaoxia; Chen, Hangrong; Zhu, Yan; Song, Yudian; Chen, Yu; Wang, Yongxia; Gong, Yun; Zhang, Guobin; Shu, Zhu; Cui, Xiangzhi; Zhao, Jinjin; Shi, Jianlin

    2013-07-22

    Dual-mesoporous ZSM-5 zeolite with highly b axis oriented large mesopores was synthesized by using nonionic copolymer F127 and cationic surfactant CTAB as co-templates. The product contains two types of mesopores--smaller wormlike ones of 3.3 nm in size and highly oriented larger ones of 30-50 nm in diameter along the b axis--and both of them interpenetrate throughout the zeolite crystals and interconnect with zeolite microporosity. The dual-mesoporous zeolite exhibits excellent catalytic performance in the condensation of benzaldehyde with ethanol and greater than 99 % selectivity for benzoin ethyl ether at room temperature, which can be ascribed to the zeolite lattice structure offering catalytically active sites and the hierarchical and oriented mesoporous structure providing fast access of reactants to these sites in the catalytic reaction. The excellent recyclability and high catalytic stability of the catalyst suggest prospective applications of such unique mesoporous zeolites in the chemical industry.

  2. DEVELOPMENT OF MESOPOROUS MEMBRANE MATERIALS FOR CO2 SEPARATION

    SciTech Connect

    Wei-Heng Shih; Tejas Patil; Qiang Zhao

    2003-03-25

    The huge emissions of carbon dioxide from fossil fuel fired power plants and industrial plants over the last century have resulted in an increase of the atmospheric carbon dioxide concentration. Climatological modeling work has predicted severe climate disruption as a result of the trapping of heat due to CO{sub 2}. As an attempt to address this global warming effect, DOE has initiated the Vision 21 concept for future power plants. We first synthesized mesoporous aluminosilicates that have high surface area and parallel pore channels for membrane support materials. Later we synthesized microporous aluminosilicates as the potential thin membrane materials for selective CO{sub 2} adsorption. The pore size is controlled to be less that 1 nm so that the adsorption of CO{sub 2} on the pore wall will block the passage of N{sub 2}. Mesoporous and precipitated alumina were synthesized as the base material for CO{sub 2} adsorbent. The porous alumina is doped with Ba to enhance its CO{sub 2} affinity due to the basicity of Ba. It is shown by gas chromatograph (GC) that the addition of Ba enhances the separation CO{sub 2} from N{sub 2}. It was found that mesoporous alumina has larger specific surface area and better selectivity of CO{sub 2} than precipitated alumina. Ba improves the affinity of mesoporous alumina with CO{sub 2}. Phase may play an important role in selective adsorption of CO{sub 2}. It is speculated that mesoporous alumina is more reactive than precipitated alumina creating the xBaO {center_dot}Al{sub 2}O{sub 3} phase that may be more affinitive to CO{sub 2} than N{sub 2}. On the other hand, the barium aluminates phase (Ba{sub 3}Al{sub 2}O{sub 6}) in the mesoporous sample does not help the adsorption of CO{sub 2}. Microporous aluminosilicate was chosen as a suitable candidate for CO{sub 2}/N{sub 2} separation because the pore size is less than 10 {angstrom}. If a CO{sub 2} adsorbent is added to the microporous silica, the adsorption of CO{sub 2} can block the

  3. Sponge mesoporous silica formation using disordered phospholipid bilayers as template.

    PubMed

    Galarneau, Anne; Sartori, Federica; Cangiotti, Michela; Mineva, Tzonka; Di Renzo, Francesco; Ottaviani, M Francesca

    2010-02-18

    Lecithin/dodecylamine/lactose mixtures in ethanol/aqueous media led to the formation of sponge mesoporous silica (SMS) materials by means of tetraethoxysilane (TEOS) as silica source. SMS materials show a "sponge-mesoporous" porosity with a pore diameter of about 5-6 nm, in accordance to the length of a lecithin bilayer. SMS synthesis was developed to create a new class of powerful biocatalysts able to efficiently encapsulate enzymes by adding a porosity control to the classical sol-gel synthesis and by using phospholipids and lactose as protecting agents for the enzymes. In the present study, the formation of SMS was investigated by using electron paramagnetic resonance (EPR) probes inserted inside phospholipid bilayers. The influence of progressive addition of each component (ethanol, dodecylamine, lactose, TEOS) on phospholipid bilayers was first examined; then, the time evolution of EPR spectra during SMS synthesis was studied. Parameters informative of mobility, structure, order, and polarity around the probes were extracted by computer analysis of the EPR line shape. The results were discussed on the basis of solids characterization by X-ray diffraction, nitrogen isotherm, transmission electron microscopy, and scanning electron microscopy. The results, together with the well-known ability of ethanol to promote membrane hemifusion, suggested that the templating structure is a bicontinuous phospholipid bilayer phase, shaped as a gyroid, resulting of multiple membrane hemifusions induced by the high alcohol content used in SMS synthesis. SMS synthesis was compared to hexagonal mesoporous silica (HMS) synthesis accomplished by adding TEOS to a dodecylamine/EtOH/water mixture. EPR evidenced the difference between HMS and SMS synthesis; the latter uses an already organized but slowly growing mesophase of phospholipids, never observed before, whereas the former shows a progressive elongation of micelles into wormlike structures. SMS-type materials represent a new

  4. Photochromic ordered mesoporous hybrid materials based on covalently grafted polyoxometalates.

    PubMed

    Luo, Xiujuan; Yang, Chun

    2011-05-07

    Novel polyoxometalate (POM)-grafting mesoporous hybrid silicas, XW(11)/MHS (X=P, Si) and TBAPW(11)Si(2)/MHS, have been prepared respectively by co-condensation and post-synthesis routes based on the employment of Keggin-type monovacant XW(11) or a Si-substituted compound TBAPW(11)Si(2) as POM precursors. Upon characterization of the samples by FT-IR, XRD, ICP-AES, TEM and N(2) adsorption-desorption measurement, it was found that Keggin units were retained perfectly in ordered hexagonal mesopore channels with SBA-15 architecture and immobilized by covalent linkages on the mesopore wall. These materials, especially the co-condensed samples, exhibited stable and reversible photochromic properties under UV irradiation although no special organic component was supplied additionally as an electron donor. An investigation of the photochromism revealed that the photochromic response depended on the centre atom of the POM species (i.e., the redox potential of the POM), the content of the POM and the synthetic route of the sample, while the bleaching process was correlated not only to the redox potential but also to the pore size of the sample. The photochromic mechanism was also studied in detail by cyclic voltammetry, ESR, FT-IR and XPS techniques. It was found that the remaining P123 template acted as a reducing agent and was oxidized during the photochromic process accompanied by the reduction of the POM to heteropolyblue. Thus, a close contact between the POM and the remaining P123 chain in the sample is necessary. Low close-contact degree results in poor photochromic behavior of the post-synthesized sample and impregnated samples.

  5. Delayed emission of cold positronium from mesoporous materials

    SciTech Connect

    Cassidy, D. B.; Hisakado, T. H.; Meligne, V. E.; Tom, H. W. K.; Mills, A. P. Jr.

    2010-11-15

    It is well known that ortho-positronium (ortho-Ps) atoms are emitted with high efficiency from various porous materials following the implantation of positrons. Since the ortho-Ps lifetime in a mesoporous material may be a substantial fraction of the ortho-Ps vacuum lifetime (142 ns), the time dependence of Ps emission may have to be considered when conducting certain types of experiments, such as time of flight measurements or pulsed ortho-Ps-laser interactions, when using this kind of target as a positronium source. By taking into account the positron implantation profile and subsequent Ps diffusion and decay in a mesoporous film we calculate the time dependent ortho-Ps emission rate {Gamma}(t), which in turn allows us to establish the total annihilation rate, arising from the decay of ortho-Ps both inside and outside the sample. Using time-delayed laser spectroscopy and single-shot lifetime measurements we have directly probed the rate at which Ps is emitted into vacuum from a target with {approx}3-nm diameter pores and have observed delayed ortho-Ps emission that is consistent with our model. From the ortho-Ps decay spectrum we find that, whereas a simple two-component lifetime fit gives a short lifetime of 25.3{+-}0.3 ns, an analysis that properly takes into account the emission rate yields an ortho-Ps lifetime inside the porous material of 32.3{+-}1.2 ns, demonstrating that the ortho-Ps escape rate into vacuum can significantly modify the apparent lifetime of ortho-Ps inside a mesoporous material. Our measurements yield a Ps diffusion coefficient D = 0.07 {+-} 0.01 cm{sup 2} s{sup -1}, which is consistent with a tunneling limited diffusion process.

  6. Silver nanoparticles incorporated onto ordered mesoporous silica from Tollen's reagent

    NASA Astrophysics Data System (ADS)

    Zienkiewicz-Strzałka, M.; Pasieczna-Patkowska, S.; Kozak, M.; Pikus, S.

    2013-02-01

    Noble metal nanostructures supported on mesoporous silica are bridge between traditional silica adsorbents and modern catalysts. In this work the Ag/SBA-15 mesoporous materials were synthesized and characterized. Various forms of nanosilver supported on ordered mesoporous template have been successfully obtained via proposed procedures. In all synthesized materials, Tollen's reagent (diammine silver complex [Ag(NH3)2]+) was used as a silver source. Silver nanoparticles were prepared by reduction of ammoniacal silver complex by formaldehyde in the solution of stabilizer. After reduction, Ag nanoparticles could be deposited on SBA-15, or added during traditional synthesis of SBA-15 giving silver or silver chloride nanoparticles in the combination with porous silica. Silver nanostructures as nanoparticles or nanowires were also embedded onto the SBA-15 by incipient wetness impregnation of silver ions. Absorbed silver ions were next reduced under hydrogen at high temperature. There are many advantages of utilized ammoniacal silver complex as a silver source. Proposed method is capable to synthesis of various metal nanostructures with controlled composition and morphology. The silver ammonia complex is composed of two ions surrounding and protecting the central silver ion, so it is possible to obtain very small nanoparticles using simple approach without any functionalization of external and internal surface of SBA-15. This approach allows obtaining greatly small silver nanoparticles on SBA-15 (4 nm) or nanowires depending on the metal loading amount. Moreover, the colloidal silver solution prepared from Tollen's reagent, in the presence of triblock copolymer, remains stable for a long time. Reduction of Tollen's reagent to silver colloidal solution seems to be efficient, fast and interesting approach for the preparation of supported silver nanostructures Obtained samples were characterized by powder X-ray diffraction, small angle X-ray scattering (SAXS), UV

  7. A mesoporous silica biomaterial for dental biomimetic crystallization.

    PubMed

    Chiang, Yu-Chih; Lin, Hong-Ping; Chang, Hao-Hueng; Cheng, Ya-Wen; Tang, Hsin-Yen; Yen, Wei-Ching; Lin, Po-Yen; Chang, Kei-Wen; Lin, Chun-Pin

    2014-12-23

    The loss of overlying enamel or cementum exposes dentinal tubules and increases the risk of several dental diseases, such as dentin hypersensitivity (causing sharp pain and anxiety), caries, and pulp inflammation. This paper presents a fast-reacting, more reliable and biocompatible biomaterial that effectively occludes exposed dentinal tubules by forming a biomimetic crystalline dentin barrier. To generate this biomaterial, a gelatin-templated mesoporous silica biomaterial (CaCO3@mesoporous silica, CCMS) containing nanosized calcium carbonate particles is mixed with 30% H3PO4 at a 1/1 molar ratio of Ca/P (denoted as CCMS-HP), which enables Ca2+ and PO4(3-)/HPO4(2-) ions to permeate the dentinal tubules and form dicalcium phosphate dihydrate (DCPD), tricalcium phosphate (TCP) or hydroxyapatite (HAp) crystals at a depth of approximately 40 μm (sub-μ-CT and nano-SEM/EDS examinations). In vitro biocompatibility tests (WST-1 and lactate dehydrogenase) and ALP assays show high cell viability and mineralization ability in a transwell dentin disc model treated with CCMS-HP (p<0.05). The in vivo efficacy and biocompatibility analyses of the biomaterial in an animal model reveal significant crystal growth (DCPD, TCP or HAp-like) and no pulp irritation after 70 days (p<0.05). The developed CCMS-HP holds great promise for treating exposed dentin by growing biomimetic crystals within dentinal tubules. These findings demonstrate that the mesoporous silica biomaterials presented here have great potential for serving as both a catalyst and carrier in the repair or regeneration of dental hard tissue.

  8. Selective catalysis utilizing bifunctionalized MCM-41 mesoporous materials

    SciTech Connect

    Strosahl, Kasey Jean

    2005-01-01

    Selective catalysis is a field that has been under intense investigation for the last 100 years. The most widely used method involves catalysts with stereochemical selectivity. In this type of catalysis, the catalyst controls which reactants will be transformed into the desired product. The secret to employing this type of catalysis, though, is to design the proper catalyst, which can be difficult. One may spend as much time developing the catalyst as spent separating the various products achieved. Another method of selective catalysis is now being explored. The method involves utilizing a multifunctional mesoporous silica catalyst with a gate-keeping capability. Properly functionalized mesoporous materials with well-defined pore morphology and surface properties can provide an ideal three-dimensional environment for anchoring various homogeneous catalysts. These materials can circumvent the multi-sited two-dimensional nature most heterogeneous systems have without adversely impacting the reactant diffusivity. These single-site nanostructured catalysts with ordered geometrical structure are advantageous in achieving high selectivity and reactivity. Mesoporous materials can be prepared to include pores lined homogeneously with tethered catalysts via co-condensation. Additionally, these materials can be reacted with another (RO)3Si~Z group by using the traditional grafting method; this group is anchored predominantly at the entrances to the pores rather than inside the pores. Thus, if these ~Z groups are chosen properly, they can select certain molecules to enter the pores and be converted to products (Scheme 1). In such multifunctional catalysts, the selectivity depends on the discrimination of the gatekeeper. Gate-keeping MCM-41 materials are at the forefront of catalytic substances.

  9. Characterization of a chiral nematic mesoporous organosilica using NMR

    NASA Astrophysics Data System (ADS)

    Manning, Alan; Shopsowitz, Kevin; Giese, Michael; MacLachlan, Mark; Dong, Ronald; Michal, Carl

    2012-10-01

    Using templation with nanocrystalline cellulose, a mesoporous organosilica film with a chiral nematic pore structure has recently been developed. [1] We have used a variety of Nuclear Magnetic Resonance (NMR) techniques to characterize the pore structure. The pore size distribution has been found by analyzing the freezing point depression of absorbed water via NMR cryoporometry. The effective longitudinal and transverse pore diameters for diffusing water were investigated with Pulsed-Field Gradient (PFG) NMR and compared to a 1-D connected-pore model. Preliminary data on testing imposed chiral ordering in absorbed liquid crystals is also presented. [4pt] [1] K.E. Shopsowitz et al. JACS 134(2), 867 (2012)

  10. Why PMO? Towards functionality and utility of periodic mesoporous organosilicas.

    PubMed

    Wang, Wendong; Lofgreen, Jennifer E; Ozin, Geoffrey A

    2010-12-06

    Creative synthetic chemistry has endowed the class of periodic mesoporous organosilica materials, dubbed PMO, with a variety of new and exciting compositions, properties, and functions since its inception a decade ago. Using a handful of recent trendsetting case histories, the multidisciplinary applications of PMO materials in chemistry and physics, materials science and engineering, biology, and medicine are demonstrated in a most powerful way. In doing so, this Review aims to inspire more collaborative and ambitious endeavors in the second decade of PMO research. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Mesoporous tertiary oxides via a novel amphiphilic approach

    SciTech Connect

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

    2016-01-01

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

  12. Recent Trends on Electrochemical Sensors Based on Ordered Mesoporous Carbon

    PubMed Central

    Walcarius, Alain

    2017-01-01

    The past decade has seen an increasing number of extensive studies devoted to the exploitation of ordered mesoporous carbon (OMC) materials in electrochemistry, notably in the fields of energy and sensing. The present review summarizes the recent achievements made in field of electroanalysis using electrodes modified with such nanomaterials. On the basis of comprehensive tables, the interest in OMC for designing electrochemical sensors is illustrated through the various applications developed to date. They include voltammetric detection after preconcentration, electrocatalysis (intrinsically due to OMC or based on suitable catalysts deposited onto OMC), electrochemical biosensors, as well as electrochemiluminescence and potentiometric sensors. PMID:28800106

  13. Method for rapidly producing microporous and mesoporous materials

    DOEpatents

    Coronado, P.R.; Poco, J.F.; Hrubesh, L.W.; Hopper, R.W.

    1997-11-11

    An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods. 3 figs.

  14. Method for rapidly producing microporous and mesoporous materials

    DOEpatents

    Coronado, Paul R.; Poco, John F.; Hrubesh, Lawrence W.; Hopper, Robert W.

    1997-01-01

    An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods.

  15. Sol Gel-Derived SBA-16 Mesoporous Material

    PubMed Central

    Rivera-Muñoz, Eric M.; Huirache-Acuña, Rafael

    2010-01-01

    The aim of this article is to review current knowledge related to the synthesis and characterization of sol gel-derived SBA-16 mesoporous silicas, as well as a review of the state of the art in this issue, to take stock of knowledge about current and future applications. The ease of the method of preparation, the orderly structure, size and shape of their pores and control, all these achievable through simple changes in the method of synthesis, makes SBA-16 a very versatile material, potentially applicable in many areas of science and molecular engineering of materials. PMID:20957080

  16. Antibacterial activity of N-halamine decorated mesoporous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Xu, Jiarong; Zhang, Yu; Zhao, Yanbao; Zou, Xueyan

    2017-09-01

    N-halamine decorated mesoporous silica nanoparticles (mSiO2/halamine NPs) were prepared by coating mSiO2 NPs with poly (1-allylhydantoin-co-methyl methacrylate) (AH-co-MMA) by the aid of the radical polymerization, followed by chlorination treatment. The sterilizing effect on the bacterial strain is investigated by incubating Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Results indicated that the mSiO2/halamine NPs had excellent antibacterial activity and no significant change occurred in antibacterial efficiency after five recycle experiments.

  17. Recent Trends on Electrochemical Sensors Based on Ordered Mesoporous Carbon.

    PubMed

    Walcarius, Alain

    2017-08-11

    The past decade has seen an increasing number of extensive studies devoted to the exploitation of ordered mesoporous carbon (OMC) materials in electrochemistry, notably in the fields of energy and sensing. The present review summarizes the recent achievements made in field of electroanalysis using electrodes modified with such nanomaterials. On the basis of comprehensive tables, the interest in OMC for designing electrochemical sensors is illustrated through the various applications developed to date. They include voltammetric detection after preconcentration, electrocatalysis (intrinsically due to OMC or based on suitable catalysts deposited onto OMC), electrochemical biosensors, as well as electrochemiluminescence and potentiometric sensors.

  18. PEG-templated mesoporous silica nanoparticles exclusively target cancer cells

    NASA Astrophysics Data System (ADS)

    Morelli, Catia; Maris, Pamela; Sisci, Diego; Perrotta, Enrico; Brunelli, Elvira; Perrotta, Ida; Panno, Maria Luisa; Tagarelli, Antonio; Versace, Carlo; Casula, Maria Francesca; Testa, Flaviano; Andò, Sebastiano; Nagy, Janos B.; Pasqua, Luigi

    2011-08-01

    Mesoporous silica nanoparticles (MSNs) have been proposed as DNA and drug delivery carriers, as well as efficient tools for fluorescent cell tracking. The major limitation is that MSNs enter cells regardless of a target-specific functionalization. Here we show that non functionalized MSNs, synthesized using a PEG surfactant-based interfacial synthesis procedure, do not enter cells, while a highly specific, receptor mediated, cellular internalization of folic acid (FOL) grafted MSNs (MSN-FOL), occurs exclusively in folate receptor (FR) expressing cells. Neither the classical clathrin pathway nor macropinocytosis is involved in the MSN endocytic process, while fluorescent MSNs (MSN-FITC) enter cells through aspecific, caveolae-mediated, endocytosis. Moreover, internalized particles seem to be mostly exocytosed from cells within 96 h. Finally, cisplatin (Cp) loaded MSN-FOL were tested on cancerous FR-positive (HeLa) or normal FR-negative (HEK293) cells. A strong growth arrest was observed only in HeLa cells treated with MSN-FOL-Cp. The results presented here show that our mesoporous nanoparticles do not enter cells unless opportunely functionalized, suggesting that they could represent a promising vehicle for drug targeting applications.Mesoporous silica nanoparticles (MSNs) have been proposed as DNA and drug delivery carriers, as well as efficient tools for fluorescent cell tracking. The major limitation is that MSNs enter cells regardless of a target-specific functionalization. Here we show that non functionalized MSNs, synthesized using a PEG surfactant-based interfacial synthesis procedure, do not enter cells, while a highly specific, receptor mediated, cellular internalization of folic acid (FOL) grafted MSNs (MSN-FOL), occurs exclusively in folate receptor (FR) expressing cells. Neither the classical clathrin pathway nor macropinocytosis is involved in the MSN endocytic process, while fluorescent MSNs (MSN-FITC) enter cells through aspecific, caveolae

  19. Anionic-cationic switchable amphoteric monodisperse mesoporous silica nanoparticles.

    PubMed

    Ma, Yanhang; Xing, Lei; Zheng, Haoquan; Che, Shunai

    2011-01-18

    Anionic-cationic switchable monodisperse mesoporous silica nanoparticles were synthesized by one-pot amino and carboxylic acid bifunctionalization based on the self-assembly of the surfactant, two types of co-structure-directing agents containing amino and carboxylic groups, and silica sources. These nanoparticles revealed properties of dispersity and reversibility, with the advantage of the pH-responsive anionic-cationic/acid-base switchability. It was demonstrated that the extracted materials achieved reutilization and controllable dispersity in aqueous solution by adjusting the static electric power among the particles during the switching process.

  20. Mesoporous silica nanoparticles for biomedical and catalytical applications

    SciTech Connect

    Sun, Xiaoxing

    2011-01-01

    Mesoporous silica materials, discovered in 1992 by the Mobile Oil Corporation, have received considerable attention in the chemical industry due to their superior textual properties such as high surface area, large pore volume, tunable pore diameter, and narrow pore size distribution. Among those materials, MCM-41, referred to Mobile Composition of Matter NO. 41, contains honeycomb liked porous structure that is the most common mesoporous molecular sieve studied. Applications of MCM-41 type mesoporous silica material in biomedical field as well as catalytical field have been developed and discussed in this thesis. The unique features of mesoporous silica nanoparticles were utilized for the design of delivery system for multiple biomolecules as described in chapter 2. We loaded luciferin into the hexagonal channels of MSN and capped the pore ends with gold nanoparticles to prevent premature release. Luciferase was adsorbed onto the outer surface of the MSN. Both the MSN and the gold nanoparticles were protected by poly-ethylene glycol to minimize nonspecific interaction of luciferase and keep it from denaturating. Controlled release of luciferin was triggered within the cells and the enzymatic reaction was detected by a luminometer. Further developments by varying enzyme/substrate pairs may provide opportunities to control cell behavior and manipulate intracellular reactions. MSN was also served as a noble metal catalyst support due to its large surface area and its stability with active metals. We prepared MSN with pore diameter of 10 nm (LP10-MSN) which can facilitate mass transfer. And we successfully synthesized an organo silane, 2,2'-Bipyridine-amide-triethoxylsilane (Bpy-amide-TES). Then we were able to functionalize LP10-MSN with bipyridinyl group by both post-grafting method and co-condensation method. Future research of this material would be platinum complexation. This Pt (II) complex catalyst has been reported for a C-H bond activation reaction as an

  1. Three-dimensional ordered mesoporous Co3O4 enhanced by Pd for oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Qu, Qing; Zhang, Jian-Hua; Wang, Jing; Li, Qing-Yu; Xu, Chang-Wei; Lu, Xihong

    2017-01-01

    Considerable efforts have been devoted recently to design and fabrication of high performance and low cost electrocatalysts for oxygen evolution reaction (OER). However, catalytic activity of current electrocatalysts is usually restricted by high onset potential and limited active sites. Herein, we fabricated three-dimensional (3D) highly ordered mesoporous Pd-Co3O4 composite materials as excellent electrocatalysts for OER in alkaline solution with high activity and stability. Three-dimensional highly ordered mesoporous Co3O4 material was firstly synthesized using mesoporous silica KIT-6 as hard template. Then, Pd-Co3O4 nanomaterials were prepared by a simple reduction method. The as-prepared 3D mesoporous Pd-Co3O4 catalysts have ordered mesoporous structure with a high surface area of 81.0 m2 g‑1. Three-dimensional highly ordered mesoporous structure can facilitate diffusion and penetration of electrolyte and oxygen. Moreover, the catalysts can also keep catalyst particles in a well dispersed condition with more catalytic active sites. Electrochemical measurements reveal that the 3D mesoporous Pd-Co3O4 catalysts exhibit superior performance in alkaline solution with low onset potential (0.415 V vs. SCE) and excellent long-duration cycling stability.

  2. Design of an ultrasmall Au nanocluster-CeO2 mesoporous nanocomposite catalyst for nitrobenzene reduction.

    PubMed

    Chong, Hanbao; Li, Peng; Xiang, Ji; Fu, Fangyu; Zhang, Dandan; Ran, Xiaorong; Zhu, Manzhou

    2013-08-21

    In this work we are inspired to explore gold nanoclusters supported on mesoporous CeO2 nanospheres as nanocatalysts for the reduction of nitrobenzene. Ultrasmall Au nanoclusters (NCs) and mesoporous CeO2 nanospheres were readily synthesized and well characterized. Due to their ultrasmall size, the as-prepared Au clusters can be easily absorbed into the mesopores of the mesoporous CeO2 nanospheres. Owing to the unique mesoporous structure of the CeO2 support, Au nanoclusters in the Au@CeO2 may effectively prevent the aggregation which usually results in a rapid decay of the catalytic activity. It is notable that the ultrasmall gold nanoclusters possess uniform size distribution and good dispersibility on the mesoporous CeO2 supports. Compared to other catalyst systems with different oxide supports, the as-prepared Au nanocluster-CeO2 nanocomposite nanocatalysts showed efficient catalytic performance in transforming nitrobenzene into azoxybenzene. In addition, a plausible mechanism was deeply investigated to explain the transforming process. Au@CeO2 exhibited efficient catalytic activity for reduction of nitrobenzene. This strategy may be easily extended to fabricate many other heterogeneous catalysts including ultrasmall metal nanoclusters and mesoporous oxides.

  3. A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

    SciTech Connect

    Qu Fengyu; Zhu Guangshan; Lin Huiming; Zhang Weiwei; Sun Jinyu; Li Shougui; Qiu Shilun . E-mail: sqiu@mail.jlu.edu.cn

    2006-07-15

    A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.

  4. High-pressure synthesis of mesoporous stishovite: potential applications in mineral physics

    NASA Astrophysics Data System (ADS)

    Stagno, Vincenzo; Mandal, Manik; Landskron, Kai; Fei, Yingwei

    2015-06-01

    Recently, we have described a successful synthesis route to obtain mesoporous quartz and its high-pressure polymorph coesite by nanocasting at high pressure using periodic mesostructured precursors, such as SBA-16 and FDU-12/carbon composite as starting materials. Periodic mesoporous high-pressure silica polymorphs are of particular interest as they combine transport properties and physical properties such as hardness that potentially enable the industrial use of these materials. In addition, synthesis of mesoporous crystalline silica phases can allow more detailed geology-related studies such as water/mineral interaction, dissolution/crystallization rate and the surface contribution to the associated thermodynamic stability (free energy and enthalpy) of the various polymorphs and their crossover. Here, we present results of synthesis of mesoporous stishovite from cubic large-pore periodic mesoporous silica LP-FDU-12/C composite as precursor with an fcc lattice. We describe the synthesis procedure using multi-anvil apparatus at 9 GPa (about 90,000 atm) and temperature of 500 °C. The synthetic mesoporous stishovite is, then, characterized by wide and small-angle X-ray diffraction, scanning/transmission electron microscopy and gas adsorption. Results show that this new material is characterized by accessible mesopores with wide pore size distribution, surface area of ~45 m2/g and volume of pores of ~0.15 cm3/g. Results from gas adsorption indicate that both porosity and permeability are retained at the high pressures of synthesis but with weak periodic order of the pores.

  5. Structure and Luminescence Properties of Eu3+-Doped Cubic Mesoporous Silica Thin Films

    PubMed Central

    2010-01-01

    Eu3+ ions-doped cubic mesoporous silica thin films with a thickness of about 205 nm were prepared on silicon and glass substrates using triblock copolymer as a structure-directing agent using sol–gel spin-coating and calcination processes. X-ray diffraction and transmission electron microscopy analysis show that the mesoporous silica thin films have a highly ordered body-centered cubic mesoporous structure. High Eu3+ ion loading and high temperature calcination do not destroy the ordered cubic mesoporous structure of the mesoporous silica thin films. Photoluminescence spectra show two characteristic emission peaks corresponding to the transitions of5D0-7F1 and 5D0-7F2 of Eu3+ ions located in low symmetry sites in mesoporous silica thin films. With the Eu/Si molar ratio increasing to 3.41%, the luminescence intensity of the Eu3+ ions-doped mesoporous silica thin films increases linearly with increasing Eu3+ concentration. PMID:20672132

  6. 2-Mercaptothiazoline modified mesoporous silica for mercury removal from aqueous media.

    PubMed

    Pérez-Quintanilla, Damián; del Hierro, Isabel; Fajardo, Mariano; Sierra, Isabel

    2006-06-30

    Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second step a multifunctionalized N, S donor compound (2-mercaptothiazoline, MTZ) was incorporated to obtain the functionalized silicas denoted as MTZ-SBA-15-Het or MTZ-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MTZ-SBA-15-Hom or MTZ-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions contaminated with Hg (II) at room temperature. SBA-15 and MCM-41 functionalized with MTZ by the homogeneous method present good mercury adsorption values (1.10 and 0.7mmolHg (II)/g of silica, respectively). This fact suggests a better applicability of such mesoporous silica supports to extract Hg (II) from aqueous solutions. In addition, it was observed the existence of a correlation between mercury adsorption with pore size and volume since, SBA-15 with lower areas and higher pore sizes functionalized with sterically demanding ligands, show better adsorption capacities than functionalized MCM-41.

  7. Three-dimensional ordered mesoporous Co3O4 enhanced by Pd for oxygen evolution reaction

    PubMed Central

    Qu, Qing; Zhang, Jian-Hua; Wang, Jing; Li, Qing-Yu; Xu, Chang-Wei; Lu, Xihong

    2017-01-01

    Considerable efforts have been devoted recently to design and fabrication of high performance and low cost electrocatalysts for oxygen evolution reaction (OER). However, catalytic activity of current electrocatalysts is usually restricted by high onset potential and limited active sites. Herein, we fabricated three-dimensional (3D) highly ordered mesoporous Pd-Co3O4 composite materials as excellent electrocatalysts for OER in alkaline solution with high activity and stability. Three-dimensional highly ordered mesoporous Co3O4 material was firstly synthesized using mesoporous silica KIT-6 as hard template. Then, Pd-Co3O4 nanomaterials were prepared by a simple reduction method. The as-prepared 3D mesoporous Pd-Co3O4 catalysts have ordered mesoporous structure with a high surface area of 81.0 m2 g−1. Three-dimensional highly ordered mesoporous structure can facilitate diffusion and penetration of electrolyte and oxygen. Moreover, the catalysts can also keep catalyst particles in a well dispersed condition with more catalytic active sites. Electrochemical measurements reveal that the 3D mesoporous Pd-Co3O4 catalysts exhibit superior performance in alkaline solution with low onset potential (0.415 V vs. SCE) and excellent long-duration cycling stability. PMID:28134348

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

    PubMed

    Park, Sung Soo; Ha, Chang-Sik

    2006-01-01

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

  9. A cationic surfactant assisted selective etching strategy to hollow mesoporous silica spheres.

    PubMed

    Fang, Xiaoliang; Chen, Cheng; Liu, Zhaohui; Liu, Pengxin; Zheng, Nanfeng

    2011-04-01

    Hollow mesoporous silica spheres have recently attracted increasing attention. However, effective synthesis of uniform hollow mesoporous spheres with controllable well-defined pore structures for fundamental research and practical applications has remained a significant challenge. In this work, a straightforward and effective "cationic surfactant assisted selective etching" synthetic strategy was developed for the preparation of high-quality hollow mesoporous silica spheres with either wormhole-like or oriented mesoporous shell. The as-prepared hollow mesoporous silica spheres have large surface area, high pore volume, and controllable structure parameters. Our experiments demonstrated that cationic surfactant plays critical roles in forming the hollow mesoporous structure. A formation mechanism involving the etching of solid SiO(2) accelerated by cationic surfactant followed by the redeposition of dissolved silica species directed by cationic surfactant is proposed. Furthermore, the strategy can be extended as a general strategy to transform silica-coated composite materials into yolk-shell structures with either wormhole-like or oriented mesoporous shell.

  10. Molecular simulation and experimental studies of a mesoporous ZSM-5 type molecular sieve.

    PubMed

    Liu, Baoyu; Wu, Yongbiao; Liu, Defei; Wu, Ying; Xi, Hongxia; Qian, Yu

    2013-02-28

    The mesoporous zeolite is a novel porous material possessing mesopores as well as the inherent micropores of zeolites. This material can exhibit the dual merits of two different pore structures and enable zeolites to have maximum structural functions. During the past few decades, various synthetic strategies have been well developed. However, up to now, there has only been a few attempts to model mesoporous zeolites. In this paper, the structural properties of a mesoporous ZSM-5 type molecular sieve, which has mesopore walls that are made up of ZSM-5 zeolite-like frameworks, were studied using an atomistic model. The full-atom model of the mesoporous ZSM-5 type molecular sieve was constructed using a molecular modeling technique. The structure model was characterized by estimating the nitrogen accessible solvent surface area, small-angle and wide-angle X-ray diffraction patterns, toluene and benzene adsorption. It was found that these simulated results match well with the experimental data. Furthermore, the present approach can be extended to construct other micro-mesoporous molecular sieve structure models in the future.

  11. Structure and luminescence properties of eu3+-doped cubic mesoporous silica thin films.

    PubMed

    Lu, Qingshan; Wang, Zhongying; Wang, Peiyu; Li, Jiangong

    2010-02-11

    Eu3+ ions-doped cubic mesoporous silica thin films with a thickness of about 205 nm were prepared on silicon and glass substrates using triblock copolymer as a structure-directing agent using sol-gel spin-coating and calcination processes. X-ray diffraction and transmission electron microscopy analysis show that the mesoporous silica thin films have a highly ordered body-centered cubic mesoporous structure. High Eu3+ ion loading and high temperature calcination do not destroy the ordered cubic mesoporous structure of the mesoporous silica thin films. Photoluminescence spectra show two characteristic emission peaks corresponding to the transitions of5D0-7F1 and 5D0-7F2 of Eu3+ ions located in low symmetry sites in mesoporous silica thin films. With the Eu/Si molar ratio increasing to 3.41%, the luminescence intensity of the Eu3+ ions-doped mesoporous silica thin films increases linearly with increasing Eu3+ concentration.

  12. Efficient photodecomposition of herbicide imazapyr over mesoporous Ga2O3-TiO2 nanocomposites.

    PubMed

    Ismail, Adel A; Abdelfattah, Ibrahim; Faisal, M; Helal, Ahmed

    2017-08-23

    The unabated release of herbicide imazapyr into the soil and groundwater led to crop destruction and several pollution-related concerns. In this contribution, heterogeneous photocatalytic technique was employed utilizing mesoporous Ga2O3-TiO2 nanocomposites for degrading imazapyr herbicide as a model pollutant molecule. Mesoporous Ga2O3-TiO2 nanocomposites with varied Ga2O3 contents (0-5wt%) were synthesized through sol-gel process. XRD and Raman spectra exhibited extremely crystalline anatase TiO2 phase at low Ga2O3 content which gradually reduced with the increase of Ga2O3 content. TEM images display uniform TiO2 particles (10±2nm) with mesoporous structure. The mesoporous TiO2 exhibits large surface areas of 167m(2)g(-1), diminished to 108m(2)g(-1) upon 5% Ga2O3 incorporation, with tunable mesopore diameter in the range of 3-9nm. The photocatalytic efficiency of synthesized Ga2O3-TiO2 nanocomposites was assessed by degrading imazapyr herbicide and comparing with commercial photocatalyst UV-100 and mesoporous Ga2O3 under UV illumination. 0.1% Ga2O3-TiO2 nanocomposite is considered the optimum photocatalyst, which degrades 98% of imazapyr herbicide within 180min. Also, the photodegradation rate of imazapyr using 0.1% Ga2O3-TiO2 nanocomposite is nearly 10 and 3-fold higher than that of mesoporous Ga2O3 and UV-100, respectively. The high photonic efficiency and long-term stability of the mesoporous Ga2O3-TiO2 nanocomposites are ascribed to its stronger oxidative capability in comparison with either mesoporous TiO2, Ga2O3 or commercial UV-100. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. One-step synthesis of degradable T1-FeOOH functionalized hollow mesoporous silica nanocomposites from mesoporous silica spheres

    NASA Astrophysics Data System (ADS)

    Peng, Yung-Kang; Tseng, Yu-Jui; Liu, Chien-Liang; Chou, Shang-Wei; Chen, Yu-Wei; Tsang, S. C. Edman; Chou, Pi-Tai

    2015-01-01

    The combination of a hollow mesoporous structure and a magnetic resonance (MR) contrast agent has shown its potential in simultaneous drug delivery and cell tracking applications. However, the preparation of this kind of nanocomposite is complicated and usually takes several days, which is unsuitable for scaled-up production. To overcome these hurdles, we report herein a facile method to synthesize iron oxide hydroxide functionalized hollow mesoporous silica spheres (FeOOH/HMSS) in a one-step manner. By carefully controlling the reaction kinetics of K2FeO4 in water, the gram-scale production of FeOOH/HMSS can be readily achieved at 60 °C for as short as 30 min. Most importantly, this synthetic process is also cost-effective and eco-friendly in both the precursor (K2FeO4 and H2O) and the product (FeOOH). The mechanism for the formation of a hollow structure was carefully investigated, which involves the synergetic effect of the surfactant CTAB and the side product KOH. Having outstanding biocompatibility, these degradable nanocolloids also demonstrate their feasibility in in vitro/vivo MR imaging and in vitro drug delivery.The combination of a hollow mesoporous structure and a magnetic resonance (MR) contrast agent has shown its potential in simultaneous drug delivery and cell tracking applications. However, the preparation of this kind of nanocomposite is complicated and usually takes several days, which is unsuitable for scaled-up production. To overcome these hurdles, we report herein a facile method to synthesize iron oxide hydroxide functionalized hollow mesoporous silica spheres (FeOOH/HMSS) in a one-step manner. By carefully controlling the reaction kinetics of K2FeO4 in water, the gram-scale production of FeOOH/HMSS can be readily achieved at 60 °C for as short as 30 min. Most importantly, this synthetic process is also cost-effective and eco-friendly in both the precursor (K2FeO4 and H2O) and the product (FeOOH). The mechanism for the formation of a

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

    SciTech Connect

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

    2006-01-01

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

  15. Thermally stable polymer composites with improved transparency by using colloidal mesoporous silica nanoparticles as inorganic fillers.

    PubMed

    Suzuki, Norihiro; Zakaria, Mohamed B; Chiang, Ya-Dong; Wu, Kevin C-W; Yamauchi, Yusuke

    2012-05-28

    The colloidal mesoporous silica nanoparticles with small particle sizes (namely, CMS) are used as inorganic fillers of polymers (i.e. epoxy and silicone). From simple calculation, almost all polymers are estimated to be confined in the mesopores. To clarify the superiority of CMS over nonporous silica particles and mesoporous silica particles with much larger size (TMPS-4) as inorganic fillers, a systematic study on mechanical strength and transparency of polymer-silica nanocomposites was conducted. Compared with nonporous silica particles, similar to TMPS-4, CMS shows a greater effect on lowering the CTE. In addition, obtained polymer-CMS nanocomposites show improved transparency than polymer-TMPS-4 nanocomposites.

  16. On-Chip Evaluation of Shear Stress Effect on Cytotoxicity of Mesoporous Silica Nanoparticles

    PubMed Central

    Kim, Donghyuk; Lin, Yu-Shen; Haynes, Christy L.

    2011-01-01

    In this work, nanotoxicity in the bloodstream was modeled and the cytotoxicity of sub-50 nm mesoporous silica nanoparticles to human endothelial cells was investigated under microfluidic flow conditions. Compared to traditional in vitro cytotoxicity assays performed under static conditions, unmodified mesoporous silica nanoparticles show higher and shear stress-dependent toxicity to endothelial cells under flow conditions. Interestingly, even under flow conditions, highly organo-modified mesoporous silica nanoparticles show no significant toxicity to endothelial cells. This paper clearly demonstrates that shear stress is an important factor to be considered in in vitro nanotoxicology assessments and provides a simple device for pursuing this consideration. PMID:22032307

  17. Mesoporous MgO: Synthesis, physico-chemical, and catalytic properties

    NASA Astrophysics Data System (ADS)

    Maerle, A. A.; Kasyanov, I. A.; Moskovskaya, I. F.; Romanovsky, B. V.

    2016-06-01

    Mesoporous MgO was obtained via the hydrothermal synthesis using both ionogenic and non-ionogenic surfactants as structure-directing templates. The materials prepared were characterized by SEM, BET-N2, XRD, and TG-DTA techniques. MgO particles are spherical 20-μm aggregates of primary oxide particles well shaped as rectangular parallelepipeds. Magnesium oxide samples have the specific surface area of 290-400 m2/g and pore sizes of 3.3-4.1 nm. Their mesoporous structure remained unchanged after calcination up to 350°C. Catalytic activity of mesoporous MgO was studied in acetone condensation reaction.

  18. Nanostructured mesoporous materials for lithium-ion battery applications

    NASA Astrophysics Data System (ADS)

    Balaya, P.; Saravanan, K.; Hariharan, S.; Ramar, V.; Lee, H. S.; Kuezma, M.; Devaraj, S.; Nagaraju, D. H.; Ananthanarayanan, K.; Mason, C. W.

    2011-06-01

    The Energy crisis happens to be one of the greatest challenges we are facing today. In this view, much effort has been made in developing new, cost effective, environmentally friendly energy conversion and storage devices. The performance of such devices is fundamentally related to material properties. Hence, innovative materials engineering is important in solving the energy crisis problem. One such innovation in materials engineering is porous materials for energy storage. Porous electrode materials for lithium-ion batteries (LIBs) offer a high degree of electrolyte-electrode wettability, thus enhancing the electrochemical activity within the material. Among the porous materials, mesoporous materials draw special attention, owing to shorter diffusion lengths for Li+ and electronic movement. Nanostructured mesoporous materials also offer better packing density compared to their nanostructured counterparts such as nanopowders, nanowires, nanotubes etc., thus opening a window for developing electrode materials with high volumetric energy densities. This would directly translate into a scenario of building batteries which are much lighter than today's commercial LIBs. In this article, the authors present a simple, soft template approach for preparing both cathode and anode materials with high packing density for LIBs. The impact of porosity on the electrochemical storage performance is highlighted.

  19. Optical detection of E. coli bacteria by mesoporous silicon biosensors.

    PubMed

    Massad-Ivanir, Naama; Shtenberg, Giorgi; Segal, Ester

    2013-11-20

    A label-free optical biosensor based on a nanostructured porous Si is designed for rapid capture and detection of Escherichia coli K12 bacteria, as a model microorganism. The biosensor relies on direct binding of the target bacteria cells onto its surface, while no pretreatment (e.g. by cell lysis) of the studied sample is required. A mesoporous Si thin film is used as the optical transducer element of the biosensor. Under white light illumination, the porous layer displays well-resolved Fabry-Pérot fringe patterns in its reflectivity spectrum. Applying a fast Fourier transform (FFT) to reflectivity data results in a single peak. Changes in the intensity of the FFT peak are monitored. Thus, target bacteria capture onto the biosensor surface, through antibody-antigen interactions, induces measurable changes in the intensity of the FFT peaks, allowing for a 'real time' observation of bacteria attachment. The mesoporous Si film, fabricated by an electrochemical anodization process, is conjugated with monoclonal antibodies, specific to the target bacteria. The immobilization, immunoactivity and specificity of the antibodies are confirmed by fluorescent labeling experiments. Once the biosensor is exposed to the target bacteria, the cells are directly captured onto the antibody-modified porous Si surface. These specific capturing events result in intensity changes in the thin-film optical interference spectrum of the biosensor. We demonstrate that these biosensors can detect relatively low bacteria concentrations (detection limit of 10(4) cells/ml) in less than an hour.

  20. Alendronate functionalized mesoporous hydroxyapatite nanoparticles for drug delivery

    SciTech Connect

    Li, Dongdong; Zhu, Yuntao; Liang, Zhiqiang

    2013-06-01

    Highlights: ► The synthesized mesoporous hydroxyapatite has nanostructure and bioactivity. ► The materials have high surface area and amino group. ► The materials show higher drug loading and slower release rate than pure HAP. - Abstract: Mesoporous nanosized hydroxyapatite (HAP) functionalized by alendronate (ALN) was synthesized using cationic surfactant CTAB as template. The structural, morphological and textural properties were fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and N{sub 2} adsorption/desorption. Then the obtained materials were performed as drug delivery carriers using ibuprofen (IBU) as a model drug to investigate their drug storage/release properties in simulated body fluid (SBF). The materials showed relatively slower release rate compared with HAP due to the ionic interaction between -NH{sub 3}{sup +} on the matrix and -COO{sup −}belongs to IBU. The system provides a new concept for improving the drug loading or slowing down the release rate.

  1. Flash freezing route to mesoporous polymer nanofibre networks

    PubMed Central

    Samitsu, Sadaki; Zhang, Rui; Peng, Xinsheng; Krishnan, Mohan Raj; Fujii, Yoshihisa; Ichinose, Izumi

    2013-01-01

    There are increasing requirements worldwide for advanced separation materials with applications in environmental protection processes. Various mesoporous polymeric materials have been developed and they are considered as potential candidates. It is still challenging, however, to develop economically viable and durable separation materials from low-cost, mass-produced materials. Here we report the fabrication of a nanofibrous network structure from common polymers, based on a microphase separation technique from frozen polymer solutions. The resulting polymer nanofibre networks exhibit large free surface areas, exceeding 300 m2 g−1, as well as small pore radii as low as 1.9 nm. These mesoporous polymer materials are able to rapidly adsorb and desorb a large amount of carbon dioxide and are also capable of condensing organic vapours. Furthermore, the nanofibres made of engineering plastics with high glass transition temperatures over 200 °C exhibit surprisingly high, temperature-dependent adsorption of organic solvents from aqueous solution. PMID:24145702

  2. Synthesis and textural evolution of alumina particles with mesoporous structures

    SciTech Connect

    Liu Xun; Peng Tianyou; Yao Jinchun; Lv Hongjin; Huang Cheng

    2010-06-15

    Alumina particles with mesostructures were synthesized through a chemical precipitation method by using different inorganic aluminum salts followed by a heterogeneous azeotropic distillation and calcination process. The obtained mesoporous {gamma}-alumina particles were systematically characterized by the X-ray diffraction, transmission electron microscopy and nitrogen adsorption-desorption measurement. Effects of the aluminum salt counter anion, pH value and the azeotropic distillation process on the structural or textural evolution of alumina particles were investigated. It is found that Cl{sup -} in the reaction solution can restrain the textural evolution of the resultant precipitates into two-dimensional crystallized pseudoboehmite lamellae during the heterogeneous azeotropic distillation, and then transformed into {gamma}-Al{sub 2}O{sub 3} particles with mesostructures after further calcination at 1173 K, whereas coexisting SO{sub 4}{sup 2-} can promote above morphology evolution and then transformed into {gamma}-Al{sub 2}O{sub 3} nanofibers after calcination at 1173 K. Moreover nearly all materials retain relatively high specific surface areas larger than 100 m{sup 2} g{sup -1} even after calcinations at 1173 K. - Graphical abstract: Co-existing Cl{sup -} is beneficial for the formation of {gamma}-alumina nanoparticles with mesostructures during the precipitation process. Interparticle and intraparticle mesopores can be derived from acidic solution and near neutral solution, respectively.

  3. A high acid mesoporous USY zeolite prepared by alumination

    NASA Astrophysics Data System (ADS)

    Ma, Jinghong; Kang, Yuhong; Ma, Ning; Hao, Wenming; Wang, Yan; Li, Ruifeng

    2013-01-01

    A high-acidity HUSY zeolite with mesoporous structure was prepared by alumination with a dilute aqueous NaAlO2 solution and characterized by XRD, N2 adsorption, IR framework vibration and 29Si MAS NMR methods. The results indicated the extra-framework aluminum was reinserted into the tetrahedral framework through isomorphic substitution of framework Si (0Al) sites by Al ions, whereas the crystal and micropore structure were unaltered. FTIR spectra of hydroxyl vibrations and pyridine adsorbed on realuminated zeolites showed that the number of Brønsted acid sites and strong Lewis acid sites increased whereas weak Lewis acid sites decreased twice. The mesoporous structure composed of inter-and intra-crystalline pores in the aluminated HUSY increased the external surface area of the zeolite, improving accessibility of molecules to the active sites and enhancing its catalytic ability. The realuminated HUSY zeolite supported with Ru catalyst exhibited a higher catalytic activity for benzene hydrogenation than the parent HUSY zeolite; the reaction rate in comparison to the mesozeolite increased by 5.5 times.

  4. Preparation and characterization of bioactive mesoporous wollastonite - Polycaprolactone composite scaffold.

    PubMed

    Wei, Jie; Chen, Fangping; Shin, Jung-Woog; Hong, Hua; Dai, Chenglong; Su, Jiancan; Liu, Changsheng

    2009-02-01

    A well-defined mesoporous structure of wollastonite with high specific surface area was synthesized using surfactant P123 (triblock copolymer) as template, and its composite scaffolds with poly(epsilon-caprolactone) (PCL) were fabricated by a simple method of solvent casting-particulate leaching. The measurements of the water contact angles suggest that the incorporation of either mesoporous wollastonite (m-WS) or conventional wollastonite (c-WS) into PCL could improve the hydrophilicity of the composites, and the former was more effective than the later. The bioactivity of the composite scaffold was evaluated by soaking the scaffolds in a simulated body fluid (SBF) and the results show that the m-WS/PCL composite (m-WPC) scaffolds can induce a dense and continuous layer of apatite after soaking for 1 week, as compared with the scattered and discrete apatite particles on the c-WS/PCL composite (c-WPC) scaffolds. The m-WPC had a significantly enhanced apatite-forming bioactivity compared with the c-WPC owing to the high specific surface area and pore volume of m-WS. In addition, attachment and proliferation of MG(63) cells on m-WPC scaffolds were significantly higher than that of c-WPC, revealing that m-WPC scaffolds had excellent biocompatibility. Such improved properties of m-WPC should be helpful for developing new biomaterials and may have potential use in hard tissue repair.

  5. Extreme Light Management in Mesoporous Wood Cellulose Paper for Optoelectronics.

    PubMed

    Zhu, Hongli; Fang, Zhiqiang; Wang, Zhu; Dai, Jiaqi; Yao, Yonggang; Shen, Fei; Preston, Colin; Wu, Wenxin; Peng, Peng; Jang, Nathaniel; Yu, Qingkai; Yu, Zongfu; Hu, Liangbing

    2016-01-26

    Wood fibers possess natural unique hierarchical and mesoporous structures that enable a variety of new applications beyond their traditional use. We dramatically modulate the propagation of light through random network of wood fibers. A highly transparent and clear paper with transmittance >90% and haze <1.0% applicable for high-definition displays is achieved. By altering the morphology of the same wood fibers that form the paper, highly transparent and hazy paper targeted for other applications such as solar cell and antiglare coating with transmittance >90% and haze >90% is also achieved. A thorough investigation of the relation between the mesoporous structure and the optical properties in transparent paper was conducted, including full-spectrum optical simulations. We demonstrate commercially competitive multitouch touch screen with clear paper as a replacement for plastic substrates, which shows excellent process compatibility and comparable device performance for commercial applications. Transparent cellulose paper with tunable optical properties is an emerging photonic material that will realize a range of much improved flexible electronics, photonics, and optoelectronics.

  6. The role of curvature in silica mesoporous crystals

    PubMed Central

    Miyasaka, Keiichi; Garcia Bennett, Alfonso; Han, Lu; Han, Yu; Xiao, Changhong; Fujita, Nobuhisa; Castle, Toen; Sakamoto, Yasuhiro; Che, Shunai; Terasaki, Osamu

    2012-01-01

    Silica mesoporous crystals (SMCs) offer a unique opportunity to study micellar mesophases. Replication of non-equilibrium mesophases into porous silica structures allows the characterization of surfactant phases under a variety of chemical and physical perturbations, through methods not typically accessible to liquid crystal chemists. A poignant example is the use of electron microscopy and crystallography, as discussed herein, for the purpose of determining the fundamental role of amphiphile curvature, namely mean curvature and Gaussian curvature, which have been extensively studied in various fields such as polymer, liquid crystal, biological membrane, etc. The present work aims to highlight some current studies devoted to the interface curvature on SMCs, in which electron microscopy and electron crystallography (EC) are used to understand the geometry of silica wall surface in bicontinuous and cage-type mesostructures through the investigation of electrostatic potential maps. Additionally, we show that by altering the synthesis conditions during the preparation of SMCs, it is possible to isolate particles during micellar mesophase transformations in the cubic bicontinuous system, allowing us to view and study epitaxial relations under the specific synthesis conditions. By studying the relationship between mesoporous structure, interface curvature and micellar mesophases using electron microscopy and EC, we hope to bring new insights into the formation mechanism of these unique materials but also contribute a new way of understanding periodic liquid crystal systems. PMID:24098848

  7. Enzymes immobilized in mesoporous silica: a physical-chemical perspective.

    PubMed

    Carlsson, Nils; Gustafsson, Hanna; Thörn, Christian; Olsson, Lisbeth; Holmberg, Krister; Åkerman, Björn

    2014-03-01

    Mesoporous materials as support for immobilized enzymes have been explored extensively during the last two decades, primarily not only for biocatalysis applications, but also for biosensing, biofuels and enzyme-controlled drug delivery. The activity of the immobilized enzymes inside the pores is often different compared to that of the free enzymes, and an important challenge is to understand how the immobilization affects the enzymes in order to design immobilization conditions that lead to optimal enzyme activity. This review summarizes methods that can be used to understand how material properties can be linked to changes in enzyme activity. Real-time monitoring of the immobilization process and techniques that demonstrate that the enzymes are located inside the pores is discussed by contrasting them to the common practice of indirectly measuring the depletion of the protein concentration or enzyme activity in the surrounding bulk phase. We propose that pore filling (pore volume fraction occupied by proteins) is the best standard for comparing the amount of immobilized enzymes at the molecular level, and present equations to calculate pore filling from the more commonly reported immobilized mass. Methods to detect changes in enzyme structure upon immobilization and to study the microenvironment inside the pores are discussed in detail. Combining the knowledge generated from these methodologies should aid in rationally designing biocatalyst based on enzymes immobilized in mesoporous materials.

  8. Mesoporous silica as carrier of antioxidant for food packaging materials

    NASA Astrophysics Data System (ADS)

    Buonocore, Giovanna Giuliana; Gargiulo, Nicola; Verdolotti, Letizia; Liguori, Barbara; Lavorgna, Marino; Caputo, Domenico

    2014-05-01

    Mesoporous silicas have been long recognized as very promising materials for the preparation of drug delivery systems. In this work SBA-15 mesoporous silica has been functionalized with amino-silane to be used as carrier of antioxidant compound in the preparation of active food packaging materials exhibiting tailored release properties. Active films have been prepared by loading the antioxidant tocopherol, the purely siliceous SBA-15 and the aminofunctionalized SBA-15 loaded with tocopherol into LDPE matrix trough a two-step process (mixing+extrusion). The aim of the present work is the study of the effect of the pore size and of the chemical functionality of the internal walls of the mesophase on the migration of tocopherol from active LDPE polymer films. Moreover, it has been proved that the addition of the active compound do not worsen the properties of the film such as optical characteristic and water vapor permeability, thus leading to the development of a material which could be favorably used mainly, but not exclusively, in the sector of food packaging.

  9. Hybrid mesoporous silica nanocarriers with thermovalve-regulated controlled release.

    PubMed

    Ribeiro, T; Coutinho, E; Rodrigues, A S; Baleizão, C; Farinha, J P S

    2017-09-01

    Mesoporous silica nanoparticles (MSNs) are excellent nanocarriers, featuring very high cargo capacity due to their large surface area and pore volume. The particle and pore dimensions can be accurately tuned, and both the internal and external surfaces allow versatile functionalization. We developed hybrid MSNs with diameters around 140 nm, with the external surface selectively modified with a temperature-responsive biocompatible copolymer to control cargo release. The nanoparticles feature either a polymer brush or a gel-like responsive shell, produced by grafting from RAFT polymerization of PEG-acrylate macromonomers. The hybrid nanoparticles have fluorescent molecules incorporated into the inorganic network providing excellent optical properties for traceability and imaging. The cargo release profiles are explained by a temperature-controlled "pumping" mechanism: at low temperature (ca. 20 °C) the polymer shell is hydrophilic and expanded, opposing cargo diffusion out of the shell and retaining the molecules released from the mesopores; above room temperature (ca. 40-50 °C) the polymer network becomes more hydrophobic and collapses onto the silica surface, releasing the cargo by a sponge-like squeezing effect. The release kinetics depends on the polymer shell type, with better results obtained for the gel-coated nanoparticles. Our proof-of-concept system shows that by modulating the temperature, it is possible to achieve a pumping regime that increases the release rate in a controlled way.

  10. Nitrogen-doped mesoporous carbons for high performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Wu, Kai; Liu, Qiming

    2016-08-01

    The mesoporous carbons have been synthesized by using α-D(+)-Glucose, D-Glucosamine hydrochloride or their mixture as carbon precursors and mesoporous silicas (SBA-15 or MCF) as hard templates. The as-prepared products show a large pore volume (0.59-0.97 cm3 g-1), high surface areas (352.72-1152.67 m2 g-1) and rational nitrogen content (ca. 2.5-3.9 wt.%). The results of electrochemical tests demonstrate that both heteroatom doping and suitable pore structure play a decisive role in the performance of supercapacitors. The representative sample of SBA-15 replica obtained using D-Glucosamine hydrochloride only exhibits high specific capacitance (212.8 F g-1 at 0.5 A g-1) and good cycle durability (86.1% of the initial capacitance after 2000 cycles) in 6 M KOH aqueous electrolyte, which is attributed to the contribution of double layer capacitance and pseudo-capacitance. The excellent electrochemical performance makes it a promising electrode material for supercapacitors.

  11. Silver-containing mesoporous bioactive glass with improved antibacterial properties.

    PubMed

    Gargiulo, Nicola; Cusano, Angela Maria; Causa, Filippo; Caputo, Domenico; Netti, Paolo Antonio

    2013-09-01

    The aim of the present work is the study of the bacteriostatic/bactericidal effect of a silver-containing mesoporous bioactive glass obtained by evaporation-induced self-assembly and successive thermal stabilization. Samples of the manufactured mesophase were characterized by means of transmission electron microscopy and N₂ adsorption/desorption at 77 K, revealing structural and textural properties similar to SBA-15 mesoporous silica. Glass samples used for bioactivity experiments were put in contact with a standardized, commercially available cell culture medium instead of lab-produced simulated body fluid, and were then characterized by means of X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. All these analyses confirmed the development of a hydroxyl carbonate apatite layer on glass particles. Moreover, the investigated mesostructure showed a very good antibacterial effect against S. aureus strain, with a strong evidence of bactericidal activity already registered at 0.5 mg/mL of glass concentration. A hypothesis about the mechanism by which Ag affects the bacterial viability, based on the intermediate formation of crystalline AgCl, was also taken into account. With respect to what already reported in the literature, these findings claim a deeper insight into the possible use of silver-containing bioactive glasses as multifunctional ceramic coatings for orthopedic devices.

  12. One-step synthesis of degradable T(1)-FeOOH functionalized hollow mesoporous silica nanocomposites from mesoporous silica spheres.

    PubMed

    Peng, Yung-Kang; Tseng, Yu-Jui; Liu, Chien-Liang; Chou, Shang-Wei; Chen, Yu-Wei; Tsang, S C Edman; Chou, Pi-Tai

    2015-02-14

    The combination of a hollow mesoporous structure and a magnetic resonance (MR) contrast agent has shown its potential in simultaneous drug delivery and cell tracking applications. However, the preparation of this kind of nanocomposite is complicated and usually takes several days, which is unsuitable for scaled-up production. To overcome these hurdles, we report herein a facile method to synthesize iron oxide hydroxide functionalized hollow mesoporous silica spheres (FeOOH/HMSS) in a one-step manner. By carefully controlling the reaction kinetics of K2FeO4 in water, the gram-scale production of FeOOH/HMSS can be readily achieved at 60 °C for as short as 30 min. Most importantly, this synthetic process is also cost-effective and eco-friendly in both the precursor (K2FeO4 and H2O) and the product (FeOOH). The mechanism for the formation of a hollow structure was carefully investigated, which involves the synergetic effect of the surfactant CTAB and the side product KOH. Having outstanding biocompatibility, these degradable nanocolloids also demonstrate their feasibility in in vitro/vivo MR imaging and in vitro drug delivery.

  13. Hollow mesoporous carbon as a near-infrared absorbing carrier compared with mesoporous carbon nanoparticles for chemo-photothermal therapy.

    PubMed

    Li, Xian; Yan, Yue; Lin, Yuanzhe; Jiao, Jian; Wang, Da; Di, Donghua; Zhang, Ying; Jiang, Tongying; Zhao, Qinfu; Wang, Siling

    2017-05-15

    In this study, hollow mesoporous carbon nanoparticles (HMCN) and mesoporous carbon nanoparticles (MCN) were used as near-infrared region (NIR) nanomaterials and drug nanocarriers were prepared using different methods. A comparison between HMCN and MCN was performed with regard to the NIR-induced photothermal effect and drug loading efficiency. The results of NIR-induced photothermal effect test demonstrated that HMCN-COOH had a better photothermal conversion efficacy than MCN-COOH. Given the prominent photothermal effect of HMCN-COOH in vitro, the chemotherapeutic drug DOX was chosen as a model drug to further evaluate the drug loading efficiencies and NIR-triggered drug release behaviors of the nanocarriers. The drug loading efficiency of DOX/HMCN-COOH was found to be up to 76.9%, which was higher than that of DOX/MCN-COOH. In addition, the use of an 808nm NIR laser markedly increased the release of DOX from both carbon carriers in pH 5.0 PBS and pH 7.4 PBS. Cellular photothermal tests involving A549 cells demonstrated that HMCN-COOH had a much higher photothermal efficacy than MCN-COOH. Cell viability experiments and flow cytometry were performed to evaluate the therapeutic effect of DOX/HMCN-COOH and the results obtained demonstrated that DOX/HMCN-COOH had a synergistic therapeutic effect in cancer treatment involving a combination of chemotherapy and photothermal therapy.

  14. Influence of spatial configurations on electromagnetic interference shielding of ordered mesoporous carbon/ordered mesoporous silica/silica composites

    PubMed Central

    Wang, Jiacheng; Zhou, Hu; Zhuang, Jiandong; Liu, Qian

    2013-01-01

    Ordered mesoporous carbons (OMCs), obtained by nanocasting using ordered mesoporous silicas (OMSs) as hard templates, exhibit unique arrangements of ordered regular nanopore/nanowire mesostructures. Here, we used nanocasting combined with hot-pressing to prepare 10 wt% OMC/OMS/SiO2 ternary composites possessing various carbon mesostructure configurations of different dimensionalities (1D isolated CS41 carbon nanowires, 2D hexagonal CMK-3 carbon, and 3D cubic CMK-1 carbon). The electric/dielectric properties and electromagnetic interference (EMI) shielding efficiency (SE) of the composites were influenced by spatial configurations of carbon networks. The complex permittivity and the EMI SE of the composites in the X-band frequency range decreased for the carbon mesostructures in the following order: CMK-3-filled > CMK-1-filled > CS41-filled. Our study provides technical directions for designing and preparing high-performance EMI shielding materials. Our OMC-based silica composites can be used for EMI shielding, especially in high-temperature or corrosive environments, owing to the high stability of the OMC/OMS fillers and the SiO2 matrix. Related shielding mechanisms are also discussed. PMID:24248277

  15. Homopiperazine grafted mesoporous silicas from rice husk ash for CO2 adsorption.

    PubMed

    Vinodh, Rajangam; Bhagiyalakshmi, Margandan; Hemalatha, Pushparaj; Ganesh, Mani; Peng, Mei Mei; Palanichamy, Muthiahpillai; Cha, Wang Seog; Jang, Hyun Tae

    2014-06-01

    Chloro-functionalized mesoporous MCM-41, SBA-15, MCM-48 and KIT-6 were synthesized by co-condensation of 3-chloropropyl-trimethoxy-silane (CPTMS) and rice husk ash sodium silicate solution, which is subsequently grafted with a heterocyclic amine, homopiperazine (HPZ). X-ray powder diffraction and BET analysis of the chloro-functionalized mesoporous silicas confirmed the similarity between their structural properties and those obtained from conventional silica sources. CO2 adsorption studies of all HPZ-grafted mesoporous silicas exhibited 8-10 wt% of adsorption capacity and are found to be selective, recyclable and thermally stable. Here, the CO2 adsorption reaction is via the traditional carbamate mechanism. The presence of both secondary and tertiary amine in HPZ influences the high CO2 adsorption capacity. Hence, these HPZ-grafted mesoporous silicas could contribute to CO2 capture as a green, tunable, selective and efficient sorbent.

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

    PubMed

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

    2014-01-30

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

  17. Mesoporous nanocarriers for the loading and stabilization of 5-aminolevulinic acid

    NASA Astrophysics Data System (ADS)

    Miletto, Ivana; Bottinelli, Emanuela; Siviero, Andrea; Fabbri, Debora; Calza, Paola; Berlier, Gloria

    2016-08-01

    Mesoporous nanoparticles bearing different surface functionalizations were proposed as host carrier for the loading and stabilization of 5-aminolevulinic acid: unmodified mesoporous silica nanoparticles exposing native silanols and aminopropyltriethoxysilane-grafted mesoporous silica nanoparticles exposing amino groups. The stability of 5-aminolevulinic acid at different steps of drug loading was monitored via electronic and vibrational spectroscopies. Unmodified mesoporous nanoparticles were found to be a host system ensuring the stability of 5-aminolevulinic acid and its availability as protoporphyrin IX precursor, whilst silica surface exposing amino groups was found to strongly favour the dimerization of 5-aminolevulinic acid, leading to the formation of the derived compound pyrazine-2,5-dipropionic acid which is considered to be the major ALA degradation product in aerated solutions, which is no longer active as precursor of protoporphyrin IX. This phenomenon is interpreted in terms of the basic character of amino-modified silica.

  18. Encapsulation of Anti-Tuberculosis Drugs within Mesoporous Silica and Intracellular Antibacterial Activities

    PubMed Central

    Xia, Xin; Pethe, Kevin; Kim, Ryangyeo; Ballell, Lluis; Barros, David; Cechetto, Jonathan; Jeon, HeeKyoung; Kim, Kideok; Garcia-Bennett, Alfonso E.

    2014-01-01

    Tuberculosis is a major problem in public health. While new effective treatments to combat the disease are currently under development, they tend suffer from poor solubility often resulting in low and/or inconsistent oral bioavailability. Mesoporous materials are here investigated in an in vitro intracellular assay, for the effective delivery of compound PA-824; a poorly soluble bactericidal agent being developed against Tuberculosis (TB). Mesoporous materials enhance the solubility of PA-824; however, this is not translated into a higher antibacterial activity in TB-infected macrophages after 5 days of incubation, where similar values are obtained. The lack of improved activity may be due to insufficient release of the drug from the mesopores in the context of the cellular environment. However, these results show promising data for the use of mesoporous particles in the context of oral delivery with expected improvements in bioavailability.

  19. Soft-templated synthesis of mesoporous carbon nanospheres and hollow carbon nanofibers

    NASA Astrophysics Data System (ADS)

    Cheng, Youliang; Li, Tiehu; Fang, Changqing; Zhang, Maorong; Liu, Xiaolong; Yu, Ruien; Hu, Jingbo

    2013-10-01

    Using coal tar pitch based amphiphilic carbonaceous materials (ACMs) as the precursor and amphiphilic triblock copolymer Plutonic P123 as the only soft template, carbon nanospheres with partially ordered mesopores and hollow carbon nanofibers were synthesized. The concentration of P123, cp, and the mass ratio of P123 to ACM, r, are the key parameters of controlling the shape of the as-prepared products. Mesoporous carbon nanospheres with diameter of 30-150 nm were prepared under the condition of cp = 13.3 g/L and r = 1.2. When cp = 26.7 g/L and r = 2, hollow carbon nanofibers with diameters of 50-200 nm and mesopores/macropores were obtained. Carbon nanospheres and hollow carbon fibers were amorphous materials. The mesoporous carbon nanospheres show good stability in the cyclic voltammograms and their specific capacitance at 10 mV s-1 is 172.1 F/g.

  20. Mesoporous silica film from a solution containing a surfactant and methods of making same

    DOEpatents

    Liu, Jun [West Richland, WA; Domansky, Karel [Cambridge, MA; Li, Xiaohong [Richland, WA; Fryxell, Glen E [Kennewick, WA; Baskaran, Suresh [Kennewick, WA; Kohler, Nathan J [Richland, WA; Thevuthasan, Suntharampillai [Kennewick, WA; Coyle, Christopher A [Richland, WA; Birnbaum, Jerome C [Richland, WA

    2001-12-11

    The present invention is a mesoporous silica film having a low dielectric constant and method of making having the steps of combining a surfactant in a silica precursor solution, spin-coating a film from this solution mixture, forming a partially hydroxylated mesoporous film, and dehydroxylating the hydroxylated film to obtain the mesoporous film. It is advantageous that the small polyoxyethylene ether surfactants used in spin-coated films as described in the present invention will result in fine pores smaller on average than about 20 nm. The resulting mesoporous film has a dielectric constant less than 3, which is stable in moist air with a specific humidity. The present invention provides a method for superior control of film thickness and thickness uniformity over a coated wafer, and films with low dielectric constant.

  1. Mechanically Enhanced Hierarchically Porous Scaffold Composed of Mesoporous Silica for Host Immune Cell Recruitment.

    PubMed

    Choi, Youngjin; Jeong, Ji Hoon; Kim, Jaeyun

    2017-04-01

    Hierarchically porous materials have been of interest in many diverse fields, including catalysis, separations, and tissue engineering, because the hierarchical porosity of the materials contributes to improvements in mechanical properties, transport properties, and molecule selectivity. In this study, we, for the first time, introduce a new approach to fabricate hierarchical macroporous and mesoporous silica scaffolds based on a salt-leaching process using as-prepared mesoporous silica as a building block. The mechanical strength of the resulting inorganic 3D scaffold was significantly improved by controlling the interfaces of mesoporous silica particles, which allowed for high structural stability during in vivo implantation. Implantation of the scaffold loaded with pro-inflammatory cytokine in mesopores into mice successfully recruited a high number of host immune cells, including dendritic cells, into the macropores, which shows their potential use for immunomodulation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Hydrophobic core/hydrophilic shell structured mesoporous silica nanospheres: enhanced adsorption of organic compounds from water.

    PubMed

    Li, Shuru; Jiao, Xuan; Yang, Hengquan

    2013-01-29

    Inspired by the structure features of micelle, we attempt to synthesize a novel functionalized mesoporous silica nanosphere consisting of a hydrophobic core and a hydrophilic shell. The obtained solid materials were structurally confirmed by N(2) sorption, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Their compositions were characterized by Fourier transfer infrared spectroscopy (FT-IR), solid state NMR, X-ray photoelectron spectroscopy (XPS), and elemental analysis. Its fundamental properties such as dispersibility in water or organic phase, wettability, and adsorption ability toward hydrophobic organics in water were investigated. It was revealed that these important properties could be facilely adjusted through varying structure and composition. In particular, these materials showed much better adsorption ability toward hydrophobic organic molecules in water than conventional monofunctionalized mesoporous materials, owing to possessing the hydrophobic/hydrophilic domain-segregated and hierarchically functionalized mesoporous structures. The intriguing properties would make mesoporous materials more accessible to many important applications, especially in aqueous systems.

  3. Encapsulation of PEG-modified myoglobin in hydrophobic mesoporous silica as studied by optical waveguide spectroscopy.

    PubMed

    Arafune, Hiroyuki; Yamaguchi, Akira; Hotta, Kazuhiro; Itoh, Tetsuji; Teramae, Norio

    2013-01-01

    The purpose of this study is to apply optical waveguide (OWG) spectroscopy to characterize the encapsulation behavior of enzymes modified with polyethylene glycol (PEG), i.e. pegylation, in a hydrophobic mesoporous silica film. For that purpose, pegylated myoglobin (PEG-Mb) was introduced into the silica mesopores modified with octadecylsilyl (ODS) groups and studied by OWG spectroscopy. OWG spectroscopy confirmed that the hydrophobic interaction between the PEG group and the surface ODS group promoted the encapsulation of PEG-Mb into the hydrophobic silica mesopores. The surface density of ODS affected the adsorbed amount of PEG-Mb and the higher surface density of the ODS group resulted in the suppression of adsorption and diffusion of PEG-Mb inside the pore. Since the desorption rate of PEG-Mb was found to be much slower than the adsorption rate, the pegylation of an enzyme could be effective for the enzyme encapsulation into the hydrophobic mesoporous silica host.

  4. A general approach to crystalline and monomodal pore size mesoporous materials.

    PubMed

    Poyraz, Altug S; Kuo, Chung-Hao; Biswas, Sourav; King'ondu, Cecil K; Suib, Steven L

    2013-01-01

    Mesoporous oxides attract a great deal of interest in many fields, including energy, catalysis and separation, because of their tunable structural properties such as surface area, pore volume and size, and nanocrystalline walls. Here we report thermally stable, crystalline, thermally controlled monomodal pore size mesoporous materials. Generation of such materials involves the use of inverse micelles, elimination of solvent effects, minimizing the effect of water content and controlling the condensation of inorganic frameworks by NO(x) decomposition. Nanosize particles are formed in inverse micelles and are randomly packed to a mesoporous structure. The mesopores are created by interconnected intraparticle voids and can be tuned from 1.2 to 25 nm by controlling the nanoparticle size. Such phenomena allow the preparation of multiple phases of the same metal oxide and syntheses of materials having compositions throughout much of the periodic table, with different structures and thermal stabilities as high as 800 °C.

  5. Mesoporous Titanium Nitride-Enabled Highly Stable Lithium-Sulfur Batteries.

    PubMed

    Cui, Zhiming; Zu, Chenxi; Zhou, Weidong; Manthiram, Arumugam; Goodenough, John B

    2016-08-01

    The TiN-S composite cathode exhibits superior performance because of higher electrical conductivity and the capture of the soluble intermediate species of the electrode reactions by 2-5 nm mesopores and strong N-S surface bonding.

  6. Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

    NASA Astrophysics Data System (ADS)

    Barry, Louse; Copley, Mark; Holmes, Justin D.; Otway, David J.; Kazakova, Olga; Morris, Michael A.

    2007-12-01

    Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO 2:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.

  7. Molecular gates in mesoporous bioactive glasses for the treatment of bone tumors and infection.

    PubMed

    Polo, Lorena; Gómez-Cerezo, Natividad; Aznar, Elena; Vivancos, José-Luis; Sancenón, Félix; Arcos, Daniel; Vallet-Regí, María; Martínez-Máñez, Ramón

    2017-03-01

    Silica mesoporous nanomaterials have been proved to have meaningful application in biotechnology and biomedicine. Particularly, mesoporous bioactive glasses are recently gaining importance thanks to their bone regenerative properties. Moreover, the mesoporous nature of these materials makes them suitable for drug delivery applications, opening new lines in the field of bone therapies. In this work, we have developed innovative nanodevices based on the implementation of adenosine triphosphate (ATP) and ε-poly-l-lysine molecular gates using a mesoporous bioglass as an inorganic support. The systems have been previously proved to work properly with a fluorescence probe and subsequently with an antibiotic (levofloxacin) and an antitumoral drug (doxorubicin). The bioactivity of the prepared materials has also been tested, giving promising results. Finally, in vitro cell culture studies have been carried out; demonstrating that this gated devices can provide useful approaches for bone cancer and bone infection treatments.

  8. Pseudorotaxane capped mesoporous silica nanoparticles for 3,4-methylenedioxymethamphetamine (MDMA) detection in water.

    PubMed

    Lozano-Torres, Beatriz; Pascual, Lluís; Bernardos, Andrea; Marcos, María D; Jeppesen, Jan O; Salinas, Yolanda; Martínez-Máñez, Ramón; Sancenón, Félix

    2017-03-23

    Mesoporous silica nanoparticles loaded with fluorescein and capped by a pseudorotaxane, formed between a naphthalene derivative and cyclobis(paraquat-p-phenylene) (CBPQT(4+)), were used for the selective and sensitive fluorogenic detection of 3,4-methylenedioxymethamphetamine (MDMA).

  9. The physicochemical properties of micro/mesoporous materials prepared by the recrystallization of zeolite BEA

    NASA Astrophysics Data System (ADS)

    Ordomskii, V. V.; Monakhova, Yu. V.; Knyazeva, E. E.; Nesterenko, N. S.; Ivanova, I. I.

    2009-06-01

    Micro-mesoporous materials with various ratios between micro- and mesopores were prepared by the recrystallization of zeolite BEA in an alkaline medium in the presence of cetyltrimethylammonium bromide. The materials were characterized by X-ray diffraction, low-temperature nitrogen adsorption, and IR spectroscopy. Recrystallization under mild conditions did not cause substantial changes in the number of acid centers but increased the accessibility of acid centers to large-sized molecules because of the creation of mesopores. An increase in the degree of recrystallization caused first partial and then complete zeolite transformation into MSM-41 mesoporous aluminosilicate, which was accompanied by a decrease in the number of acid centers. The IR spectra were used to determine the diffusion coefficients of cumene in the initial and recrystallized samples. Recrystallization increased the diffusion coefficient by 3-4 times.

  10. TEMPLATED SYNTHESIS OF MESOPOROUS TITANIUM PHOSPHATES FOR THE SEQUESTRATION OF RADIONUCLIDES

    SciTech Connect

    X. Shari Li; A.R. Courtney, W. Yantasee; S.V. Mattigod

    2005-10-11

    Several mesoporous titanium phosphate phases, with varying pore sizes, were prepared using non-ionic surfactants and easily handled titanium precursors under mild reaction conditions. Preliminary testing reveals that these materials have high affinity for certain radionuclides of environmental concern.

  11. Synthesis and characterization of novel mesoporous aluminosilicate MCM-41 containing aluminophosphate building units.

    PubMed

    Conesa, Tomás D; Mokaya, Robert; Campelo, Juan M; Romero, Antonio A

    2006-05-07

    Novel MCM-41 aluminosilicate/aluminophosphate materials that exhibit good mesostructural ordering have been synthesized and characterised; the synthesis of these silicoaluminophosphates involved the use of gel mixtures containing amorphous mesoporous aluminosilicate and aluminophosphate phases as precursor.

  12. Adsorption of Pb(II) from aqueous solution by a poly-elemental mesoporous adsorbent

    NASA Astrophysics Data System (ADS)

    Wu, Xiu-Wen; Ma, Hong-Wen; Yang, Jing; Wang, Feng-Jiao; Li, Zhi-Hong

    2012-05-01

    A poly-elemental mesoporous adsorbent was hydrothermally prepared from microcline in an alkaline condition with cetyltrimethylammonium bromide as synthesis directing agent. The properties of the mesoporous adsorbent were determined by X-ray powder diffraction, high-resolution transmission electron microscope, N2 adsorption, and solid-state Magic Angle Spinning Nuclear Magnetic Resonance. The pore size distribution was detected by small angle X-ray scattering. The particles size was observed by Scanning electron microscope imagine. The chemical content of SiO2 in the mesoporous adsorbent was determined by spectrometry of the silicone molybdenum and sulfosalicylic acid complexes, and Al2O3 determined by complexometry with ethylene diamine tetraacetic acid in the presence of KF-Zn(Ac)2 tests. The adsorption properties of the mesoporous adsorbent to Pb(II) were studied, and three main factors, the adsorption time, solution pH, and initial concentration of Pb(II), were considered in the adsorption experiments.

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

    DOE PAGES

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

    2017-06-23

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

  14. Anion Binding in Self-Assembled Monolayers in Mesoporous Supports (SAMMS)

    SciTech Connect

    Mattigod, Shas V.; Fryxell, Glen E.; Parker, Kent E.

    2007-02-19

    The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity. By lining the pore surfaces of mesoporous silica with self-assembled monolayer of organosilanes terminated with chemically selective ligands, a powerful new class of heavy metal sorbents has been realized, called self-assembled monolayers on mesoporous supports (SAMMS) [1-18]. When this interfacial functionality is composed of cationic transition metal complexes, a valuable new class of anion exchange material came into being [19]. Yoshitake and co-workers, have extended this concept to include other transition metal cations in similar cationic complexes inside mesoporous silica [20-23]. Other amine-based ligands (including polymer-based systems) were also explored, and the highest binding capacity was found with the diethylenetriamine ligand [20]. This synthetic strategy allows the chemist to easily modify both the metal center and ligand field, thereby tailoring chemical selectivity at multiple levels.

  15. Multicompartment mesoporous silica nanoparticles with branched shapes: an epitaxial growth mechanism.

    PubMed

    Suteewong, Teeraporn; Sai, Hiroaki; Hovden, Robert; Muller, David; Bradbury, Michelle S; Gruner, Sol M; Wiesner, Ulrich

    2013-04-19

    Mesoporous nanomaterials have attracted widespread interest because of their structural versatility for applications including catalysis, separation, and nanomedicine. We report a one-pot synthesis method for a class of mesoporous silica nanoparticles (MSNs) containing both cubic and hexagonally structured compartments within one particle. These multicompartment MSNs (mc-MSNs) consist of a core with cage-like cubic mesoporous morphology and up to four branches with hexagonally packed cylindrical mesopores epitaxially growing out of the cubic core vertices. The extent of cylindrical mesostructure growth can be controlled via a single additive in the synthesis. Results suggest a path toward high levels of architectural complexity in locally amorphous, mesostructured nanoparticles, which could enable tuning of different pore environments of the same particle for specific chemistries in catalysis or drug delivery.

  16. Morphology and photocatalysis of mesoporous titania thin films annealed in different atmosphere for degradation of methyl orange

    NASA Astrophysics Data System (ADS)

    Ma, Qing; Qin, Tian Pang; Liu, Shao Jun; Weng, Lv Qian; Dong, Wen Yi

    2011-07-01

    The effect of different annealing atmosphere on the morphology and photocatalytic activity of mesoporous TiO2 thin films by dip-coating technique is investigated. The annealing temperature and atmosphere causes significant change of the morphology, thermal stability, photoluminescence, and photocatalytic properties of mesoporous TiO2 films. As-prepared mesoporous thin films have an amorphous structure that is transformed to crystalline TiO2 with well-maintained mesoporous structure at 450°C in various annealing atmosphere except that the mesoporous structure is fully destroyed for films annealed in air. Films annealed in N2 show the enhanced UV photodegradation of methyl orange (MO) resulting from the enhanced crystallinity in these films evidenced by XRD and Raman spectra. These findings can be used to tailor the structure and morphology of mesoporous TiO2 films and thus improve their photocatalytic activity for efficient removal of dye effluents in wastewater.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  18. Synthesis of mesoporous nanoparticles of TiO2 from ilmenite

    NASA Astrophysics Data System (ADS)

    Rostami Gharakhlou, Amir; Nasiri Sarvi, Mehdi

    2017-02-01

    In this study, a surfactant assisted hydrometallurgical procedure was proposed for preparation of mesoporous nanoparticles of titanium dioxide (TiO2) from ilmenite concentrate. Initially, Fe was removed from ilmenite concentrate using HCl and then the titanium was dissolved from the remaining solid in an alkaline condition of NH3 or NaOH in assistance of H2O2 as oxidizing agent in order to prepare the titanium solution (Ti-sol). Afterwards, the prepared Ti-sol was used as titanium source for preparation of a mesoporous nanoparticles of TiO2 in assistance of hexadecyltrimethyl ammonium bromide (HDTMA-Br) as structure directing agent. Different methods were used to characterize the mesoporous nanoparticles of TiO2 structures such as XRD, SEM, and BET. The results showed that the HDTMA helps the formation of slit-shaped mesopores in the range of 1.5 nm when the synthesis was carried out at room temperature despite the media which Ti-sol was prepared, NH3 or NaOH. When a hydrothermal treatment was added to the synthesis process similar mesoporous structure was formed when the Ti-sol was prepared in NH3 with nitrogen sorption hysteresis of H3 type. However, when the NaOH prepared Ti-sol was used the nitrogen sorption hysteresis loop changed to H4 type showing existence of large mesopores (12 nm) in addition to smaller mesopores (2–5 nm). The HRTEM results showed mesoporous structure with nano-rod like particles with particle size around 30–60 nm.

  19. Continuous mesoporous titania nanocrystals: their growth in confined space and scope for application.

    PubMed

    Dutta, Saikat; Bhaumik, Asim

    2013-11-01

    Enjoying the single lifestyle: With an overwhelming efficiency compared to thermally sintered preformed nanocrystals, mesoporous single crystals (MSCs) of TiO2 constitute a new class of semiconductor materials for low-cost solar power, solar fuel, photocatalysis, and energy storage applications. This Highlight explores the benefits of template-directed seed-mediated growth in the confined space of a preseeded mesoporous template, and possible research avenues for further improvements.

  20. Large-scale template-free synthesis of ordered mesoporous platinum nanocubes and their electrocatalytic properties

    NASA Astrophysics Data System (ADS)

    Cao, Yanqin; Yang, Yong; Shan, Yufeng; Fu, Chaoli; Viet Long, Nguyen; Huang, Zhengren; Guo, Xiangxin; Nogami, Masayuki

    2015-11-01

    Here we report a facile, one-pot and template-free approach to synthesize mesoporous monocrystalline Pt nanocubes with uniform shapes and sizes, in which small Pt particles with a size of ~5 nm are three-dimensionally and periodically built up into cubes with a size of ~50 nm. The forming process is illustrated through a novel meso-crystal self-assembly mechanism. Very interestingly, the mesoporous structures are ordered, which are thought to be beneficial to increase their catalytic activity. Compared with nonporous Pt nanoparticles and porous Pt nanoparticles without order, the ordered mesoporous Pt nanocubes exhibit a highly improved electrocatalytic ability for methanol and formic acid oxidation, and are potentially applicable as electrocatalysts for direct methanol and formic acid fuel cells. Furthermore, this approach can be used to synthesize other Pt-series metallic mesoporous nanoparticles, such as Pd.Here we report a facile, one-pot and template-free approach to synthesize mesoporous monocrystalline Pt nanocubes with uniform shapes and sizes, in which small Pt particles with a size of ~5 nm are three-dimensionally and periodically built up into cubes with a size of ~50 nm. The forming process is illustrated through a novel meso-crystal self-assembly mechanism. Very interestingly, the mesoporous structures are ordered, which are thought to be beneficial to increase their catalytic activity. Compared with nonporous Pt nanoparticles and porous Pt nanoparticles without order, the ordered mesoporous Pt nanocubes exhibit a highly improved electrocatalytic ability for methanol and formic acid oxidation, and are potentially applicable as electrocatalysts for direct methanol and formic acid fuel cells. Furthermore, this approach can be used to synthesize other Pt-series metallic mesoporous nanoparticles, such as Pd. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05772h

  1. Carbohydrate-Conjugated Hollow Oblate Mesoporous Silica Nanoparticles as Nanoantibiotics to Target Mycobacteria.

    PubMed

    Hao, Nanjing; Chen, Xuan; Jeon, Seaho; Yan, Mingdi

    2015-12-30

    Engineering nanomaterials with enhanced antibacterial activities remains a critical and practical challenge. Hollow oblate mesoporous silica nanoparticles (HOMSNs) are synthesized by a simple protocol of ammonia hydrothermal treatment of oblate mesoporous silica nanoparticles prepared using dibenzyl ether as a cosolvent. When conjugated with trehalose as the targeting ligand, the antibiotic-encapsulated HOMSNs exhibit high binding affinity and antibacterial efficacy toward mycobacteria. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Carbohydrate-Conjugated Hollow Oblate Mesoporous Silica Nanoparticles as Nanoantibiotics to Target Mycobacteria

    PubMed Central

    Hao, Nanjing; Chen, Xuan; Jeon, Seaho

    2015-01-01

    Engineering nanomaterials with enhanced antibacterial activities remains a critical and practical challenge. Hollow oblate mesoporous silica nanoparticles (HOMSNs) are synthesized by a simple protocol of ammonia hydrothermal treatment of oblate mesoporous silica nanoparticles prepared using dibenzyl ether as a co-solvent. When conjugate with trehalose as the targeting ligand, the antibiotic-encapsulated HOMSNs exhibit high binding affinity and antibacterial efficacy towards mycobacteria. PMID:26450697

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

    PubMed

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

    2016-04-06

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

  4. Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica

    DOEpatents

    Pham, Hien N.; Datye, Abhaya K.

    2003-04-15

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

  5. Study of CO2 adsorption capacity of mesoporous carbon and activated carbon modified by triethylenetetramine (TETA)

    NASA Astrophysics Data System (ADS)

    Sulistianti, I.; Krisnandi, Y. K.; Moenandar, I.

    2017-04-01

    Mesoporous carbon was synthesized by soft template method using phloroglucinol and formaldehyde as a carbon source; and Pluronic F-127 as a mesoporous template. The synthesized mesoporous carbon and commercial activated carbon were modified with triethylenetetramine (TETA) to increase CO2 adsorption capacity. Based on FTIR characterization, the synthesized mesoporous carbon and the activated carbon without modification process has similarity pattern. After the modification, both of them showed absorption peaks in the area around 1580 to 1650 cm-1 which is known as N-H bending vibration and absorption peaks in the area around 3150 to 3380 cm-1 which is known as N-H stretching vibration. The XRD results showed two peaks at 2θ = 24.21° and 2θ = 43.85°, according to JCPDS index No. 75-1621 those peak are the typical peaks for hexagonal graphite carbon. In BET analysis, the synthesized mesoporous carbon and activated carbon modified TETA have surface area, pore volume and pore diameter lower than without modification process. In carbon dioxide adsorption testing, the synthesized mesoporous carbon showed better performance than the commercial activated carbon for CO2 adsorption both without modification and by modification. The synthesized mesoporous carbon obtained CO2 adsorption of 9.916 mmol/g and the activated carbon of 3.84 mmol/g for on 3.5 hours of adsorption. It is three times better than activated carbon for adsorption of carbon dioxide. The modified mesoporous carbon has the best performance for adsorption of gas CO2 if compared by unmodified.

  6. Synthesis and characterization of mesoporous silica functionalized with calix[4]arene derivatives.

    PubMed

    Alahmadi, Sana M; Mohamad, Sharifah; Maah, Mohd Jamil

    2012-10-23

    This work reports a new method to covalently attach calix[4]arene derivatives onto MCM-41, using a diisocyanate as a linker. The modified mesoporous silicates were characterized by fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA) and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalently attached to the mesoporous silica. The preservation of the MCM-41 channel system was checked by X-ray diffraction and nitrogen adsorption analysis.

  7. Controlling nanostructures of mesoporous silica fibers by supramolecular assembly of genetically modifiable bacteriophages.

    PubMed

    Mao, Chuanbin; Wang, Fuke; Cao, Binrui

    2012-06-25

    A useful virus: The synthesis of a new family of mesoporous silica fibers is reported. Monodisperse filamentous bacteriophages self-assembled into highly ordered hexagonal lattices that were used as templates for the formation of silica nanostructures. Removal of the bacteriophage assembly through calcination led to the formation of mesoporous silica fibers with pore structures precisely defined by the bacteriophage assembly (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Prevention of bacterial adhesion to zwitterionic biocompatible mesoporous glasses.

    PubMed

    Sánchez-Salcedo, Sandra; García, Ana; Vallet-Regí, María

    2017-07-15

    Novel materials, based on Mesoporous Bioactive Glasses (MBGs) in the ternary system SiO2-CaO-P2O5, decorated with (3-aminopropyl)triethoxysilane (APTES) and subsequently with amino acid Lysine (Lys), by post-grafting method on the external surface of the glasses (named MBG-NH2 and MBG-Lys), are reported. The surface functionalization with organic groups did not damage the mesoporous network and their structural and textural properties were also preserved despite the high solubility of MBG matrices. The incorporation of Lys confers a zwitterionic nature to these MBG materials due to the presence of adjacent amine and carboxylic groups in the external surface. At physiologic pH, this coexistence of basic amine and carboxilic acid groups from anchored Lys provided zero surface charge named zwitterionic effect. This behaviour could give rise to potential applications of antibacterial adhesion. Therefore, in order to assess the influence of zwitterionic nature in in vitro bacterial adhesion, studies were carried out with Staphylococcus aureus. It was demonstrated that the efficient interaction of these zwitterionic pairs onto the MBG surfaces reduced bacterial adhesion up to 99.9% compared to bare MBGs. In order to test the suitability of zwitterionic MBGs materials as bone grafts, their cytocompatibility was investigated in vitro with MC3T3-E1 preosteoblasts. These findings suggested that the proposed surface functionalization strategy provided MBG materials with notable antibacterial adhesion properties, hence making these materials promising candidates for local bone infection therapy. The present research work is focused in finding a preventive treatment of bone infection based on Mesoporous Bioactive Glasses (MBGs) with antibacterial adhesion properties obtained by zwitterionic surface modification. MBGs exhibit unique nanostructural, textural and bioactive characteristics. The novelty and originality of this manuscript is based on the design and optimization of a

  9. Bone tissue engineering using silica-based mesoporous nanobiomaterials:Recent progress.

    PubMed

    Shadjou, Nasrin; Hasanzadeh, Mohammad

    2015-10-01

    Bone disorders are of significant concern due to increase in the median age of our population. It is in this context that tissue engineering has been emerging as a valid approach to the current therapies for bone regeneration/substitution. Tissue-engineered bone constructs have the potential to alleviate the demand arising from the shortage of suitable autograft and allograft materials for augmenting bone healing. Silica based mesostructured nanomaterials possessing pore sizes in the range 2-50 nm and surface reactive functionalities have elicited immense interest due to their exciting prospects in bone tissue engineering. In this review we describe application of silica-based mesoporous nanomaterials for bone tissue engineering. We summarize the preparation methods, the effect of mesopore templates and composition on the mesopore-structure characteristics, and different forms of these materials, including particles, fibers, spheres, scaffolds and composites. Also, the effect of structural and textural properties of mesoporous materials on development of new biomaterials for production of bone implants and bone cements was discussed. Also, application of different mesoporous materials on construction of manufacture 3-dimensional scaffolds for bone tissue engineering was discussed. It begins by giving the reader a brief background on tissue engineering, followed by a comprehensive description of all the relevant components of silica-based mesoporous biomaterials on bone tissue engineering, going from materials to scaffolds and from cells to tissue engineering strategies that will lead to "engineered" bone.

  10. Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

    PubMed Central

    Vivero-Escoto, Juan L; Chiang, Ya-Dong; Wu, Kevin; Yamauchi, Yusuke

    2012-01-01

    This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications. PMID:27877467

  11. Phosphate adsorption on aluminum-impregnated mesoporous silicates: surface structure and behavior of adsorbents.

    PubMed

    Shin, Eun Woo; Han, James S; Jang, Min; Min, Soo-Hong; Park, Jae Kwang; Rowell, Roger M

    2004-02-01

    Phosphorus from excess fertilizers and detergents ends up washing into lakes, creeks, and rivers. This overabundance of phosphorus causes excessive aquatic plant and algae growth and depletes the dissolved oxygen supply in the water. In this study, aluminum-impregnated mesoporous adsorbents were tested for their ability to remove phosphate from water. The surface structure of the materials was investigated with X-ray diffraction (XRD), a N2 adsorption-desorption technique, Fourier transform-infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) to understand the effect of surface properties on the adsorption behavior of phosphate. The mesoporous materials were loaded with Al components by reaction with surface silanol groups. In the adsorption test, the Al-impregnated mesoporous materials showed fast adsorption kinetics as well as high adsorption capacities, compared with activated alumina. The uniform mesopores of the Al-impregnated mesoporous materials caused the diffusion rate in the adsorption process to increase, which in turn caused the fast adsorption kinetics. High phosphate adsorption capacities of the Al-impregnated mesoporous materials were attributed to not only the increase of surface hydroxyl density on Al oxide due to well-dispersed impregnation of Al components but also the decrease in stoichiometry of surface hydroxyl ions to phosphate by the formation of monodentate surface complexes.

  12. Effect of secondary template polarity to the properties of mesoporous ZSM-5 zeolites

    NASA Astrophysics Data System (ADS)

    Karim, T. M.; Nuzuliyah, R.; Nurani, D. A.; Krisnandi, Y. K.

    2017-07-01

    Synthesis and characterization of mesoporous ZSM-5 using two kinds of secondary templates with different polarity, polydiallyldimethylammonium chloride (PDDA-Cl) or cetyltrimethylammonium bromide (CTABr) were studied. The weight lost after calcination at 550 °C for 5 hours were 30.93 wt% and 25.87 wt% for PDDA-Cl-templated ZSM-5 (ZSM-5pc) and CTABr-templated ZSM-5 (ZSM-5cs), respectively. Both as-synthesized mesoporous ZSM-5 zeolites then were characterized by XRD, FTIR, SEM, and EDX. Based on wide angle XRD analysis that both mesoporous ZSM-5 showed similar diffraction patterns and the typical peaks of ZSM-5 in which 2θ = 7°-9° (doublet peaks) and 22°-25° (triplet peaks) appeared. For the analysis of functional group, FTIR analysis showed that both mesoporous ZSM-5 gave strong band at 550 cm-1, which is attributed to asymmetric stretching vibration of the double 5-rings from MFI zeolites. Meanwhile, the result of EDX calculation showed mesoporous ZSM-5pc had Si/Al ratio of and ZSM-5cs had Si/Al ratio of 12.62. Furthermore, the SEM images exhibited mesoporous ZSM-5pc had morphology of hexagonal (coffin-like) while ZSM-5cs had ellipse form.

  13. Novel mesoporous Si@C microspheres as anodes for lithium-ion batteries.

    PubMed

    Ma, Xiaomei; Liu, Mingxian; Gan, Lihua; Tripathi, Pranav K; Zhao, Yunhui; Zhu, Dazhang; Xu, Zijie; Chen, Longwu

    2014-03-07

    In this paper, we demonstrate the design and synthesis of novel mesoporous Si@C microspheres as anode materials for high-performance lithium-ion batteries. SiO2 nanoparticles modified with hexadecyl trimethyl ammonium bromide are enveloped within resorcinol-formaldehyde polymer microspheres which form in the ethanol-water-ammonia system. Mesoporous voids between Si nanoparticles and the carbon framework are generated after carbonization at 800 °C and magnesiothermic reduction at 650 °C. The resultant Si@C microspheres show regular spherical shapes with a mean diameter of about 500 nm, a mesopore size of 3.2 nm and specific surface areas of 401-424 m(2) g(-1). Mesoporosity of Si@C microspheres effectively buffers the volume expansion/shrinkage of Si nanoparticles during Li ion insertion/extraction, which endows mesoporous Si@C microspheres with excellent electrochemical performance and cycle stability when they are used as lithium-ion battery anode materials. A typical sample of mesoporous Si@C microspheres presents a specific capacity of 1637 and 1375 mA h g(-1) at first discharge and charge under a current density of 50 mA g(-1). After 100 cycles, the charge capacity remains 1053 mA h g(-1) with a coulombic efficiency of 99%, showing good cycle stability of the anode. This finding highlights the potential application of mesoporous Si@C microspheres in lithium-ion battery anode materials.

  14. Interfacial confined formation of mesoporous spherical TiO2 nanostructures with improved photoelectric conversion efficiency.

    PubMed

    Shao, Wei; Gu, Feng; Li, Chunzhong; Lu, Mengkai

    2010-06-21

    Uniform mesoporous TiO(2) nanospheres were successfully developed via an interfacial confined formation process for application in dye-sensitized solar cells. The mesoporous spherical structures greatly promote the dye-loading capacity, electron transfer, and light scattering, resulting in remarkable enhancement of the cell performance. The designed interfacial platform caused a reaction-limited aggregation of the TiO(2) nanocrystals, resulting in the formation of mesoporous spherical nanostructures with sphere diameter of 216 nm and pore size of 8 nm. The oriented attachment of adjacent TiO(2) nanocrystals facilitated the electron transfer process when the mesoporous TiO(2) nanospheres were used as electrode films. The dye coverage was enhanced remarkably in the mesoporous spherical TiO(2) samples. Owing to the enhanced light-harvesting efficiency, solar conversion efficiency was enhanced about 30% for the dye-sensitized solar cell (DSSC) based on mesoporous spherical TiO(2) in comparison with that made by commercial TiO(2) nanoparticles.

  15. Application of mesoporous silicon dioxide and silicate in oral amorphous drug delivery systems.

    PubMed

    Qian, Ken K; Bogner, Robin H

    2012-02-01

    Aqueous solubility of an active pharmaceutical ingredient is an important consideration to ensure successful drug development. Mesoporous materials have been investigated as an amorphous drug delivery system owing to their nanosized capillaries and large surface areas. The complex interactions of crystalline compounds with mesoporous media and their implication in drug delivery are not well understood. Molecules interacting with porous media behave very differently than those in bulk phase. Their altered dynamics and thermodynamics play an important role in the properties and product performance of the amorphous system. In this review, application of mesoporous silicon dioxide and silicates in drug amorphization is the main focus. First, as background, the nature of gas-porous media interactions is summarized. The synthesis of various types of mesoporous silica, which are used by many investigators in this field, is described. Second, the behavior of molecules confined in mesopores is compared with those in bulk, crystalline phase. The molecular dynamics of compounds due to confinement, analyzed using various techniques, and their consequences in drug delivery are discussed. Finally, the preparation and performance of drug delivery systems using mesoporous silica are examined.

  16. Supported mesoporous carbon ultrafiltration membrane and process for making the same

    SciTech Connect

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

    2004-04-13

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

  17. A simple large-scale synthesis of mesoporous In2O3 for gas sensing applications

    NASA Astrophysics Data System (ADS)

    Zhang, Su; Song, Peng; Yan, Huihui; Yang, Zhongxi; Wang, Qi

    2016-08-01

    In this paper, large-scale mesoporous In2O3 nanostructures were synthesized by a facile Lewis acid catalytic the furfural alcohol resin (FAR) template route for the high-yield. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG) and the Brunauer-Emmett-Teller (BET) approach. The as-obtained mesoporous In2O3 nanostructures possess excellent mesoporous and network structure, which increases the contact area with the gases, it is conducive for adsorption-desorption of gas on the surface of In2O3. The In2O3 particles and pores were both about 15 nm and very uniform. In gas-sensing measurements with target gases, the gas sensor based on mesoporous In2O3 nanostructures showed a good response, short response-recovery time, good selectivity and stability to ethanol. These properties are due to the large specific surface area of mesoporous structure. This synthetic method could use as a new design concept for functional mesoporous nanomaterials and for mass production.

  18. Cefazolin-loaded mesoporous silicon microparticles show sustained bactericidal effect against Staphylococcus aureus

    PubMed Central

    Yazdi, Iman K; Murphy, Matthew B; Loo, Christopher; Liu, Xuewu; Ferrari, Mauro; Weiner, Bradley K

    2014-01-01

    Cefazolin is an antibiotic frequently used in preoperative prophylaxis of orthopedic surgery and to fight secondary infections post-operatively. Although its systemic delivery in a bulk or bolus dose is usually effective, the local and controlled release can increase its effectiveness by lowering dosages, minimizing total drug exposure, abating the development of antibiotic resistance and avoiding the cytotoxic effect. A delivery system based on mesoporous silicon microparticles was developed that is capable of efficiently loading and continuously releasing cefazolin over several days. The in vitro release kinetics from mesoporous silicon microparticles with three different nanopore sizes was evaluated, and minimal inhibitory concentration of cefazolin necessary to eliminate a culture of Staphylococcus aureus was identified to be 250 µg/mL. A milder toxicity toward mesenchymal stem cells was observed from mesoporous silicon microparticles over a 7-day period. Medium pore size-loaded mesoporous silicon microparticles exhibited long-lasting bactericidal properties in a zone inhibition assay while they were able to kill all the bacteria growing in suspension cultures within 24 h. This study demonstrates that the sustained release of cefazolin from mesoporous silicon microparticles provides immediate and long-term control over bacterial growth both in suspension and adhesion while causing minimal toxicity to a population of mesenchymal stem cell. Mesoporous silicon microparticles offer significant advantageous properties for drug delivery applications in tissue engineering as it favorably extends drug bioavailability and stability, while reducing concomitant cytotoxicity to the surrounding tissues. PMID:24904728

  19. Development of mesophase pitch derived mesoporous carbons through a commercially nanosized template.

    PubMed

    Qiao, W M; Song, Y; Hong, S H; Lim, S Y; Yoon, S-H; Korai, Y; Mochida, I

    2006-04-11

    Mesoporous carbons (MCs) with a high surface area (up to 900 m2/g), large pore volume (up to 2.1 cm3/g), high mesopore ratio (94%), and high yield (70%) were successfully prepared from an AR mesophase pitch, using a commercially nanosized silica template. The removal of the template provided some larger mesopores of 25-50 nm (pore I) with a surface area of ca. 300 m2/g, while the successive carbonization opened the closed pores within the carbon body to give smaller mesopores of 2-10 nm (pore II) with a similar surface area. During the carbonization of pitch precursor, the evaporation of volatile components swells the carbon to introduce the second mesopores among the domains and even microdomain units because of their rearrangements and overlappings in the process. The addition of iron salt with the silica template resulted in a remarkable increase of the surface area (ca. 300 m2/g) by introducing mesopores of 3-5 nm. The resultant MCs maintained some graphitizable natures derived from the anisotropic precursor. Their graphitization at 2400 degrees C provided the graphitic structure with large surface areas (270-460 m2/g) and mesoporosity.

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

    PubMed Central

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

    2010-01-01

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

  1. Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes.

    PubMed

    Lozano-Sanchez, Pablo; Elliott, Joanne M

    2008-02-01

    Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

  2. Hollow/rattle-type mesoporous nanostructures by a structural difference-based selective etching strategy.

    PubMed

    Chen, Yu; Chen, Hangrong; Guo, Limin; He, Qianjun; Chen, Feng; Zhou, Jian; Feng, Jingwei; Shi, Jianlin

    2010-01-26

    A novel "structural difference-based selective etching" strategy has been developed to fabricate hollow/rattle-type mesoporous nanostructures, which was achieved by making use of the structural differences, rather than traditional compositional differences, between the core and the shell of a silica core/mesoporous silica shell structure to create hollow interiors. Highly dispersed hollow mesoporous silica spheres with controllable particle/pore sizes could be synthesized by this method, which show high loading capacity (1222 mg/g) for anticancer drug (doxorubicin). Hemolyticity and cytotoxicity assays of hollow mesoporous silica spheres were conducted, and the synthesized hollow mesoporous silica spheres with large pores show ultrafast immobilization of protein-based biomolecules (hemoglobin). On the basis of this strategy, different kinds of heterogeneous rattle-type nanostructures with inorganic nanocrystals, such as Au, Fe(2)O(3), and Fe(3)O(4) nanoparticles, as the core and mesoporous silica as the shell were also prepared. This strategy could be extended as a general approach to synthesize various hollow/rattle-type nanostructures by creating adequate structural differences between cores and shells in core/shell structures in nanoscale.

  3. One-step synthesis of hydrophobic mesoporous silica and its application in nonylphenol adsorption

    NASA Astrophysics Data System (ADS)

    Zhao, Yanling; Song, Jinliang; Wu, Dong; Tang, Tao; Sun, Yuhan

    2015-11-01

    Highly CH3-functionalized mesoporous silica with nearly spherical morphology was synthesized under acidic conditions by co-condensation of two different silica precursors polymethylhydrosiloxane (PMHS) and tetraethoxysilane (TEOS) in the presence of triblock copolymer P123 as template. XRD, N2 adsorption-desorption, HRTEM, SEM and 29Si MAS NMR were used to identify its highly-ordered mesopore array structure, nearly spherical particle morphology and CH3 functionalization of the as-synthesized material. The resulting hydrophobic mesoporous silica possessed regular mesochannel arrays, indicating that the introduction of PMHS had little impact on the formation of an ordered mesostructure. Also, PMHS played an important role in morphology control and organic functionalization, ensuring nearly spherical particle morphology and high CH3 functionalization degree of the obtained mesoporous silica material. As compared with pristine mesoporous silica SBA-15, the hydrophobic mesoporous silica showed the higher adsorption performance when they were used as adsorbents to remove organic pollutant nonylphenol at a very low concentration from aqueous solution.

  4. The effects of structural properties on the lithium storage behavior of mesoporous TiO2

    NASA Astrophysics Data System (ADS)

    Xiao, Liang; Meng, Wen; Wang, Shiyao; Liu, Dan; Qu, Deyu; Xie, Zhizhong; Deng, Bohua; Liu, Jinping

    2017-06-01

    Understanding the effects of structural properties on the lithium storage behavior of mesoporous TiO2 is crucial for further optimizing its performance through rational structure design. To achieve this, herein, the surface area and the grain size of the prepared mesoporous TiO2 are intentionally adjusted by controlling the calcination temperatures. It is found that the capacities of the mesoporous TiO2 contain both the lithium-ion insertion into the bulk phase (Q in) and the additional surface lithium storage (Q as). The Q in gradually increases with grain sizes to a steady level and then slightly drops. By contrast, the Q as is directly proportional to the specific surface area of the mesoporous TiO2 and is ascribed to the capacity originated from the lithium-ion insertion into the surface layer. The experimental comparison and analysis demonstrate that the fast kinetics of the Q as ensure both the better rate performance and capacity retention of mesoporous TiO2 than bulk ones. Specially, the mesoporous TiO2 calcinated at 350 °C shows the highest reversible specific capacity of 250.2 mA h g-1, the best rate capability (132.5 mA h g-1 at 2C) and good cycling stability. Our findings shed great light on the design of high-performance nanostructured TiO2 with surface lithium storage.

  5. Synthesis, characterization, and application of surface-functionalized ordered mesoporous nanoparticles

    SciTech Connect

    Chung, Po-Wen

    2009-01-01

    The dissertation begins with Chapter 1, which is a general introduction of the fundamental synthesis of mesoporous silica materials, the selective functionlization of mesoporous silica materials, and the synthesis of nanostructured porous materials via nanocasting. In Chapter 2, the thermo-responsive polymer coated mesoporous silica nanoparticles (MSN) was synthesized via surface-initated polymerization and exhibited unique partition activities in a biphasic solution with the thermally induced change. In Chapter 3, the monodispersed spherical MSN with different mesoporous structure (MCM-48) was developed and employed as a template for the synthesis of mesoporous carbon nanoparticles (MCN) via nanocasting. MCN was demonstrated for the delivery of membrane impermeable chemical agents inside the cells. The cellular uptake efficiency and biocompabtibility of MCN with human cervical cancer cells were also investigated. In addition to the biocompabtibility of MCN, MCN was demonstrated to support Rh-Mn nanoparticles for catalytic reaction in Chapter 4. Owing to the unique mesoporosity, Rh-Mn nanoparticles can be well distributed inside the mesoporous structure and exhibited interesting catalytic performance on CO hydrogenation. In Chapter 5, the synthesis route of the aforementioned MCM-48 MSN was discussed and investigated in details and other metal oxide nanoparticles were also developed via nanocasting by using MCM-48 MSN as a template. At last, there is a general conclusion summarized in Chapter 6.

  6. Monodisperse spherical mesoporous silica particles: fast synthesis procedure and fabrication of photonic-crystal films.

    PubMed

    Trofimova, E Yu; Kurdyukov, D A; Yakovlev, S A; Kirilenko, D A; Kukushkina, Yu A; Nashchekin, A V; Sitnikova, A A; Yagovkina, M A; Golubev, V G

    2013-04-19

    A procedure for the synthesis of monodisperse spherical mesoporous silica particles (MSMSPs) via the controlled coagulation of silica/surfactant clusters into spherical aggregates with mean diameters of 250-1500 nm has been developed. The synthesis is fast (taking less than 1 h) because identical clusters are simultaneously formed in the reaction mixture. The results of microscopic, x-ray diffraction, adsorption and optical measurements allowed us to conclude that the clusters are ∼15 nm in size and have hexagonally packed cylindrical pore channels. The channel diameters in MSMSPs obtained with cethyltrimethylammonium bromide and decyltrimethylammonium bromide as structure-directing agents were 3.1 ± 0.15 and 2.3 ± 0.12 nm, respectively. The specific surface area and the pore volume of MSMSP were, depending on synthesis conditions, 480-1095 m(2) g(-1) and 0.50-0.65 cm(3) g(-1). The MSMSP were used to grow opal-like photonic-crystal films possessing a hierarchical macro-mesoporous structure, with pores within and between the particles. A selective filling of mesopore channels with glycerol, based on the difference between the capillary pressures in macro- and mesopores, was demonstrated. It is shown that this approach makes it possible to control the photonic bandgap position in mesoporous opal films by varying the degree of mesopore filling with glycerol.

  7. Monodisperse spherical mesoporous silica particles: fast synthesis procedure and fabrication of photonic-crystal films

    NASA Astrophysics Data System (ADS)

    Trofimova, E. Yu; Kurdyukov, D. A.; Yakovlev, S. A.; Kirilenko, D. A.; Kukushkina, Yu A.; Nashchekin, A. V.; Sitnikova, A. A.; Yagovkina, M. A.; Golubev, V. G.

    2013-04-01

    A procedure for the synthesis of monodisperse spherical mesoporous silica particles (MSMSPs) via the controlled coagulation of silica/surfactant clusters into spherical aggregates with mean diameters of 250-1500 nm has been developed. The synthesis is fast (taking less than 1 h) because identical clusters are simultaneously formed in the reaction mixture. The results of microscopic, x-ray diffraction, adsorption and optical measurements allowed us to conclude that the clusters are ˜15 nm in size and have hexagonally packed cylindrical pore channels. The channel diameters in MSMSPs obtained with cethyltrimethylammonium bromide and decyltrimethylammonium bromide as structure-directing agents were 3.1 ± 0.15 and 2.3 ± 0.12 nm, respectively. The specific surface area and the pore volume of MSMSP were, depending on synthesis conditions, 480-1095 m2 g-1 and 0.50-0.65 cm3 g-1. The MSMSP were used to grow opal-like photonic-crystal films possessing a hierarchical macro-mesoporous structure, with pores within and between the particles. A selective filling of mesopore channels with glycerol, based on the difference between the capillary pressures in macro- and mesopores, was demonstrated. It is shown that this approach makes it possible to control the photonic bandgap position in mesoporous opal films by varying the degree of mesopore filling with glycerol.

  8. Superior electrode performance of mesoporous hollow TiO2 microspheres through efficient hierarchical nanostructures

    NASA Astrophysics Data System (ADS)

    Zhang, Feng; Zhang, Yu; Song, Shuyan; Zhang, Hongjie

    2011-10-01

    Mesoporous hollow TiO2 microspheres with controlled size and hierarchical nanostructures are designed from a process employing in suit template-assisted and hydrothermal methods. The results show that the hollow microspheres composed of mesoporous nanospheres possess very stable reversible capacity of 184 mAh g-1 at 0.25C and exhibit extremely high power of 122 mAh g-1 at the high rate of 10C. The superior high-rate and high-capacity performance of the sample is attributed to the efficient hierarchical nanostructures. The hollow structure could shorten the diffusion length for lithium ion in the microspheres. The large mesoporous channels between the mesoporous nanospheres provide an easily-accessed system which facilitates electrolyte transportation and lithium ion diffusion within the electrode materials. The electrolyte, flooding the mesoporous channels, can also lead to a high electrolyte/electrode contact area, facilitating transport of lithium ions across the electrolyte/electrode interface. The small mesopores in the meosporous nanospheres can make the electrolyte and lithium ion further diffuse into the interior of electrode materials and increase electrolyte/electrode contact area. The small nanoparticles can also ensure high reversible capacity.

  9. Study on the pyrolysis of cellulose for bio-oil with mesoporous molecular sieve catalysts.

    PubMed

    Yu, Feng-wen; Ji, Deng-xiang; Nie, Yong; Luo, Yao; Huang, Cheng-jie; Ji, Jian-bing

    2012-09-01

    Mesoporous materials possess a hexagonal array of uniform mesopores, high surface areas, and moderate acidity. They are one of the important catalysts in the field of catalytic pyrolysis. In this paper, mesoporous materials of Al-MCM-41, La-Al-MCM-41, and Ce-Al-MCM-41 were synthesized, characterized, and tested as catalysts in the cellulose catalytic pyrolysis process using a fixed bed pyrolysis reactor. The results showed that mesoporous materials exhibited a strong influence on the pyrolytic behavior of cellulose. The presence of these mesoporous molecular sieve catalysts could vary the yield of products, which was that they could decrease the yield of liquid and char and increase the yield of gas product, and could promote high-carbon chain compounds to break into low-carbon chain compounds. Mesoporous molecular sieve catalysts were benefit to the reaction of dehydrogenation and deoxidation and the breakdown of carbon chain. Further, La-Al-MCM-41 and Ce-Al-MCM-41 catalysts can produce more toluene and 2-methoxy-phenol, as compared to the non-catalytic runs.

  10. Enhancing adsorption efficiency of dichloroacetic acid onto mesoporous carbons: Procedure optimization, mechanism and characterization.

    PubMed

    Ding, Ying; Zhu, Jianzhong; Ji, Dongliang; Cao, Yang; Ling, Xiaojia; Chen, Wei

    2015-08-15

    Highly ordered mesoporous carbon may be directly synthesized via supramolecular self-assembly with in situ evaporation-induced crystallization process by controlling thermal reaction temperatures and carbon mass loading. In the present study, the effects of thermal reaction temperatures on the structural characterization and adsorption capacity of mesoporous carbon have been investigated and analyzed with orthogonal test experiments. The results show the carbonization temperature (R=32.1) plays a more important role than the self-assembly temperature (R=8.5) and thermal polymerization temperature (R=10.1) in manipulating the pore texture structures. The optimization grouping temperature was 40-110-500 °C. The optimum mesoporous carbon sample had the highest BET specific surface area (474 m(2)/g), the largest pore volume (0.46 cm(3)/g), and with reasonable uniform pore size distribution. The adsorption evaluation also shows the adsorption capacity is strongly correlated with the pore structure of mesoporous carbon, the optimized mesoporous carbon sample displayed the largest adsorption capacity (350 mg/g) at an initial concentration of 20.0 mg/L of dichloroacetic acid. The study results indicate optimization of thermal reaction parameters is an effective approach for synthesis of ordered mesoporous carbons.

  11. Mesoporous TiO2 single crystals: facile shape-, size-, and phase-controlled growth and efficient photocatalytic performance.

    PubMed

    Zheng, Xiaoli; Kuang, Qin; Yan, Keyou; Qiu, Yongcai; Qiu, Jianhang; Yang, Shihe

    2013-11-13

    In this work, we have succeeded in preparing rutile and anatase TiO2 mesoporous single crystals with diverse morphologies in a controllable fashion by a simple silica-templated hydrothermal method. A simple in-template crystal growth process was put forward, which involved heterogeneous crystal nucleation and oriented growth within the template, a sheer spectator, and an excluded volume, i.e., crystal growth by faithful negative replication of the silica template. A series of mesoporous single-crystal structures, including rutile mesoporous TiO2 nanorods with tunable sizes and anatase mesoporous TiO2 nanosheets with dominant {001} facets, have been synthesized to demonstrate the versatility of the strategy. The morphology, size, and phase of the TiO2 mesoporous single crystals can be tuned easily by varying the external conditions such as the hydrohalic acid condition, seed density, and temperature rather than by the silica template, which merely serves for faithful negative replication but without interfering in the crystallization process. To demonstrate the application value of such TiO2 mesoporous single crystals, photocatalytic activity was tested. The resultant TiO2 mesoporous single crystals exhibited remarkable photocatalytic performance on hydrogen evolution and degradation of methyl orange due to their increased surface area, single-crystal nature, and the exposure of reactive crystal facets coupled with the three-dimensionally connected mesoporous architecture. It was found that {110} facets of rutile mesoporous single crystals can be considered essentially as reductive sites with a key role in the photoreduction, while {001} facets of anatase mesoporous single crystals provided oxidation sites in the oxidative process. Such shape- and size-controlled rutile and anatase mesoporous TiO2 single crystals hold great promise for building energy conversion devices, and the simple solution-based hydrothermal method is extendable to the synthesis of other

  12. Synthesis of Ordered Mesoporous Phenanthrenequinone-Carbon via π-π Interaction-Dependent Vapor Pressure for Rechargeable Batteries

    PubMed Central

    Kwon, Mi-Sook; Choi, Aram; Park, Yuwon; Cheon, Jae Yeong; Kang, Hyojin; Jo, Yong Nam; Kim, Young-Jun; Hong, Sung You; Joo, Sang Hoon; Yang, Changduk; Lee, Kyu Tae

    2014-01-01

    The π-π interaction-dependent vapour pressure of phenanthrenequinone can be used to synthesize a phenanthrenequinone-confined ordered mesoporous carbon. Intimate contact between the insulating phenanthrenequinone and the conductive carbon framework improves the electrical conductivity. This enables a more complete redox reaction take place. The confinement of the phenanthrenequinone in the mesoporous carbon mitigates the diffusion of the dissolved phenanthrenequinone out of the mesoporous carbon, and improves cycling performance. PMID:25490893

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

    NASA Astrophysics Data System (ADS)

    Bhaway, Sarang M.

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

  14. Selective functionalization of the mesopores of SBA-15

    DOE PAGES

    Webb, Jonathan D.; Seki, Tomohiro; Goldston, Jennifer F.; ...

    2014-10-23

    In this study, a method has been developed that permits the highly selective functionalization of the interior and exterior surfaces of the ubiquitous mesoporous material, SBA-15. The key step is reloading the as-synthesized material with structure-directing agent, Pluronic® P123, prior to selective functionalization of the external surface with a silylating agent. This new approach represents a significant improvement over literature procedures. Results from physisorption analyses as well as solid-state NMR permit a detailed, quantitative assessment of functionalized SBA-15. This work also provides insight into the stability of the silyl layer during extraction procedures – an issue often neglected in othermore » studies but of significant importance as decomposition of this layer could result in the introduction of new silanols and reduce the effectiveness of any selective grafting procedure.« less

  15. Preparation method: structure-bioactivity correlation in mesoporous bioactive glass

    NASA Astrophysics Data System (ADS)

    Shih, Shao-Ju; Chou, Yu-Jen; Borisenko, Konstantin B.

    2013-06-01

    Mesoporous bioactive glasses (MBGs) are receiving increased attention because of their superior bioactive properties and possible applications as drug-releasing carriers, bone implants and sealing materials in dentistry. We report here the results of investigation of structures and bioactivities of two types of MBG particles prepared by two different techniques, the sol-gel method and spray pyrolysis (SP). In this study, we used transmission electron microscopy and selected area electron diffraction to characterize particle morphology and atomistic structures of the particles correlating these observations with nitrogen adsorption measurements to determine surface areas of the particles and in vitro bioactivity tests. It is found that the preparation method can influence the final composition of the particles and that SP method offers a better control over the composition. The SP particles have higher bioactivity than the sol-gel particles due to their higher surface area and possibly more favourable atomistic structure for promoting deposition of pure hydroxyl apatite phase.

  16. Amine-functionalized magnetic mesoporous silica nanoparticles for DNA separation

    NASA Astrophysics Data System (ADS)

    Sheng, Wei; Wei, Wei; Li, Junjian; Qi, Xiaoliang; Zuo, Gancheng; Chen, Qi; Pan, Xihao; Dong, Wei

    2016-11-01

    We report a modified approach for the functionalized magnetic mesoporous silica nanoparticles (MMSN) using polymer microspheres incorporated with magnetic nanoparticles in the presence of cetyltrimethylammonium bromide (CTAB) and the core-shell magnetic silica nanoparticles (MSN). These particles were functionalized with amino groups via the addition of aminosilane directly to the particle sol. We then evaluate their DNA separation abilities and find the capacity of DNA binding significantly increased (210.22 μg/mg) compared with normal magnetic silica spheres (138.44 μg/mg) by using an ultraviolet and visible spectrophotometer (UV). The morphologies, magnetic properties, particle size, pore size, core-shell structure and Zeta potential are characterized by Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), Transmission electron microscopy (TEM), Powder X-ray diffraction (XRD), and dynamic light scattering (DLS). This work demonstrates that our MMSN own an excellent potential application in bioseparation and drug delivery.

  17. Functionalized mesoporous silica nanoparticles for oral delivery of budesonide

    NASA Astrophysics Data System (ADS)

    Yoncheva, K.; Popova, M.; Szegedi, A.; Mihaly, J.; Tzankov, B.; Lambov, N.; Konstantinov, S.; Tzankova, V.; Pessina, F.; Valoti, M.

    2014-03-01

    Non-functionalized and amino-functionalized mesoporous silica nanoparticle were loaded with anti-inflammatory drug budesonide and additionally post-coated with bioadhesive polymer (carbopol). TEM images showed spherical shape of the nanoparticles and slightly higher polydispersity after coating with carbopol. Nitrogen physisorption and thermogravimetic analysis revealed that more efficient loading and incorporation into the pores of nanoparticles was achieved with the amino-functionalized silica carrier. Infrared spectra indicated that the post-coating of these nanoparticles with carbopol led to the formation of bond between amino groups of the functionalized carrier and carboxyl groups of carbopol. The combination of amino-functionalization of the carrier with the post-coating of the nanoparticles sustained budesonide release. Further, an in vitro model of inflammatory bowel disease showed that the cytoprotective effect of budesonide loaded in the post-coated silica nanoparticles on damaged HT-29 cells was more pronounced compared to the cytoprotection obtained with pure budesonide.

  18. Facile Aqueous Route to Nitrogen-Doped Mesoporous Carbons.

    PubMed

    Zhang, Jianan; Song, Yang; Kopeć, Maciej; Lee, Jaejun; Wang, Zongyu; Liu, Siyuan; Yan, Jiajun; Yuan, Rui; Kowalewski, Tomasz; Bockstaller, Michael R; Matyjaszewski, Krzysztof

    2017-09-20

    An aqueous-based approach for the scalable synthesis of nitrogen-doped porous carbons with high specific surface area (SSA) and high nitrogen content is presented. Low molecular weight polyacrylonitrile (PAN) is solubilized in water in the presence of ZnCl2 that also acts as a volatile porogen during PAN pyrolysis to form mesoporous structures with significantly increased SSA. By templating with commercial SiO2 nanoparticles, nanocellulose fillers or filter paper, nanocarbons with SSA = 1776, 1366, and 1501 m(2)/g, respectively and 10 wt % N content were prepared. The materials formed by this benign process showed excellent catalytic activity in oxygen reduction reaction via the four-electron mechanism.

  19. Mesoporous silica nanoparticles deliver DNA and chemicals into plants

    NASA Astrophysics Data System (ADS)

    Torney, François; Trewyn, Brian G.; Lin, Victor S.-Y.; Wang, Kan

    2007-05-01

    Surface-functionalized silica nanoparticles can deliver DNA and drugs into animal cells and tissues. However, their use in plants is limited by the cell wall present in plant cells. Here we show a honeycomb mesoporous silica nanoparticle (MSN) system with 3-nm pores that can transport DNA and chemicals into isolated plant cells and intact leaves. We loaded the MSN with the gene and its chemical inducer and capped the ends with gold nanoparticles to keep the molecules from leaching out. Uncapping the gold nanoparticles released the chemicals and triggered gene expression in the plants under controlled-release conditions. Further developments such as pore enlargement and multifunctionalization of these MSNs may offer new possibilities in target-specific delivery of proteins, nucleotides and chemicals in plant biotechnology.

  20. Breakable mesoporous silica nanoparticles for targeted drug delivery.

    PubMed

    Maggini, Laura; Cabrera, Ingrid; Ruiz-Carretero, Amparo; Prasetyanto, Eko A; Robinet, Eric; De Cola, Luisa

    2016-04-07

    "Pop goes the particle". Here we report on the preparation of redox responsive mesoporous organo-silica nanoparticles containing disulfide (S-S) bridges (ss-NPs) that, even upon the exohedral grafting of targeting ligands, retained their ability to undergo structural degradation, and increase their local release activity when exposed to a reducing agent. This degradation could be observed also inside glioma C6 cancer cells. Moreover, when anticancer drug-loaded pristine and derivatized ss-NPs were fed to glioma C6 cells, the responsive hybrids were more effective in their cytotoxic action compared to non-breakable particles. The possibility of tailoring the surface functionalization of this hybrid, yet preserving its self-destructive behavior and enhanced drug delivery properties, paves the way for the development of effective biodegradable materials for in vivo targeted drug delivery.