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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. 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. PMID:25424473

  3. Phosphatation of zeolite H-ZSM-5: a combined microscopy and spectroscopy study.

    PubMed

    van der Bij, Hendrik E; Aramburo, Luis R; Arstad, Bjørnar; Dynes, James J; Wang, Jian; Weckhuysen, Bert M

    2014-02-01

    A variety of phosphated zeolite H-ZSM-5 samples are investigated by using a combination of Fourier transfer infrared (FTIR) spectroscopy, single pulse (27)Al, (29)Si, (31)P, (1)H-(31)P cross polarization (CP), (27)Al-(31)P CP, and (27)Al 3Q magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, scanning transmission X-ray microscopy (STXM) and N2 physisorption. This approach leads to insights into the physicochemical processes that take place during phosphatation. Direct phosphatation of H-ZSM-5 promotes zeolite aggregation, as phosphorus does not penetrate deep into the zeolite material and is mostly found on and close to the outer surface of the zeolite, acting as a glue. Phosphatation of pre-steamed H-ZSM-5 gives rise to the formation of a crystalline tridymite AlPO4 phase, which is found in the mesopores of dealuminated H-ZSM-5. Framework aluminum species interacting with phosphorus are not affected by hydrothermal treatment. Dealuminated H-ZSM-5, containing AlPO4 , retains relatively more framework Al atoms and acid sites during hydrothermal treatment than directly phosphated H-ZSM-5.

  4. In situ DRIFTS investigation for the oxidation of toluene by ozone over Mn/HZSM-5, Ag/HZSM-5 and Mn-Ag/HZSM-5 catalysts

    NASA Astrophysics Data System (ADS)

    Li, Jiao; Na, Hongbo; Zeng, Xiaolan; Zhu, Tianle; Liu, Zhiming

    2014-08-01

    The mechanism of toluene oxidation at room temperature over Mn/HZSM-5, Ag/HZSM-5 and Mn-Ag/HZSM-5 catalysts was investigated by in situ DRIFTS. The results show that only a little toluene can be partially oxidized into benzyl alcohol in the absence of O3, while it can be further oxidized into benzaldehyde, benzoic acid, maleic anhydride, and ultimately mineralized to CO2 in the presence of O3. The lattice oxygen is the oxygen species of oxidizing toluene into benzyl alcohol, and the active oxygen species generated from ozone decomposition on the oxygen vacancy over the catalysts are responsible for its complete oxidation. Compared with Mn/HZSM-5 and Ag/HZSM-5 catalysts, the Mn-Ag/HZSM-5 catalyst shows higher catalytic activity for toluene oxidation by ozone, which is attributed to more oxygen vacancy in this catalyst, based on the XPS characterization results.

  5. Furan production from glycoaldehyde over HZSM-5

    DOE PAGESBeta

    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 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

  6. 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.

  7. Solid state 13C NMR studies of methane dehydroaromatization reaction on Mo/HZSM-5 and W/HZSM-5 catalysts.

    PubMed

    Yang, Jun; Ma, Ding; Deng, Feng; Luo, Qing; Zhang, Mingjin; Bao, Xinhe; Ye, Chaohui

    2002-12-21

    Methane dehydroaromatization on Mo/HZSM-5 and W/HZSM-5 catalysts was studied by solid state 13C NMR spectroscopy, both variation of the state of transition metal component and products such as ethane, benzene, ethene adsorbed on or in zeolite were observed after high temperature (900-1000 K) reaction.

  8. Biodiesel production by free fatty acid esterification using Lanthanum (La3+) and HZSM-5 based catalysts.

    PubMed

    Vieira, Sara S; Magriotis, Zuy M; Santos, Nadiene A V; Saczk, Adelir A; Hori, Carla E; Arroyo, Pedro A

    2013-04-01

    In this work the use of the heterogeneous catalysts pure (LO) and sulfated (SLO) lanthanum oxide, pure HZSM-5 and SLO/HZSM-5 (HZSM-5 impregnated with sulfated lanthanum oxide (SO4(2-)/La2O3)) was evaluated. The structural characterization of the materials (BET) showed that the sulfation process led to a reduction of the SLO and SLO/HZSM-5 surface area values. FTIR showed bands characteristic of the materials and, FTIR-pyridine indicated the presence of strong Brønsted sites on the sulfated material. In the catalytic tests the temperature was the parameter that most influenced the reactions. The best reaction conditions were: 10% catalyst, 100°C temperature and 1:5 m(OA)/m(meOH) for LO, SLO, SLO/HZSM-5 and 10% catalyst, 100°C temperature and 1:20 m(OA)/m(meOH) for HZSM-5. Under these conditions the conversions were: 67% and 96%, for LO and SLO, respectively and 80% and 100%, for HZSM-5 and SLO/HZSM-5, respectively. All catalysts deactivated after the first use, but the deactivation of SLO/HZSM-5 was smaller.

  9. Hydrogen reduction of Ga-Pt loaded HZSM-5

    SciTech Connect

    Price, G.L. )

    1991-08-01

    Catalysts containing 1.2, 3.1, 6.1, and 10.0 g Ga as Ga(NO{sub 3}) per 100 g HZSM-5 prepared by incipient wetness impregnation have been subjected to hydrogen reduction at 848 K in a microbalance and the reduction rates and capacities compared with identical materials further impregnated with 0.5 g Pt as Pt(NH{sub 3}){sub 4} (NO{sub 3}){sub 2} per 100 g HZSM-5. Weight loss stoichiometry suggests that supported Ga(NO{sub 3}){sub 3} is converted to Ga{sub 2}O{sub 3} upon calcination in 3% O{sub 2} in He while weight loss stoichiometry upon hydrogen reduction at 848 K in all cases can be correlated (within certain bounds which are discussed) as Ga{sub 2}O{sub 3} + 2H{sup +}Z{sup {minus}} {yields} 2Ga{sup +}Z{sup {minus}} + 3H{sub 2}O, where Z{sup {minus}} is the anionic zeolitic framework. The addition of Pt does not increase the total amount of Ga{sub 2}O{sub 3} which can be reduced even in cases where the cation capacity of the zeolite limits the reduction reaction but does increase the maximum rate of Ga{sub 2}O{sub 3} reduction.

  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. Catalytic ozonation of bisphenol A in aqueous solution using Mn-Ce/HZSM-5 as catalyst.

    PubMed

    Liu, Yanfang; Zhao, Junna; Li, Zaixing; Li, Guixia; Li, Wei; Gao, Xiang

    2015-01-01

    Mixed manganese and cerium oxide supported on HZSM-5 were synthesized and used as heterogeneous catalysts for ozonation of bisphenol A (BPA) in aqueous solution. The prepared catalysts of Mn-Ce/HZSM-5 were characterized by X-ray diffraction, scanning electron microscopy and Fourier transform-infrared spectroscopy. The results indicated that Mn-Ce/HZSM-5 exhibits extraordinary catalytic activity for the degradation of BPA. Removal of 89.3% of BPA and 90.4% of total organic carbon (TOC) was achieved in 30 min, compared to non-catalytic ozonation, where only 50.5% BPA and 28.1% TOC removal were reached under the same conditions. Adsorption of BPA on HZSM-5 support and Mn-Ce/HZSM-5 catalysts was negligible. The strong inhibition of BPA removal by tert-butyl alcohol indicated that the attack of hydroxyl radicals was responsible for the improvement of catalytic ozonation. It was observed that at neutral pH, which is near the point of zero charge of the catalyst, the catalytic activity reached its maximum. Increasing the amount of Mn-Ce/HZSM-5 catalyst until it exceeded 3 g/L did not show a strong effect on BPA removal. The catalysts showed high stability and reusability.

  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. PMID:24472700

  13. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  15. Local silico-aluminophosphate interfaces within phosphated H-ZSM-5 zeolites.

    PubMed

    van der Bij, Hendrik E; Weckhuysen, Bert M

    2014-06-01

    In order to elucidate phosphorus-zeolite H-ZSM-5 interactions, a variety of phosphorus-modified zeolite H-ZSM-5 materials were studied in a multi-spectroscopic manner. By deploying single pulse (27)Al, (31)P MAS NMR, 2D heteronuclear (27)Al-(31)P correlation (HETCOR), (27)Al MQ MAS NMR spectroscopy, TPD of pyridine monitored by FT-IR spectroscopy, and Scanning Transmission X-ray Microscopy (STXM) the interplay and influence of acidity, thermal treatment and phosphorus on the structure and acidity of H-ZSM-5 were established. It was found that while acid treatment did not affect the zeolite structure, thermal treatment leads to the breaking of Si-OH-Al bonds, a decrease in the strong acid site number and the formation of terminal Al-OH groups. No extra-framework aluminium species was observed. Phosphorus precursors interact with the zeolitic framework through hydrogen bonds and physical coordination, as phosphorus species can be simply washed out with hot water. After phosphatation and thermal treatment two effects occur simultaneously, namely (i) phosphorus species transform into water insoluble condensed poly-phosphoric acid and (ii) phosphoric acid binds irreversibly to the terminal Al-OH groups of partially dislodged four-coordinated framework aluminium, forming local silico-aluminophosphate interfaces. These interfaces are potentially the promoters of hydrothermal stability in phosphated zeolite H-ZSM-5.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  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. Titania-supported bimetallic catalysts combined with HZSM-5 for Fischer-Tropsch synthesis

    SciTech Connect

    Jothimurugesan, K.; Gangwal, S.K.

    1998-04-01

    The Fischer-Tropsch synthesis (FTS) can convert coal or natural gas derived synthesis gas (CO + H{sub 2}) to liquid fuels and high-value chemicals. Fischer-Tropsch synthesis was studied in a fixed-bed reactor over single-metal and bimetallic alloy catalysts, selected from Co, Ni, and Fe, supported on TiO{sub 2} at a total metal loading of 10 wt%. The catalysts, prepared by incipient wetness impregnation using nitrate precursors, were tested as is and in combination with a HZSM-5 zeolite. The test conditions were 1 MPa, 250 C, H{sub 2}/CO = 1, and weight hourly space velocity (WHSV) = 0.77 h{sup {minus}1}. Alloying of metals resulted in a significant enhancement in CO conversion without an increase in methane selectivity. A 50:50 weight ratio Co-Ni catalyst physically mixed with HZSM-5 (5% Co-5% Ni/TiO{sub 2} + HZSM-5) gave the highest CO conversion (45.2%) at the conditions tested. This compares to conversion of 8.9% and 10.5% with Co-only and Ni-only catalysts, respectively. Mixing the Co-Ni catalyst with HZSM-5 resulted in a significant reduction in methane selectivity and a significant increase in C{sub 4}{sup +} selectivity. The aromatic fraction increased from 1.5 to 8.1 wt%, the C{sub 2}{sup +} olefins were nearly eliminated, and i-C{sub 4}H{sub 10} increased from 2.3 to 58.5 wt % in the C{sub 4} fraction.

  19. 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.

  20. 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

  1. 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.

  2. In situ solid-state NMR study of methanol-to-gasoline chemistry in zeolite HZSM-5

    SciTech Connect

    Munson, E.J.; Kheir, A.A.; Lazo, N.D.; Haw, J.F.

    1992-09-17

    This paper uses {sup 13}C solid-state NMR to study the chemistry of a variety of absorbates related to the methanol-to-gasoline process. This study has resulted in a better understanding of the chemical reaction occurring inside the zeolite HZSM-5 used in this process. It is shown that ethylene is the first olefin formed and ethyl methyl ether is also formed during this hydrocarbon synthesis on zeolite HZSM-5.

  3. Hydrogen Production by Low-temperature Steam Reforming of Bio-oil over Ni/HZSM-5 Catalyst

    NASA Astrophysics Data System (ADS)

    Qiu, Song-bai; Gong, Lu; Liu, Lu; Hong, Cheng-gui; Yuan, Li-xia; Li, Quan-xin

    2011-04-01

    We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni20/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 °C, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni20/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.

  4. 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.

  5. 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.

  6. 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.

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

    DOE PAGESBeta

    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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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. PMID:25504857

  13. Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

    PubMed

    Dai, Weili; Wang, Chuanming; Yi, Xianfeng; Zheng, Anmin; Li, Landong; Wu, Guangjun; Guan, Naijia; Xie, Zaiku; Dyballa, Michael; Hunger, Michael

    2015-07-20

    Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia. PMID:26096840

  14. Hexane cracking over steamed phosphated zeolite H-ZSM-5: promotional effect on catalyst performance and stability.

    PubMed

    van der Bij, Hendrik E; Meirer, Florian; Kalirai, Sam; Wang, Jian; Weckhuysen, Bert M

    2014-12-15

    The nature behind the promotional effect of phosphorus on the catalytic performance and hydrothermal stability of zeolite H-ZSM-5 has been studied using a combination of (27) Al and (31) P MAS NMR spectroscopy, soft X-ray absorption tomography and n-hexane catalytic cracking, complemented with NH3 temperature-programmed desorption and N2 physisorption. Phosphated H-ZSM-5 retains more acid sites and catalytic cracking activity after steam treatment than its non-phosphated counterpart, while the selectivity towards propylene is improved. It was established that the stabilization effect is twofold. First, the local framework silico-aluminophosphate (SAPO) interfaces, which form after phosphatation, are not affected by steam and hold aluminum atoms fixed in the zeolite lattice, preserving the pore structure of zeolite H-ZSM-5. Second, the four-coordinate framework aluminum can be forced into a reversible sixfold coordination by phosphate. These species remain stationary in the framework under hydrothermal conditions as well. Removal of physically coordinated phosphate after steam-treatment leads to an increase in the number of strong acid sites and increased catalytic activity. We propose that the improved selectivity towards propylene during catalytic cracking can be attributed to local SAPO interfaces located at channel intersections, where they act as impediments in the formation of bulky carbenium ions and therefore suppress the bimolecular cracking mechanism.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Predicting adsorption enthalpies on silicalite and HZSM-5: A benchmark study on DFT strategies addressing dispersion interactions.

    PubMed

    Chiu, Cheng-chau; Vayssilov, Georgi N; Genest, Alexander; Borgna, Armando; Rösch, Notker

    2014-04-15

    We evaluated the accuracy of periodic density functional calculations for adsorption enthalpies of water, alkanes, and alcohols in silicalite and HZSM-5 zeolites using a gradient-corrected density functional with empirical dispersion corrections (PBE-D) as well as a nonlocal correlation functional (vdW-DF2). Results of both approaches agree in acceptable fashion with experimental adsorption energies of alcohols in silicalite, but the adsorption energies for n-alkanes in both zeolite models are overestimated, by 21-46 kJ mol(-1). For PBE-D calculations, the adsorption of alkanes is exclusively determined by the empirical dispersion term, while the generalized gradient approximation-DFT part is purely repulsive, preventing the molecule to come too close to the zeolite walls. The vdW-DF2 results are comparable to those of PBE-D calculations, but the latter values are slightly closer to the experiment in most cases. Thus, both computational approaches are unable to reproduce available experimental adsorption energies of alkanes in silicalite and HZSM-5 zeolite with chemical accuracy. PMID:24550154

  1. 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. PMID:22858493

  2. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  4. 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. PMID:26773959

  5. 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.

  6. 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.

  7. 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%. PMID:27065226

  8. Structures and reaction mechanisms of glycerol dehydration over H-ZSM-5 zeolite: a density functional theory study.

    PubMed

    Kongpatpanich, Kanokwan; Nanok, Tanin; Boekfa, Bundet; Probst, Michael; Limtrakul, Jumras

    2011-04-14

    The initial stage of glycerol conversion over H-ZSM-5 zeolite has been investigated using density functional theory (DFT) calculations on an embedded cluster model consisting of 128 tetrahedrally coordinated atoms. It is found that glycerol dehydration to acrolein and acetol proceeds favourably via a stepwise mechanism. The formation of an alkoxide species upon the first dehydration requires the highest activation energy (42.5 kcal mol(-1)) and can be considered as the rate determining step of the reaction. The intrinsic activation energies for the first dehydration are virtually the same for both acrolein and acetol formation, respectively, suggesting the competitive removal of the primary and secondary OH groups. A high selectivity to acrolein at moderate temperatures can be attributed to the selective activation of the stronger adsorption mode of glycerol through the secondary OH group and the kinetically favoured subsequent consecutive steps. In addition, the less reactive nature of acrolein relative to acetol precludes it from being converted to other products upon conversion to glycerol. In accordance with typical endothermic reactions, the forward rate constant for glycerol dehydration significantly increases with increasing reaction temperature. PMID:21369602

  9. Reactive molecular simulations of protonation of water clusters and depletion of acidity in H-ZSM-5 zeolite.

    PubMed

    Joshi, Kaushik L; Psofogiannakis, George; van Duin, Adri C T; Raman, Sumathy

    2014-09-14

    Using reactive molecular dynamics (RMD), we present an atomistic insight into the interaction between water molecules and acidic centers of H-ZSM-5 zeolite. The reactive force field method, ReaxFF, was used to evaluate the adsorption and diffusion of water as well as to study the protonation of water molecules inside zeolite channels. The existing Si/Al/O/H parameters were refitted against DFT calculations to improve the ReaxFF description of interaction between water molecules and the acidic sites of zeolites. The diffusion coefficient of water in the zeolite obtained from refitted parameters is in excellent agreement with experimental results. The molecular dynamics (MD) simulations indicate that protonation of water molecules and acidity of the zeolite catalyst depend on water loadings and temperature and the observed trends compare favorably with existing experimental and theoretical studies. At higher water loadings, protonation of water molecules is more frequent leading to formation and growth of protonated water clusters inside zeolite channels. From the analysis of various reaction channels that were observed during the simulations, we found that such water clusters have relatively short life due to frequent interchange of protons and water molecules among the water clusters. Such proton hopping events play a key role in moving the protons between different acidic centers of zeolite. These simulations show the capability of ReaxFF in providing atomistic details of complex chemical interactions between the water phase and solid acid zeolites.

  10. 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

  11. 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

    2016-01-01

    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

  12. Microwave-assisted catalytic fast pyrolysis of biomass for bio-oil production using chemical vapor deposition modified HZSM-5 catalyst.

    PubMed

    Zhang, Bo; Zhong, Zhaoping; Chen, Paul; Ruan, Roger

    2015-12-01

    Chemical vapor deposition with tetra-ethyl-orthosilicate as the modifier was applied to deposit the external acid sites of HZSM-5, and the modified HZSM-5 samples were used for the microwave-assisted catalytic fast pyrolysis (MACFP) of biomass for bio-oil production. The experimental results showed that the external acid sites of HZSM-5 decreased significantly when SiO2 deposited amount increased from 0% to 5.9%. For product distribution, the coke yield decreased, the oil fraction yield decreased at first and then increased, and the yields of water and gas first increased and then decreased over the range of SiO2 deposited amount studied. For chemical compositions in oil fraction, the relative contents of aliphatic hydrocarbons, aromatic hydrocarbons and oxygen-containing aromatic compounds first increased to maximum values and then decreased, while the relative content of oxygen-containing aliphatic compounds first decreased and then increased with increasing SiO2 deposited amount. PMID:26318925

  13. 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). PMID:27209452

  14. 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.

  15. 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.

  16. Insight into the formation of the tert-butyl cation confined inside H-ZSM-5 zeolite from NMR spectroscopy and DFT calculations.

    PubMed

    Huang, Mengdi; Wang, Qiang; Yi, Xianfeng; Chu, Yueying; Dai, Weili; Li, Landong; Zheng, Anmin; Deng, Feng

    2016-08-23

    Solid-state NMR experiments and DFT calculations have been carried out to determine the complex structures of coadsorbed (13)C-labeled tert-butanol and NH3 in acidic H-ZSM-5 zeolite. It is found, besides the physically adsorbed tert-butanol/NH4(+) complex on Brønsted acid sites, the tert-butylamine cation is formed as well, confirming the presence of the tert-butyl cation confined in zeolite channels. Furthermore, (13)C-(27)Al double-resonance solid-state NMR spectroscopy is adopted to determine the host/guest interaction between the carbocation and the zeolite framework. PMID:27400892

  17. 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. PMID:27372139

  18. 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.

  19. 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.

  20. 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

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

    2015-11-23

    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.

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

    PubMed

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

    2016-05-14

    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.

  2. 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

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

    2015-11-23

    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

  3. 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

  4. 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

  5. Preparation, characterization and application of nanosized CuO/HZSM-5 as an efficient and heterogeneous catalyst for the N-formylation of amines at room temperature.

    PubMed

    Tajbakhsh, Mahmood; Alinezhad, Heshmatollah; Nasrollahzadeh, Mahmoud; Kamali, Taghi A

    2016-06-01

    An efficient and new method for the synthesis of formamides using HZSM-5 zeolite supported copper oxide nanoparticles as an efficient and heterogeneous catalyst is reported. The catalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS), Brunauer-Emmett-Teller (BET), energy dispersive X-ray spectroscopy (EDS), temperature programmed desorption of ammonia (TPD-NH3) and Fourier transformed infrared spectroscopy (FT-IR). This method has the advantages of eliminating homogeneous catalysts and provides simple methodology with easy work up. Excellent yields of the corresponding formamides were obtained through this cost-effective protocol under solvent-free conditions with shorter reaction time. The catalyst was easily isolated from the reaction mixture by filtration and reused several times without significant loss in its catalytic. PMID:26971067

  6. Preparation, characterization and application of nanosized CuO/HZSM-5 as an efficient and heterogeneous catalyst for the N-formylation of amines at room temperature.

    PubMed

    Tajbakhsh, Mahmood; Alinezhad, Heshmatollah; Nasrollahzadeh, Mahmoud; Kamali, Taghi A

    2016-06-01

    An efficient and new method for the synthesis of formamides using HZSM-5 zeolite supported copper oxide nanoparticles as an efficient and heterogeneous catalyst is reported. The catalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS), Brunauer-Emmett-Teller (BET), energy dispersive X-ray spectroscopy (EDS), temperature programmed desorption of ammonia (TPD-NH3) and Fourier transformed infrared spectroscopy (FT-IR). This method has the advantages of eliminating homogeneous catalysts and provides simple methodology with easy work up. Excellent yields of the corresponding formamides were obtained through this cost-effective protocol under solvent-free conditions with shorter reaction time. The catalyst was easily isolated from the reaction mixture by filtration and reused several times without significant loss in its catalytic.

  7. Beckmann rearrangement of 15N-cyclohexanone oxime on zeolites silicalite-1, H-ZSM-5, and H-[B]ZSM-5 studied by solid-state NMR spectroscopy.

    PubMed

    Marthala, V R Reddy; Jiang, Yijiao; Huang, Jun; Wang, Wei; Gläser, Roger; Hunger, Michael

    2006-11-22

    By means of solid-state 15N NMR spectroscopy, evidence for the formation of nitrilium ions as intermediates of the Beckmann rearrangement of 15N-cyclohexanone oxime to epsilon-caprolactam on silicalite-1, H-ZSM-5, and H-[B]ZSM-5 is reported. The zeolites under study are characterized by different acid strengths (silicalite-1 < H-[B]ZSM-5 < H-ZSM-5). Depending on the nature of catalytically active surface OH groups, reactant and product molecules exist in the nonprotonated or protonated state. In addition, formation of byproducts such as 5-cyano-1-pentene and epsilon-aminocapric acid as a result of dehydration and hydrolysis of the reactant and product molecules, respectively, were observed.

  8. The influence of chemisorbed molecules on mass transfer in H-ZSM-5-type zeolites and the location of Broensted acid sites

    SciTech Connect

    Caro, J.; Buelow, M. ); Kaerger, J.; Pfeifer, H. )

    1988-11-01

    Heterogeneous catalysis is one of the most important applications of zeolites. Therefore, various methods have been developed to determine the strength and concentration of Bronsted acid sites in zeolites. Among them, in the last few years, {sup 1}H MAS NMR has become a powerful tool. In addition to the accessibility of the acid sites probed by chemisorption of N-bases, the steric environment of these catalytically active sites is of importance since it imposes constraints on the geometry of the transition state. However, only a few studies have been reported on this topic. Information was obtained from quantum chemical calculations, catalytic experiments, I.R. spectroscopy, and the arrangement of guest molecules. From these investigations it has been concluded that in H-ZSM-5 the channel intersections should be preferential location centers for the Bronsted acid sites. In adsorption technology, in the use of zeolites as shape-selective adsorbents, modification of the molecular sieve properties by chemisorption of nitrogen-containing bases (N-compounds) has become a common technique. The authors have applied the NMR pulsed field gradient technique to study the influence of chemisorbed N-compounds on transport properties of molecular sieves, considering the chemisorbed compounds as transport obstacles.

  9. Catalytic conversion of canola oil over potassium-impregnated HZSM-5 catalysts: C{sub 2}-C{sub 4} olefin production and model reaction studies

    SciTech Connect

    Katikaneni, S.P.R.; Adjaye, J.D.; Idem, R.O.; Bakhshi, N.N.

    1996-10-01

    The influence of catalyst acidity, reaction temperature, and canola oil space velocity on the conversion of canola oil was evaluated using a fixed-bed microreactor at atmospheric pressure at reaction temperatures and space velocities (WHSV) in the ranges 400--500 C and 1.8--3.6 h{sup {minus}1}, respectively, over potassium-impregnated HZSMs-5 catalysts. These catalysts were thoroughly characterized using XRD, N{sub 2} adsorption measurements, {sup 1}H NMR, TPD of NH{sub 3}, FT-IR, C{sub 2}-C{sub 4} olefins from canola oil were determined. The incorporation of potassium into HZSM-5 catalyst resulted in both the dilution and poisoning of Bronsted and total acid sites. These acidity changes only severely affected the acid catalyzed reactions, such as oligomerization and aromatization, and resulted in drastic modifications in product distribution. The maximum C{sub 2}C{sub 4} olefin yield of 25.8 wt % was obtained at 500 C and 1.8 h{sup {minus}1} space velocity with catalyst K1 of relatively low Bronsted and total acidity.

  10. Correlation of zeolite ZSM-5 acid strength with catalytic activity and selectivity. Final report. [Cobalt and cobalt/thorium impregnated H-ZSM-5

    SciTech Connect

    Hayhurst, D.T.

    1984-04-01

    Isosteric heats of ammonia adsorption were determined for several cobalt and cobalt/thorium impregnated H-ZSM-5. Samples were impregnated to the 3, 6 and 9 wt % levels using an incipient wetness technique and either acetone or water for dissolving the metal nitrate salt. The metal impregnation resulted in a lowering of the maximum heat of ammonia adsorption and in a corresponding lowering of the maximum acid site strength. The ammonia adsorption capacity and adsorption heat was unaltered by a reduction of the metal-impregnated samples in hydrogen, indicating that the incipient wetness method leads to cobalt which was most likely ion-exchanged into the zeolite rather than impregnated into the sieve in a reducable form. In addition, the impregnated cobalt caused a slight steric hinderance to the diffusion of n-butane into the metal-loaded zeolite. The use of either water or acetone for dissolving the metal nitrate salt altered the acid-strength distribution. Water was found to lower the acid-site strength to a greater degree than the acetone. 11 references, 8 figures.

  11. 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.

  12. Mesoporous aluminosilicates with ordered hexagonal structure, strong acidity, and extraordinary hydrothermal stability at high temperatures.

    PubMed

    Zhang, Z; Han, Y; Xiao, F S; Qiu, S; Zhu, L; Wang, R; Yu, Y; Zhang, Z; Zou, B; Wang, Y; Sun, H; Zhao, D; Wei, Y

    2001-05-30

    Highly ordered hexagonal mesoporous aluminosilicates (MAS-5) with uniform pore sizes have been successfully synthesized from assembly of preformed aluminosilcate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. The aluminosilicate precursors were obtained by heating, at 100--140 degrees C for 2--10 h, aluminasilica gels at the Al(2)O(3)/SiO(2)/TEAOH/H(2)O molar ratios of 1.0/7.0--350/10.0--33.0/500--2000. Mesoporous MAS-5 shows extraordinary stability both in boiling water (over 300 h) and in steam (800 degrees C for 2 h). Temperature-programmed desorption of ammonia shows that the acidic strength of MAS-5 is much higher than that of MCM-41 and is comparable to that of microporous Beta zeolite. In catalytic cracking of 1,3,5-triisopropylbenzene and alkylation of isobutane with butene, MAS-5 exhibits greater catalytic activity and selectivity, as compared with MCM-41 and HZSM-5. The MAS-5 samples were characterized with infrared, UV--Raman, and NMR spectroscopy and numerous other techniques. The results suggest that MAS-5 consists of both mesopores and micropores and that the pore walls of MAS-5 contain primary and secondary structural building units, similar to those of microporous zeolites. Such unique structural features might be responsible for the observed strong acidity and high thermal stability of the mesoporous aluminosilicates with well-ordered hexagonal symmetry.

  13. New insight into the hydrocarbon-pool chemistry of the methanol-to-olefins conversion over zeolite H-ZSM-5 from GC-MS, solid-state NMR spectroscopy, and DFT calculations.

    PubMed

    Wang, Chao; Chu, Yueying; Zheng, Anmin; Xu, Jun; Wang, Qiang; Gao, Pan; Qi, Guodong; Gong, Yanjun; Deng, Feng

    2014-09-22

    Over zeolite H-ZSM-5, the aromatics-based hydrocarbon-pool mechanism of methanol-to-olefins (MTO) reaction was studied by GC-MS, solid-state NMR spectroscopy, and theoretical calculations. Isotopic-labeling experimental results demonstrated that polymethylbenzenes (MBs) are intimately correlated with the formation of olefin products in the initial stage. More importantly, three types of cyclopentenyl cations (1,3-dimethylcyclopentenyl, 1,2,3-trimethylcyclopentenyl, and 1,3,4-trimethylcyclopentenyl cations) and a pentamethylbenzenium ion were for the first time identified by solid-state NMR spectroscopy and DFT calculations under both co-feeding ([(13) C6 ]benzene and methanol) conditions and typical MTO working (feeding [(13) C]methanol alone) conditions. The comparable reactivity of the MBs (from xylene to tetramethylbenzene) and the carbocations (trimethylcyclopentenyl and pentamethylbenzium ions) in the MTO reaction was revealed by (13) C-labeling experiments, evidencing that they work together through a paring mechanism to produce propene. The paring route in a full aromatics-based catalytic cycle was also supported by theoretical DFT calculations.

  14. 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.

  15. 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.

  16. Mesoporous siliconiobium phosphate as a pure Brønsted acid catalyst with excellent performance for the dehydration of glycerol to acrolein.

    PubMed

    Choi, Youngbo; Park, Dae Sung; Yun, Hyeong Jin; Baek, Jayeon; Yun, Danim; Yi, Jongheop

    2012-12-01

    The development of solid acid catalysts that contain a high density of Brønsted acid sites with suitable acidity, as well as a long lifetime, is one of great challenges for the efficient dehydration of glycerol to acrolein. Herein, we report on a mesoporous siliconiobium phosphate (NbPSi-0.5) composite, which is a promising solid Brønsted acid that is a potential candidate for such a high-performance catalyst. A variety of characterization results confirm that NbPSi-0.5 contains nearly pure Brønsted acid sites and has well-defined large mesopores. In addition, NbPSi-0.5 contains a similar amount of acid sites and exhibits weaker acidity than that of the highly acidic niobium phosphate and HZSM-5 zeolite. NbPSi-0.5 is quite stable and has a high activity for the dehydration of glycerol. The stability of NbPSi-0.5 is about three times higher than that of the reported catalyst. The significantly enhanced catalytic performance of NbPSi-0.5 can be attributed to 1) nearly pure Brønsted acidity, which suppresses side reactions that lead to coke formation; 2) a significant reduction of pore blocking due to the mesopores; and 3) a decrease in the amount and oxidation temperature of coke.

  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. 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.

  19. 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.

  20. Transversal spin freezing and re-entrant spin glass phases in chemically disordered Fe-containing perovskite multiferroics.

    PubMed

    Stephanovich, V A; Laguta, V V

    2016-03-14

    We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-containing perovskite multiferroics like PbFe1/2Nb1/2O3 and PbFe1/2Ta1/2O3. The theoretical part is based on our model of coexistence of the long-range magnetic order and spin glass in the above compounds. In our model, the exchange interaction is anisotropic, coupling antiferromagnetically z spin components of Fe(3+) ions. At the same time, the xy components are coupled by much weaker exchange interaction of ferromagnetic sign. In the system with spatial disorder (half of the corresponding lattice sites are occupied by spinless Nb(5+) ions) such frustrating interaction results in the fact that the antiferromagnetic order is formed by the z projection of the spins, while their xy components contribute to spin glass behaviour. Our theoretical findings are supported by the experimental evidence of such a coexistence of antiferromagnetic and spin glass phases in chemically disordered Fe-containing complex perovskite multiferroics. PMID:26890550

  1. 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.

  2. 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.

  3. 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.

  4. Mesoporous aluminum phosphite

    SciTech Connect

    El Haskouri, Jamal; Perez-Cabero, Monica; Guillem, Carmen; Latorre, Julio; Beltran, Aurelio; Beltran, Daniel; Amoros, Pedro

    2009-08-15

    High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S{sup +}I{sup -} surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acidic properties of the final materials. While phosphate groups in ALPO act as network building blocks (bridging Al atoms), the phosphite entities become basically attached to the pore surface, what gives practically empty channels. The mesoporous nature of the final materials is confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and N{sub 2} adsorption-desorption isotherms. The materials present regular unimodal pore systems whose order decreases as the phosphite content increases. NMR spectroscopic results confirm the incorporation of oxo-phosphorus entities to the framework of these materials and also provide us useful information concerning the mechanism through which they are formed. - Abstract: TEM image of the mesoporous aluminum phosphite showing the hexagonal disordered pore array that is generated by using surfactant micelles as template. Also a scheme emphasizing the presence of an alumina-rich core and an ALPO-like pore surface is presented.

  5. 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.

  6. Carbocation Stability in H-ZSM5 at High Temperature.

    PubMed

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

    2015-11-19

    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 tert-butyl 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. PMID:26501585

  7. Controlled synthesis of mixed-valent Fe-containing metal organic frameworks for the degradation of phenol under mild conditions.

    PubMed

    Sun, Qiao; Liu, Min; Li, Keyan; Han, Yitong; Zuo, Yi; Wang, Junhu; Song, Chunshan; Zhang, Guoliang; Guo, Xinwen

    2016-05-10

    A series of MIL-53(Fe)-type materials, Fe(BDC)(DMF,F), were prepared by using different ratios of n(FeCl3)/n(FeCl2), which have varied amounts of Fe(2+) in their frameworks. From FeCl3 to FeCl2, the structures of the synthesized samples transform from MIL-53(Fe) to Fe(BDC)(DMF,F). Along with this structure transformation, the crystal morphology goes through a striking change from a small irregular shape to a big triangular prism. This phenomenon indicates that the addition of FeCl2 is beneficial for the formation of a Fe(BDC)(DMF,F) structure. The catalytic activity of these iron-containing MOFs was tested in phenol degradation with hydrogen peroxide as an oxidant at near neutral pH and 35 °C. The degradation efficiency of these samples increases gradually from MIL-53(Fe) to Fe(BDC)(DMF,F). (57)Fe Mössbauer spectra reveal that Fe(2+) and Fe(3+) coexist in the Fe(BDC)(DMF,F) framework, and the highest amount of Fe(2+) in the sample prepared with mixed FeCl3 and FeCl2 is 26.0%. The result illustrates that the amount of Fe(2+) in the samples can be controlled using varied n(FeCl3)/n(FeCl2) in the feed. The diverse amount of Fe(2+) in this series of FeMOF materials exactly explains the distinction of reaction efficiency. The iron leaching tests, structures of the fresh and used catalysts, and the data of the recycling runs show that the Fe-containing MOFs are stable in this liquid-phase reaction. PMID:26862863

  8. Mesoporous materials for antihydrogen production.

    PubMed

    Consolati, Giovanni; Ferragut, Rafael; Galarneau, Anne; Di Renzo, Francesco; Quasso, Fiorenza

    2013-05-01

    Antimatter is barely known by the chemist community and this article has the vocation to explain how antimatter, in particular antihydrogen, can be obtained, as well as to show how mesoporous materials could be used as a further improvement for the production of antimatter at very low temperatures (below 1 K). The first experiments with mesoporous materials highlighted in this review show very promising and exciting results. Mesoporous materials such as mesoporous silicon, mesoporous material films, pellets of MCM-41 and silica aerogel show remarkable features for antihydrogen formation. Yet, the characteristics for the best future mesoporous materials (e.g. pore sizes, pore connectivity, shape, surface chemistry) remain to be clearly identified. For now among the best candidates are pellets of MCM-41 and aerogel with pore sizes between 10 and 30 nm, possessing hydrophobic patches on their surface to avoid ice formation at low temperature. From a fundamental standpoint, antimatter experiments could help to shed light on open issues, such as the apparent asymmetry between matter and antimatter in our universe and the gravitational behaviour of antimatter. To this purpose, basic studies on antimatter are necessary and a convenient production of antimatter is required. It is exactly where mesoporous materials could be very useful.

  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.

  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. 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).

  14. Bimodal mesoporous silica with bottleneck pores.

    PubMed

    Reber, M J; Brühwiler, D

    2015-11-01

    Bimodal mesoporous silica consisting of two sets of well-defined mesopores is synthesized by a partial pseudomorphic transformation of an ordered mesoporous starting material (SBA-15 type). The introduction of a second set of smaller mesopores (MCM-41 type) establishes a pore system with bottlenecks that restricts the access to the core of the bimodal mesoporous silica particles. The particle size and shape of the starting material are retained, but micropores present in the starting material disappear during the transformation, leading to a true bimodal mesoporous product. A varying degree of transformation allows the adjustment of the pore volume contribution of the two mesopore domains. Information on the accessibility of the mesopores is obtained by the adsorption of fluorescence-labeled poly(amidoamine) dendrimers and imaging by confocal laser scanning microscopy. This information is correlated with nitrogen sorption data to provide insights regarding the spatial distribution of the two mesopore domains. The bimodal mesoporous materials are excellent model systems for the investigation of cavitation effects in nitrogen desorption isotherms. PMID:26399172

  15. Magnetic mesoporous material for the sequestration of algae

    SciTech Connect

    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. Dealloying of mesoporous PtCu alloy film for the synthesis of mesoporous Pt films with high electrocatalytic activity.

    PubMed

    Li, Cuiling; Malgras, Victor; Aldalbahi, Ali; Yamauchi, Yusuke

    2015-02-01

    Mesoporous Pt film with highly electrocatalytic activity is successfully synthesized by dealloying of mesoporous PtCu alloy film prepared through electrochemical micelle assembly. The resulting mesoporous electrode exhibits high current density and superior stability toward the methanol oxidation reaction.

  17. 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.

  18. Mesoporous Silica: A Suitable Adsorbent for Amines

    PubMed Central

    2009-01-01

    Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices. PMID:20628459

  19. 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

  20. Magnetic Mesoporous Photonic Cellulose Films.

    PubMed

    Giese, Michael; Blusch, Lina K; Schlesinger, Maik; Meseck, Georg R; Hamad, Wadood Y; Arjmand, Mohammad; Sundararaj, Uttandaraman; MacLachlan, Mark J

    2016-09-13

    Novel hybrid materials of cellulose and magnetic nanoparticles (NPs) were synthesized and characterized. The materials combine the chiral nematic structural features of mesoporous photonic cellulose (MPC) with the magnetic properties of cobalt ferrite (CoFe2O4). The photonic, magnetic, and dielectric properties of the hybrid materials were investigated during the dynamic swelling and deswelling of the MPC films. It was observed that the dielectric properties of the generated MPC films increased tremendously following swelling in water, endorsing efficient swelling ability of the generated mesoporous films. The high magnetic permeability of the developed MPC films in conjunction with their superior dielectric properties, predominantly in the swollen state, makes them interesting for electromagnetic interference shielding applications. PMID:27588561

  1. 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.

  2. Ultrastable Mesoporous Aluminosilicates by Grafting Routes.

    PubMed

    Mokaya

    1999-10-01

    A combination of postsynthesis grafting and hydrothermal treatment offers an excellent route for the synthesis of ultrastable mesoporous aluminosilicates with enhanced acidity and catalytic activity. The stability observed (>150 h in boiling water; 4 h at 1000 degrees C) is, for mesoporous silicates, remarkable. Unusually the hydrothermal treatment is beneficial with respect to the use of the stable aluminosilicates as solid acid catalysts.

  3. 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.

  4. 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.

  5. Ecodesign of ordered mesoporous silica materials.

    PubMed

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

    2013-05-01

    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. PMID:23407854

  6. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGESBeta

    Luo, Hongmei; Lin, Qianglu; Baber, Stacy; Naalla, Mahesh

    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

  7. 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.

  8. 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.

  9. Mesoporous Carbon Membranes for Selective Gas Separations

    SciTech Connect

    2009-04-01

    This factsheet describes a study whose focus is on translating a novel class of material developed at Oak Ridge National Laboratory—selfassembled mesoporous carbon—into robust, efficient membrane systems for selective industrial gas separations.

  10. 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

    2015-12-01

    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.

  11. 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

  12. 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.

  13. A simple synthesis of mesoporous carbons with tunable mesopores using a colloidal template-mediated vapor deposition polymerization.

    PubMed

    Jang, Jyongsik; Lim, Byungkwon; Choi, Moonjung

    2005-09-01

    Mesoporous carbons with highly uniform and tunable mesopores were fabricated by one-step vapor deposition polymerization (VDP) using colloidal silica particles as templates and polyacrylonitrile (PAN) as a carbon precursor. PMID:16100607

  14. A functional mesoporous ionic crystal based on polyoxometalate.

    PubMed

    Kawahara, Ryosuke; Niinomi, Kazuma; Kondo, Junko N; Hibino, Mitsuhiro; Mizuno, Noritaka; Uchida, Sayaka

    2016-02-21

    A mesoporous ionic crystal is synthesized with a polyoxometalate and a macrocation with polar cyano groups. The compound possesses one-dimensional mesopores with an opening of 3.0 × 2.0 nm. The compound shows high proton conductivity and catalytic activity, which are due to the water molecules in the mesopores. PMID:26804446

  15. 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.

  16. 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.

  17. Carbon Nanotube Synthesis Using Mesoporous Silica Templates

    SciTech Connect

    Zheng, Feng; Liang, Liang; Gao, Yufei; Sukamto, Johanes H.; Aardahl, Chris L.

    2002-07-01

    Well-aligned carbon nanotubes (CNTs) were grown on mesoporous silica films by chemical vapor deposition (CVD). Ethylene was used as the carbon source and CVD was performed at 1023 K and atmospheric pressure. The films were doped with Fe during gelation, and three different structure directing agents were used for mesoporous silica synthesis: polyoxyethylene (10) cetyl ether (C16EO10), Pluronic tri-block copolymer (P123), and cetyltriethylammonium chloride (CTAC). A high degree of CNT alignment on C16EO10-mesoporous silica films was produced at Fe:Si molar ratio of 1.80. Similar alignment of CNTs was achieved on the other two types of films but on CTAC-mesoporous silica films, CNTs only grew parallel to the substrate surface from the cracks in the films because of the in-plane arrangement of the mesopores in such films. Considerable progress has been made in producing multi-walled carbon nanotubes (CNTs) by catalytic CVD techniques. If CNTs are to be integrated into certain useful devices, it is critical to be able to grow highly aligned arrays of CNTs with narrow size distribution and at specific locations on a substrate. Long-range alignment normal to the substrate results from steric crowding if the initial catalyst sites are sufficiently dense. Alignment may be improved with better control of the density of catalytic sites by means of a template of appropriate pore structure. The confinement of CNTs by the pores during the initial growth may also help align CNTs.

  18. 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.

  19. 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. PMID:26549760

  20. 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.

  1. A Single-Crystalline Mesoporous Quartz Superlattice.

    PubMed

    Matsuno, Takamichi; Kuroda, Yoshiyuki; Kitahara, Masaki; Shimojima, Atsushi; Wada, Hiroaki; Kuroda, Kazuyuki

    2016-05-10

    There has been significant interest in the crystallization of nanostructured silica into α-quartz because of its physicochemical properties. We demonstrate a single-crystalline mesoporous quartz superlattice, a silica polymorph with unprecedentedly ordered hierarchical structures on both the several tens of nanometers scale and the atomic one. The mesoporous quartz superlattice consists of periodically arranged α-quartz nanospheres whose crystalline axes are mostly oriented in an assembly. The superlattice is prepared by thermal crystallization of amorphous silica nanospheres constituting a colloidal crystal. We found that the deposition of a strong flux of Li(+) only on the surface of silica nanospheres is effective for crystallization.

  2. 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.

  3. Ordered mesoporous alumina-supported metal oxides.

    PubMed

    Morris, Stacy M; Fulvio, Pasquale F; Jaroniec, Mietek

    2008-11-12

    The one-pot synthesis of alumina-supported metal oxides via self-assembly of a metal precursor and aluminum isopropoxide in the presence of triblock copolymer (as a structure directing agent) is described in detail for nickel oxide. The resulting mesoporous mixed metal oxides possess p6 mm hexagonal symmetry, well-developed mesoporosity, relatively high BET surface area, large pore widths, and crystalline pore walls. In comparison to pure alumina, nickel aluminum oxide samples exhibited larger mesopores and improved thermal stability. Also, long-range ordering of the aforementioned samples was observed for nickel molar percentages as high as 20%. The generality of the recipe used for the synthesis of mesoporous nickel aluminum oxide was demonstrated by preparation of other alumina-supported metal oxides such as MgO, CaO, TiO 2, and Cr 2O 3. This method represents an important step toward the facile and reproducible synthesis of ordered mesoporous alumina-supported materials for various applications where large and accessible pores with high loading of catalytically active metal oxides are needed.

  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

    2015-12-01

    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.

  5. Mesoporous metal and semiconductor nanowires and nanotubes

    NASA Astrophysics Data System (ADS)

    Luo, Hongmei

    Nanowires and nanotubes are central elements in nanoscience and nanotechnology for applications such as nanoelectronic devices, chemical sensors, and high-density data storage. Among various synthesis methods, the template assisted electrodeposition is particularly attractive because it provides an efficient route to fabricate arrays of nanomatenals of desired composition, size, and aspect ratio. Advanced applications need morphological control. Mesoporous materials with uniform and arranged pores with pore diameters between 2 and 50 nm have attracted much attention due to their unique structures and applications. This dissertation presents the fabrication, structure, and property investigation of magnetic, superconducting metal, and semiconductor nanostructures. We will report three-dimensional (3D) macroporous magnetic and superconducting metal films using opal templates, 2D hexagonal and 3D cubic metal nanowire thin films with tunable 3-10 nm wire diameters using mesoporous silica as templates, mesoporous cobalt and nickel films with hexagonal and lamellar structures direct templated by lyotropic liquid crystal phases. Compared with bulk and dense films, the porous magnetic films show higher coercivities. The cobalt nanowire thin films exhibit enhanced coercivities and controllable magnetic anisotropy through tuning the mesostructure and dimension of the nanowires. We will present a novel method, confined-assembly-template assisted (CATA) electrodeposition, by combination of nanoconfinement, supramolecular templating and electrodeposition technique to prepare mesoporous metal and semiconductor nanowires and nanotubes. Mesoporous palladium and cobalt nanowires are obtained by electrodeposition of hexagonal liquid crystal in porous membranes, mesoporous platinum and nickel nanotubes with controlled length are obtained by electrodeposition of lamellar liquid crystal, mesoporous zinc oxide nanowires are obtained by electrodeposition of interfacial SDS surfactant

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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),...

  7. The catalytic cracking of hydrocarbons: paraffins in the HZSM-5 zeolite.

    PubMed

    Magadán, J M; Mercado, S M; Santamaria, R

    2001-11-19

    An elementary reaction during cracking of a hydrocarbon in a nanoporous silicalite catalyst includes ejection of a hydrid ion as shown in the picture. The reaction was simulated by means of quantum molecular dynamics.

  8. Insights into the Reaction Mechanism of Ethanol Conversion into Hydrocarbons on H-ZSM-5.

    PubMed

    Van der Borght, Kristof; Batchu, Rakesh; Galvita, Vladimir V; Alexopoulos, Konstantinos; Reyniers, Marie-Françoise; Thybaut, Joris W; Marin, Guy B

    2016-10-01

    Ethanol dehydration to ethene is mechanistically decoupled from the production of higher hydrocarbons due to complete surface coverage by adsorbed ethanol and diethyl ether (DEE). The production of C3+ hydrocarbons was found to be unaffected by water present in the reaction mixture. Three routes for the production of C3+ hydrocarbons are identified: the dimerization of ethene to butene and two routes involving two different types of surface species categorized as aliphatic and aromatic. Evidence for the different types of species involved in the production of higher hydrocarbons is obtained via isotopic labeling, continuous flow and transient experiments complemented by UV/Vis characterization of the catalyst and ab initio microkinetic modeling.

  9. 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.

  10. 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.

  11. Mesoporous Molecular Sieves as Supports for Metathesis Catalysts

    NASA Astrophysics Data System (ADS)

    Balcar, Hynek; Cejka, Jirí

    Mesoporous molecular sieves represent a new family of inorganic oxides with regular nanostructure, large surface areas, large void volumes, and narrow pore size distribution of mesopores. These materials offer new possibilities for designing highly active and selective catalysts for olefin metathesis and metathesis polymerization. Siliceous sieves MCM-41, MCM-48, SBA-15, and organized mesoporous alumina (OMA) were used as supports for preparation of new molybdenum and rhenium oxide catalysts, as well as for heterogenization of well-defined homogeneous catalysts.

  12. Mesoporous carbon/zirconia composites: a potential route to chemically functionalized electrically-conductive mesoporous materials.

    PubMed

    Oh, Jung-Min; Kumbhar, Amar S; Geiculescu, Olt; Creager, Stephen E

    2012-02-14

    Mesoporous nanocomposite materials in which nanoscale zirconia (ZrO(2)) particles are embedded in the carbon skeleton of a templated mesoporous carbon matrix were prepared, and the embedded zirconia sites were used to accomplish chemical functionalization of the interior surfaces of mesopores. These nanocomposite materials offer a unique combination of high porosity (e.g., ∼84% void space), electrical conductivity, and surface tailorability. The ZrO(2)/carbon nanocomposites were characterized by thermogravimetric analysis, nitrogen-adsorption porosimetry, helium pychnometry, powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Comparison was made with templated mesoporous carbon samples prepared without addition of ZrO(2). Treatment of the nanocomposites with phenylphosphonic acid was undertaken and shown to result in robust binding of the phosphonic acid to the surface of ZrO(2) particles. Incorporation of nanoscale ZrO(2) surfaces in the mesoporous composite skeleton offers unique promise as a means for anchoring organophosphonates inside of pores through formation of robust covalent Zr-O-P bonds. PMID:22248432

  13. Photodegradation of Orange II by mesoporous TiO2.

    PubMed

    Kuang, Liyuan; Zhao, Yaping; Liu, Lu

    2011-09-01

    Mesoporous TiO(2) microspheres were prepared by a hydrothermal reaction and are characterized in this paper. Decoloration and mineralization during photodegradation of Orange II by mesoporous TiO(2) at different pH values, formation of sulfate, relative luminosity to luminous bacteria and recycling experiments of the catalyst were studied. The FTIR results further suggested that the novel mesoporous TiO(2) can not only decolor and mineralize dyes completely but also can be effectively reused several times. On the basis of the research, mesoporous TiO(2) would be a promising photocatalyst for practical use. PMID:21833403

  14. 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).

  15. Recycle of silicate waste into mesoporous materials.

    PubMed

    Kim, Jung Ho; Kim, Minwoo; Yu, Jong-Sung

    2011-04-15

    Template synthesis of porous carbon materials usually requires selective removal of template silica from the carbon/silica composites. It not only involves waste of valuable chemicals, but also poses significant environmental concerns including high waste treatment cost. Recycling of silicates released from such nanocasting methods is successfully performed for the first time to regenerate valuable mesoporous MCM and SBA type silica materials, which will not only help in saving valuable chemicals, but also in decreasing chemical waste, contributing in improvement of our environmental standards. This approach can thus improve cost effectiveness for the mass production of nanostructured carbon and others utilizing silica directed nanocasting method by recycling otherwise silicate waste into highly desirable valuable mesoporous silica.

  16. Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor.

    PubMed

    Kruk, Michal; Dufour, Bruno; Celer, Ewa B; Kowalewski, Tomasz; Jaroniec, Mietek; Matyjaszewski, Krzysztof

    2005-05-19

    Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs. PMID:16852101

  17. 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.

  18. 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.

  19. Zeolite Nanoclusters Coated onto the Mesopore Walls of SBA-15

    SciTech Connect

    Do, Trong-On; Nossov, Andrei; Springuel-Huet, Marie-Anne; Schneider, Celine M.; Bretherton, Jeremy L.; Fyfe, Colin A.; Kaliaguine, Serge

    2004-11-10

    Hydrothermal stability and acidity are both essential for the application of mesoporous materials in catalysis.1,2 Several approaches have been aimed at improving these properties;3-8 for example, hydrothermally stable and strongly acidic mesoporous aluminosilicates have been assembled using protozeolitic seeds.

  20. Phosphorylated Mesoporous Carbon as a Solid Acid Catalyst

    SciTech Connect

    Dai, Sheng; Mayes, Richard T; Fulvio, Pasquale F; Ma, Zhen

    2011-01-01

    Mesoporous carbon catalyst supports are attractive due to their wide chemical stability while potentially increasing masstransport through and providing a path for larger molecules to access catalytic sites. Herein we report the synthesis of a 10 phosphorylated mesoporous carbon solid-acid catalyst characterized by NH3-TPD and isopropanol dehydration.

  1. 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

  2. Shape matters when engineering mesoporous silica-based nanomedicines.

    PubMed

    Hao, Nanjing; Li, Laifeng; Tang, Fangqiong

    2016-04-01

    Mesoporous silica nanomaterials have been successfully employed in the development of novel carriers for drug delivery. Numerous studies have been reported on engineering mesoporous silica-based carriers for drug loading, release, cellular uptake, and biocompatibility. A number of design parameters that govern the in vitro and in vivo performance of the carriers, including particle diameter, surface chemistry, and pore size, have been tuned to optimize nanomedicine efficacy. However, particle shape, which may generate a high impact on nanomedicine performance, has still not been thoroughly investigated. This is probably due to the limited availability of strategies and techniques to produce non-spherical mesoporous silica nanomaterials. Recent breakthroughs in controlling the particle shape of mesoporous silica nanomaterials have confirmed the important roles of shape on nanomedicine development. This review article introduces various fabrication methods for non-spherical mesoporous silica nanomaterials, including rod, ellipsoid, film, platelet/sheet, and cube, and the roles of particle shape in nanomedicine applications. PMID:26818852

  3. 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

  4. [Study on absorbing volatile oil with mesoporous carbon].

    PubMed

    Yan, Hong-mei; Jia, Xiao-bin; Zhang, Zhen-hai; Sun, E; Yang Nan

    2014-11-01

    Clove oil and turmeric oil were absorbed by mesoporous carbon. The absorption ratio of mesoporous carbon to volatile oil was optimized with the eugenol yield and curcumol yield as criteria Curing powder was characterized by scanning electron microscopy (SEM) and differential scanning calorietry (DSC). The effects of mesoporous carbon on dissolution in vitro and thermal stability of active components were studied. They reached high adsorption rate when the absorption ratio of mesoporous carbon to volatile oil was 1:1. When volatile oil was absorbed, dissolution rate of active components had a little improvement and their thermal stability improved after volatile oil was absorbed by the loss rate decreasing more than 50%. Absorbing herbal volatile oil with mesoporous carbon deserves further studying. PMID:25850263

  5. Mesoporous gallium oxide structurally stabilized by yttrium oxide

    SciTech Connect

    Yada, Mitsunori; Ohya, Masahumi; Machida, Masato; Kijima, Tsuyoshi

    2000-05-16

    Since the synthesis of mesoporous silicas such as MCM-41 and FSM-16 with large internal surface areas and uniform pore sizes, the surfactant templating method has been used to synthesize mesoporous metal oxides, including titanium, aluminum, niobium, and tantalum oxides. The mesostructured metal oxides are taken to be useful not only as catalysts and separating or adsorbing agents but also as functional host materials with optically, electrically, or magnetically unique properties, owing to the shape-specific and/or quantum effects of their thin inorganic skeletons. Mesoporous zirconium oxide and phosphate and hafnium oxide are promising as acid catalysts. Layered and hexagonal mesostructured titanium oxides, for example, were observed to be photocatalytically active. Aluminum and gallium oxides with a mesoporous structure are also expected to serve as a catalytic of other functional material. In this paper, the authors report the synthesis and characterization of mesoporous gallium oxide stabilized by yttrium oxide.

  6. A highly ordered cubic mesoporous silica/graphene nanocomposite

    NASA Astrophysics Data System (ADS)

    Lee, Chang-Wook; Roh, Kwang Chul; Kim, Kwang-Bum

    2013-09-01

    A highly ordered cubic mesoporous silica (KIT-6)/graphene nanocomposite and 2D KIT-6 nanoflakes were synthesized using a novel synthesis methodology. The non-ionic triblock copolymer, P123, played a dual role as a structure-directing agent in the formation of the cubic mesoporous structure and as a cross-linking agent between mesoporous silica and graphene. The prepared (KIT-6)/graphene nanocomposite could act as a template for the preparation of mesoporous material/graphene nanocomposites.A highly ordered cubic mesoporous silica (KIT-6)/graphene nanocomposite and 2D KIT-6 nanoflakes were synthesized using a novel synthesis methodology. The non-ionic triblock copolymer, P123, played a dual role as a structure-directing agent in the formation of the cubic mesoporous structure and as a cross-linking agent between mesoporous silica and graphene. The prepared (KIT-6)/graphene nanocomposite could act as a template for the preparation of mesoporous material/graphene nanocomposites. Electronic supplementary information (ESI) available: S1: TEM images of disordered mesoporous silica/graphene nanocomposite; S2: TEM images of KIT-6/GO nanocomposite; S3: Thermogravimetric analysis of KIT-6/GO and KG-400-700; S4: SEM and TEM images of KIT-6; S5: Low angle XRD, Raman spectra, N2 adsorption isotherms, pore size distribution and photographic images of the prepared samples; S6: TEM image and N2 adsorption isotherms of mesoporous carbon/graphene nanocomposite; S7: XPS C1s spectra of the prepared samples. See DOI: 10.1039/c3nr03108j

  7. New insight into mesoporous silica for nano metal-organic framework.

    PubMed

    Kondo, Atsushi; Takanashi, Shinji; Maeda, Kazuyuki

    2012-10-15

    A micropore- and mesopore-integrated material was synthesized by using a mesoporous silica and a metal-organic framework (MOF). The composite was composed of nano MOF crystals and mesoporous silica showing high porosity based on the intrinsic micropores of MOF and mesopores of mesoporous silica and additional pore spaces that should be from the void between nano MOF crystals. The composite shows higher adsorption rate of ethanol at 303 K than that of the bulk MOF.

  8. The formation of helical mesoporous silica nanotubes

    NASA Astrophysics Data System (ADS)

    Wan, Xiaobing; Pei, Xianfeng; Zhao, Huanyu; Chen, Yuanli; Guo, Yongmin; Li, Baozong; Hanabusa, Kenji; Yang, Yonggang

    2008-08-01

    Three chiral cationic gelators were synthesized. They can form translucent hydrogels in pure water. These hydrogels become highly viscous liquids under strong stirring. Mesoporous silica nanotubes with coiled pore channels in the walls were prepared using the self-assemblies of these gelators as templates. The mechanism of the formation of this hierarchical nanostructure was studied using transmission electron microscopy at different reaction times. The results indicated that there are some interactions between the silica source and the gelator. The morphologies of the self-assemblies of gelators changed gradually during the sol-gel transcription process. It seems that the silica source directed the organic self-assemblies into helical nanostructures.

  9. 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.

  10. 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.

  11. Silica-based mesoporous nanoparticles for controlled drug delivery

    PubMed Central

    Kwon, Sooyeon; Singh, Rajendra K; Perez, Roman A; Abou Neel, Ensanya A

    2013-01-01

    Drug molecules with lack of specificity and solubility lead patients to take high doses of the drug to achieve sufficient therapeutic effects. This is a leading cause of adverse drug reactions, particularly for drugs with narrow therapeutic window or cytotoxic chemotherapeutics. To address these problems, there are various functional biocompatible drug carriers available in the market, which can deliver therapeutic agents to the target site in a controlled manner. Among the carriers developed thus far, mesoporous materials emerged as a promising candidate that can deliver a variety of drug molecules in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles are widely used as a delivery reagent because silica possesses favourable chemical properties, thermal stability and biocompatibility. Currently, sol-gel-derived mesoporous silica nanoparticles in soft conditions are of main interest due to simplicity in production and modification and the capacity to maintain function of bioactive agents. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release. The properties of mesopores, including pore size and porosity as well as the surface properties, can be altered depending on additives used to fabricate mesoporous silica nanoparticles. Active surface enables functionalisation to modify surface properties and link therapeutic molecules. The tuneable mesopore structure and modifiable surface of mesoporous silica nanoparticle allow incorporation of various classes of drug molecules and controlled delivery to the target sites. This review aims to present the state of knowledge of currently available drug delivery system and identify properties of an ideal drug carrier for specific application, focusing on mesoporous silica nanoparticles. PMID:24020012

  12. 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.

  13. 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.

  14. 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. PMID:27072776

  15. 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.

  16. 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

  17. 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. PMID:26249601

  18. Gated Silica Mesoporous Materials in Sensing Applications.

    PubMed

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

    2015-08-01

    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

  19. Electrochemical design of mesoporous Pt-Ru alloy films with various compositions toward superior electrocatalytic performance.

    PubMed

    Wang, Hongjing; Imura, Masataka; Nemoto, Yoshihiro; Wang, Liang; Jeong, Hu Young; Yokoshima, Tokihiko; Terasaki, Osamu; Yamauchi, Yusuke

    2012-10-01

    Mesoporous Pt-Ru alloy films with various compositions were synthesized by electrochemical plating in an aqueous surfactant solution. After the removal of surfactants, continuous mesoporous Pt-Ru alloy films possessing uniform mesopores with diameter about 7 nm were obtained. The Ru content in the films could be controlled from 0 to 13 at % by changing the precursor compositions. For all the films, the mesostructural periodicities and the mesopore sizes in the films were not changed. Due to the mesoporous structure and the doped Ru content, our mesoporous Pt-Ru films showed superior electrocatalytic activity for methanol oxidation reaction in comparison with the commercially available Pt catalyst.

  20. Phosphorus recovery by mesoporous structure material from wastewater.

    PubMed

    Lee, S H; Lee, B C; Lee, K W; Lee, S H; Choi, Y S; Park, K Y; Iwamoto, M

    2007-01-01

    This study was designed to investigate the fundamental aspects of a possible removal of phosphorous from wastewater by using the mesoporous structure materials for wastewater reuse. The zirconium sulphate with mesoporous structure as a new type of ion exchangers was synthesised by hydrothermal reaction. From the results of X-ray diffraction and transmission electron microscope, it was discovered that the synthesised material had hexagonal mesoporous structure with a pore size of approximately 40-50A. Experimental results showed that the zirconium sulphate with mesoporous structure had very high sorption capacity for the phosphorus. The novel ion exchange occurred between PO4(3-) and SO4(2-), OH-. The amount of phosphate ions exchanged into the solid was as great as 3.4 mmol/g-ZS. Furthermore, it is possible to obtain a higher removal efficiency than other ion exchange media and adsorbents.

  1. 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.

  2. Responsive mesoporous photonic cellulose films by supramolecular cotemplating.

    PubMed

    Giese, Michael; Blusch, Lina K; Khan, Mostofa K; Hamad, Wadood Y; MacLachlan, Mark J

    2014-08-18

    Cellulose-based materials have been and continue to be exceptionally important for humankind. Considering the bioavailability and societal relevance of cellulose, turning this renewable resource into an active material is a vital step towards sustainability. Herein we report a new form of cellulose-derived material that combines tunable photonic properties with a unique mesoporous structure resulting from a new supramolecular cotemplating method. A composite of cellulose nanocrystals and a urea-formaldehyde resin organizes into a chiral nematic assembly, which yields a chiral nematic mesoporous continuum of desulfated cellulose nanocrystals after alkaline treatment. The mesoporous photonic cellulose (MPC) films undergo rapid and reversible changes in color upon swelling, and can be used for pressure sensing. These new active mesoporous cellulosic materials have potential applications in biosensing, optics, functional membranes, chiral separation, and tissue engineering. PMID:24981200

  3. Novel method to incorporate Si into monodispersed mesoporous carbon spheres.

    PubMed

    Yano, Kazuhisa; Tatsuda, Narihito; Masuda, Takashi; Shimoda, Tatsuya

    2016-10-01

    Liquid silicon precursor is used as a silicon source and very simple and easy method for the incorporation of Si into mesoporous carbon spheres is presented. By using capillary condensation, the liquid precursor, Cyclopentasilane, penetrates into mesopores of carbon spheres homogeneously and subsequent heating brings the decomposition of the precursor and the formation of silicon inside meso-channels of carbon even though the decomposition is done much higher than the boiling point of the precursor. The homogeneous distribution of silicon is verified by EDX mapping of the composite as well as SEM observation of the calcined one. More than 45wt% of Si can be incorporated into mesopores by just one operation. The Si@mesoporous carbon composite works as an anode for a Lithium ion battery. PMID:27344486

  4. 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...

  5. 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. PMID:18253526

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Antibacterial mesoporous molecular sieves modified with polymeric N-halamine.

    PubMed

    Wang, Yingfeng; Li, Lin; Liu, Ying; Ren, Xuehong; Liang, Jie

    2016-12-01

    In this research, a new kind of porous N-halamine material with high antibacterial efficacies was prepared. Poly [5,5-dimethyl-3-(3'-triethoxysilylpropyl)-hydantoin] (PSPH), an N-halamine precursor, was synthesized and grafted onto the surface of mesoporous molecular sieves (SBA-15). The mesoporous molecular sieves modified with the N-halamine polymer could be rendered biocidal upon exposure to dilute household bleach. The modified mesoporous molecular sieves were characterized by SEM, TEM, FTIR, XPS, TGA, XRD and BET analysis. It was found that the PSPH has been successfully grafted on the surface of mesoporous molecular sieves, and the morphology and structure of the modified mesoporous molecular sieves were slightly affected. The N-halamine modified mesoporous molecular sieves showed excellent antibacterial property, and inactivated 100% of S. aureus and E. coli O157:H7 with 8.05 and 7.92 log reductions within 1min of contact, respectively. The modified SBA-15 with high-antibacterial efficiency has potential application in water treatment and biomaterials areas. PMID:27612805

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. Styrene oligomerization as a molecular probe reaction for Brønsted acidity at the nanoscale.

    PubMed

    Aramburo, Luis R; Wirick, Sue; Miedema, Piter S; Buurmans, Inge L C; de Groot, Frank M F; Weckhuysen, Bert M

    2012-05-21

    The Brønsted acid-catalyzed oligomerization of 4-fluorostyrene has been studied on a series of H-ZSM-5 zeolite powders, steamed under different conditions, with a combination of UV-Vis micro-spectroscopy and Scanning Transmission X-ray Microscopy (STXM). UV-Vis micro-spectroscopy and STXM have been used to monitor the relative formation of cyclic and linear dimeric carbocations as a function of the steaming post-treatment (i.e., parent vs. steaming at 600, 700 and 800 °C). It was found that the UV-Vis band intensity ratios of linear to cyclic dimeric species increase from 0.79 (parent H-ZSM-5) over 1.41 (H-ZSM-5 steamed at 600 °C) and 1.88 (H-ZSM-5 steamed at 700 °C) to 2.33 (H-ZSM-5 steamed at 800 °C). STXM confirms this trend in reaction product selectivity, as the relative intensities of the transitions attributed to the presence of the cyclic dimer in the carbon K-edge spectra decrease with increasing severity of the steaming post-treatment. Furthermore, STXM reveals spatial heterogeneities in reaction product formation within the H-ZSM-5 zeolite powders at the nanoscale. More specifically, a shrinking carbon core-shell distribution was detected within the zeolite aggregates, in which the relative amount of cyclic dimeric species is higher in the core relative to the shell of the zeolite aggregate and the relative amount of cyclic dimeric species in the zeolite core gradually decreases with increasing severity of the steaming post-treatment. These differences are rationalized in terms of spatial differences in Brønsted acidity within H-ZSM-5 zeolite powders as well as by changes in the formation process of linear and dimeric carbocations within H-ZSM-5 micro- and mesopores.

  20. 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.

  1. Porosity control in mesoporous polymers using CO2-swollen block copolymer micelles as templates and their use as catalyst supports.

    PubMed

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

    2014-10-14

    Mesoporous polymers with tunable large mesopores and thin mesopore walls were synthesized through a CO2-swollen micelle templating route. The mesopore size and porosity properties of the polymers can be easily modulated by adjusting CO2 pressure. The as-synthesized mesocellular polymers are excellent candidate supports for preparing heterogeneous catalysts.

  2. 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.

  3. 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

  4. Mesoporous materials used in medicine and environmental applications.

    PubMed

    Gunduz, Oguzhan; Yetmez, Mehmet; Sonmez, Maria; Georgescu, Mihai; Alexandrescu, Laura; Ficai, Anton; Ficai, Denisa; Andronescu, Ecaterina

    2015-01-01

    Mesoporous materials synthesized in the presence of templates, are commonly used for environment and medical applications. Due to the properties it holds, mesoporous silica nanoparticles is an excellent material for use in medical field, biomaterials, active principles delivery systems, enzyme immobilization and imaging. Their structure allows embedding large and small molecules, DNA adsorption and genetic transfer. Using mesoporous silica nanoparticles for delivery of bioactive molecules can protect them against degradation under physiological conditions, allow controlled drugs release and minimize side effects on healthy tissues. Cellular tests performed on mesoporous silica nanoparticles demonstrate that MSN's cytotoxicity is dependent on the size and concentration and suggests the use of larger size nanoparticles is optimal for medical applications. Mesoporous materials possess high biological compatibility, are non-toxic and can be easily modified by functionalizing the surface or inside the pores by grafting or co-condensation method. The structure, composition and pores size of this material can be optimized during synthesis by varying the stoichiometric reactants, reaction conditions, nature of the template's molecules or by functionalization method. PMID:25877095

  5. 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.

  6. DEVELOPMENT OF MESOPOROUS MEMBRANE MATERIALS FOR CO2 SEPARATION

    SciTech Connect

    Wei-Heng Shih; Qiang Zhao; Nanlin Wang

    2002-05-01

    Mesoporous and precipitated alumina were synthesized as the base material for CO{sub 2} adsorbent. The porous alumina is doped with Ba to enhance it 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 affinity to CO{sub 2} than N{sub 2}. On the other hand, the barium aluminate phase (Ba{sub 3}Al{sub 2}O{sub 6}) in the mesoporous sample does not help the adsorption of CO{sub 2}.

  7. Synthesis of mesoporous platinum-copper films by electrochemical micelle assembly and their electrochemical applications.

    PubMed

    Li, Cuiling; Yamauchi, Yusuke

    2014-01-13

    We have electrochemically synthesized mesoporous platinum-copper films with various compositions in an aqueous surfactant solution. By tuning the composition ratios of the platinum and copper sources in the precursor solutions, mesoporous bimetallic films with copper contents that dramatically change from 0 to 70 mol % can be successfully prepared. The obtained bimetallic films possess uniformly sized mesopores over the entire area. These mesoporous platinum-copper films are electrochemically active and show composition-dependent catalytic activity and stability for the methanol oxidation reaction. The bimetallic mesoporous films are a promising new class of electrocatalyst for the future.

  8. 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

  9. Unusual reinforcement of silicone rubber compounds containing mesoporous silica particles as inorganic fillers.

    PubMed

    Suzuki, Norihiro; Kiba, Shosuke; Kamachi, Yuichiro; Miyamoto, Nobuyoshi; Yamauchi, Yusuke

    2012-03-14

    We fabricate mesoporous silica/silicone composites in a simple way and systematically examine their thermal stability, swelling characteristic, mechanical strength, and transparency. Simple calculations show that more than 90 vol% of mesopores are filled with silicone rubbers. Compared to non-porous silica/silicone composites, mesoporous silica/silicone composites showed a lower coefficient of linear thermal expansion (CTE). In addition, dramatic improvements of the tensile strength and Young's modulus are obtained with mesoporous silica/silicone composites. Furthermore, mesoporous silica/silicone composites show higher transparency than non-porous silica/silicone composites.

  10. Enzyme-Powered Hollow Mesoporous Janus Nanomotors.

    PubMed

    Ma, Xing; Jannasch, Anita; Albrecht, Urban-Raphael; Hahn, Kersten; Miguel-López, Albert; Schäffer, Erik; Sánchez, Samuel

    2015-10-14

    The development of synthetic nanomotors for technological applications in particular for life science and nanomedicine is a key focus of current basic research. However, it has been challenging to make active nanosystems based on biocompatible materials consuming nontoxic fuels for providing self-propulsion. Here, we fabricate self-propelled Janus nanomotors based on hollow mesoporous silica nanoparticles (HMSNPs), which are powered by biocatalytic reactions of three different enzymes: catalase, urease, and glucose oxidase (GOx). The active motion is characterized by a mean-square displacement (MSD) analysis of optical video recordings and confirmed by dynamic light scattering (DLS) measurements. We found that the apparent diffusion coefficient was enhanced by up to 83%. In addition, using optical tweezers, we directly measured a holding force of 64 ± 16 fN, which was necessary to counteract the effective self-propulsion force generated by a single nanomotor. The successful demonstration of biocompatible enzyme-powered active nanomotors using biologically benign fuels has a great potential for future biomedical applications. PMID:26437378

  11. 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. PMID:24699503

  12. 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.

  13. Photoluminescence of carbon dots from mesoporous silica

    NASA Astrophysics Data System (ADS)

    Nelson, D. K.; Razbirin, B. S.; Starukhin, A. N.; Eurov, D. A.; Kurdyukov, D. A.; Stovpiaga, E. Yu; Golubev, V. G.

    2016-09-01

    Photophysical properties of carbon dots were investigated under various excitation conditions and over a wide temperature region - from room to liquid helium temperatures. The carbon dots (CDs) were synthesized using mesoporous silica particles as a reactor and (3-aminopropyl)triethoxysilane (APTES) as a precursor. The photoluminescence spectra of CDs exhibit a strong dependence on the excitation wavelength and demonstrate a significant inhomogeneous broadening. Lowering sample temperature reveals the doublet structure of the spectra, which is associated with the vibronic structure of radiative transitions. The vibration energy ∼1200 cm-1 is close to the energy of Csbnd O stretching vibration. Long-lived phosphorescence of carbon dots with its decay time ∼0.2 s at T = 80 K was observed. The fluorescence and phosphorescence spectra are shown to be spectrally separated. The long-lived component of the emission was ascribed to optically forbidden triplet-singlet transitions. The value of the singlet-triplet splitting was found to be about 0.3 eV. Photo-induced polarization of the luminescence of carbon dots was revealed. The degree of the linear polarization is dependent on the wavelengths of both excitation and emitted light. The effect indicates a hidden anisotropy of optical dipole transitions in the dots and demonstrates the loss of the dipole orientation during the electron energy relaxation.

  14. 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.

  15. Mesoporous junctions and nanocrystalline solar cells

    NASA Astrophysics Data System (ADS)

    Graetzel, Michael

    2000-03-01

    Learning from the concepts used by green plants, we have developed a molecular photovoltaic system based on the sensitization of nanocrystalline TiO2 films. In analogy to photosyntesis, light is absorbed by a monolayer of dye attached to the surface of a wide-band-gap oxide. The mesoporous morphology of the layer provides a substrate characterized by a very large surface area. The roughness factor of a 10-micron thick film reaches easily 1000. Light penetrating the dye loaded TiO2 nanocrystals is therefore collected in an efficient manner, similar to the thylakoid vesicles in green leafs which are stacked in order to enhance solar light harvesting. The excited dye injects an electron in the conduction band of the oxide resulting in efficient and very rapid charge separation. Nearly quantitative conversion of photons in electric current have been achieved with these devices over the whole visible and near-IR range of the spectrum. The overall AM 1.5 solar-to electric power conversion efficiency has reached already 11unravel the dynamics of interfacial charge transfer reactions at these dye- sensitized heterojunctions.

  16. 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.

  17. 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.

  18. 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. PMID:26585498

  19. 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.

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

    PubMed

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

    2005-03-01

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

  1. 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. PMID:15787373

  2. 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.

  3. 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.

  4. Transport properties of hierarchical micro-mesoporous materials.

    PubMed

    Schneider, Daniel; Mehlhorn, Dirk; Zeigermann, Philipp; Kärger, Jörg; Valiullin, Rustem

    2016-06-13

    Adding mesopore networks in microporous materials using the principles of hierarchical structure design is recognized as a promising route for eliminating their transport limitations and, therefore, for improving their value in technological applications. Depending on the routes of physico-chemical procedures or post-synthesis treatments used, very different geometries of the intentionally-added transport mesopores can be obtained. Understanding the structure-dynamics relationships in these complex materials with multiple porosities under different thermodynamical conditions remains a challenging task. In this review, we summarize the results obtained so far on experimental and theoretical studies of diffusion in micro-mesoporous materials. By considering four common classes of bi-porous materials, which are differing by the inter-connectivities of their sup-spaces as one of the most important parameter determining the transport rates, we discuss their generic transport properties and correlate the results delivered by the equilibrium and non-equilibrium techniques of diffusion measurements.

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

    PubMed

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

    2013-10-01

    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.

  6. 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.

  7. Brick-and-Mortar Self-Assembly Approach to Graphitic Mesoporous Carbon Nanocomposites

    SciTech Connect

    Dai, Sheng; Fulvio, Pasquale F; Mayes, Richard T; Wang, Xiqing; Mahurin, Shannon Mark; Bauer, Christopher; Presser, Volker; Mcdonough, John; Gogotsi, Yury

    2011-01-01

    Mesoporous carbon materials do not have sufficient ordering at the atomic scale to exhibit good electronic conductivity. To date, mesoporous carbons having uniform mesopores and high surface areas have been prepared from partially-graphitizable precursors in the presence of templates. High temperature thermal treatments above 2000 C, which are usually required to increase conductivity, result in a partial or total collapse of the mesoporous structures and reduced surface areas induced by growth of graphitic domains, limiting their applications in electric double layer capacitors and lithium-ion batteries. In this work, we successfully implemented a 'brick-and-mortar' approach to obtain ordered graphitic mesoporous carbon nanocomposites with tunable mesopore sizes below 850 C without using graphitization catalysts or high temperature thermal treatments. Phenolic resin-based mesoporous carbons act as mortar to highly conductive carbon blacks and carbon onions (bricks). The capacitance and resistivity of final materials can be tailored by changing the mortar to brick ratios.

  8. 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.

  9. 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.

  10. Hypercrosslinked phenolic polymers with well developed mesoporous frameworks

    DOE PAGESBeta

    Zhang, Jinshui; Qiao, Zhenan -An; Mahurin, Shannon Mark; Jiang, Xueguang; Chai, Song -Hai; Lu, Hanfeng; Nelson, Kimberly M.; Dai, Sheng

    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.

  11. 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.

  12. 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.

  13. 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

  14. Hypercrosslinked phenolic polymers with well-developed mesoporous frameworks.

    PubMed

    Zhang, Jinshui; Qiao, Zhen-An; Mahurin, Shannon M; Jiang, Xueguang; Chai, Song-Hai; Lu, Hanfeng; Nelson, Kimberly; Dai, Sheng

    2015-04-01

    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. Moreover, this soft chemistry synthetic protocol can be further extended to nanotexture other arene-based polymers with robust frameworks. PMID:25683637

  15. Low temperature crystallisation of mesoporous TiO2.

    PubMed

    Kohn, Peter; Pathak, Sandeep; Stefik, Morgan; Ducati, Caterina; Wiesner, Ulrich; Steiner, Ullrich; Guldin, Stefan

    2013-11-01

    Conducting mesoporous TiO2 is rapidly gaining importance for green energy applications. To optimise performance, its porosity and crystallinity must be carefully fine-tuned. To this end, we have performed a detailed study on the temperature dependence of TiO2 crystallisation in mesoporous films. Crystal nucleation and growth of initially amorphous TiO2 derived by hydrolytic sol-gel chemistry is compared to the evolution of crystallinity from nanocrystalline building blocks obtained from non-hydrolytic sol-gel chemistry, and mixtures thereof. Our study addresses the question whether the critical temperature for crystal growth can be lowered by the addition of crystalline nucleation seeds.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  17. Further evidence on the change of acid properties of H-ZSM-5 by Ga and Pt

    SciTech Connect

    Meriaudeau, P.; Naccache, C.

    1995-12-01

    The effects of oxidizing and reducing treatments over Ga/H-ZSM-5 aromatization catalysts are studied. The respective roles of the dehydrogenation function and of the acid function are discussed and it appears that the acid function is depressed through the reducing treatment. To explain the role of gallium in propane activation, the concept of the dual-site mechanism is preferred to the concept of the {open_quotes}porthole{close_quotes} mechanism. 19 refs., 1 fig., 4 tabs.

  18. 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.

  19. 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. PMID:25000419

  20. 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.

  1. Adsorption of mycotoxins in beverages onto functionalized mesoporous silicas

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  2. Chemical vapor deposition of mesoporous graphene nanoballs for supercapacitor.

    PubMed

    Lee, Jung-Soo; Kim, Sun-I; Yoon, Jong-Chul; Jang, Ji-Hyun

    2013-07-23

    A mass-producible mesoporous graphene nanoball (MGB) was fabricated via a precursor-assisted chemical vapor deposition (CVD) technique for supercapacitor application. Polystyrene balls and reduced iron created under high temperature and a hydrogen gas environment provide a solid carbon source and a catalyst for graphene growth during the precursor-assisted CVD process, respectively. Carboxylic acid and sulfonic acid functionalization of the polystyrene ball facilitates homogeneous dispersion of the hydrophobic polymer template in the metal precursor solution, thus, resulting in a MGB with a uniform number of graphene layers. The MGB is shown to have a specific surface area of 508 m(2)/g and is mesoporous with a mean mesopore diameter of 4.27 nm. Mesopores are generated by the removal of agglomerated iron domains, permeating down through the soft polystyrene spheres and providing the surface for subsequent graphene growth during the heating process in a hydrogen environment. This technique requires only drop-casting of the precursor/polystyrene solution, allowing for mass-production of multilayer MGBs. The supercapacitor fabricated by the use of the MGB as an electrode demonstrates a specific capacitance of 206 F/g and more than 96% retention of capacitance after 10,000 cycles. The outstanding characteristics of the MGB as an electrode for supercapacitors verify the strong potential for use in energy-related areas. PMID:23782238

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Novel organic-inorganic hybrid mesoporous materials and nanocomposites

    NASA Astrophysics Data System (ADS)

    Feng, Qiuwei

    Organic-inorganic hybrid mesoporous materials have been prepared successfully via the nonsurfactant templated sol-gel pathway using dibenzoyl-L-tartaric acid (DBTA) as the templating compound. Styrene and methyl methacrylate polymers have been incorporated into the mesoporous silica matrix on the molecular level. The synthetic conditions have been systematically studied and optimized. Titania based mesoporous materials have also been made using nonionic polyethylene glycol surfactant as the pore forming or structure-directing agent. In all of the above mesoporous materials, pore structures have been studied in detail by Transmission Electron Microscopy (TEM), X-ray diffraction and Brunauer-Emmett-Teller (BET) characterizations. The relationship between the template concentration and the pore parameters has been established. This nonsurfactant templated pathway possesses many advantages over the known surfactant approaches such as low cost, environment friendly and biocompatability. To overcome the drawback of nonsurfactant templated mesoporous materials that lack a well ordered pore structure, a flow induced synthesis has been attempted to orientate the sol-gel solution in order to obtain aligned pore structures. The versatility of this nonsurfactant templated pathway can even be extended to the making of organic-inorganic hybrid nanocomposite materials. On the basis of this approach, polymer-silica nanocomposite materials have been prepared using a polymerizable template. It is shown that the organic monomer such as hydroxyethyl methacrylate can act as a template in making nanoporous silica materials and then be further polymerized through a post synthesis technique. The properties and morphology of this new material have been studied by Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM) and Infrared Absorption Spectroscopy (FTIR). Electroactive organic-inorganic hybrid materials have also been synthesized via the sol-gel process. A

  8. 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. PMID:18668502

  9. 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).

  10. 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).

  11. 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.

  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. 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

  14. 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

  15. 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

  16. 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

  17. Direct coating of mesoporous titania on CTAB-capped gold nanorods

    NASA Astrophysics Data System (ADS)

    Zhao, Junwei; Xu, Pengyu; Li, Yue; Wu, Jian; Xue, Junfei; Zhu, Qiannan; Lu, Xuxing; Ni, Weihai

    2016-03-01

    We demonstrate a CTAB-templated approach towards direct coating of mesoporous titania on gold nanorods in aqueous solutions. The formation of the mesoporous shell is found to be closely correlated with CTAB concentration and the amount of the titania precursor. This approach can be readily extended to form mesoporous titania shells on other CTAB-capped nanoparticles.We demonstrate a CTAB-templated approach towards direct coating of mesoporous titania on gold nanorods in aqueous solutions. The formation of the mesoporous shell is found to be closely correlated with CTAB concentration and the amount of the titania precursor. This approach can be readily extended to form mesoporous titania shells on other CTAB-capped nanoparticles. Electronic supplementary information (ESI) available: Experimental details including chemicals, sample preparation, and characterization methods. UV-Vis extinction spectra, SEM images, and TEM images of AuNR@mTiO2 nanostructures. See DOI: 10.1039/c5nr05692f

  18. Post-treatment and characterization of novel luminescent hybrid bimodal mesoporous silicas

    NASA Astrophysics Data System (ADS)

    Li, Yuzhen; Sun, Jihong; Wu, Xia; Lin, Li; Gao, Lin

    2010-08-01

    A novel luminescent hybrid bimodal mesoporous silicas (LHBMS) were synthesized via grafting 1,8-Naphthalic anhydride into the pore channels of bimodal mesoporous silicas (BMMs) for the first time. The resulting samples were characterized by powder X-ray diffraction (XRD), N 2 adsorption/desorption measurement, Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM), UV-vis absorption spectroscopy, and Photoluminescence spectroscopy (PL). The results show that 1,8-Naphthalic anhydride organic groups have been successfully introduced into the mesopores of the BMMs and the hybrid silicas are of bimodal mesoporous structure with the ordered small mesopores of around 3 nm and the large mesopores of uniform intra-nanoparticle. The excellent photoluminescent performance of LHBMS has a blue shift compared to that of 2-[3-(triethoxysilyl) propyl-1 H-Benz [de]isoquinoline-1, 3(2 H)-dione, suggesting the existence of the quantum confinement effectiveness.

  19. Synthesis of mesoporous Beta and Sn-Beta zeolites and their catalytic performances.

    PubMed

    Jin, Junjiang; Ye, Xinxin; Li, Yongsheng; Wang, Yanqin; Li, Liang; Gu, Jinlou; Zhao, Wenru; Shi, Jianlin

    2014-06-14

    Mesoporous Beta zeolite has been successfully prepared through hydrothermal synthesis in the presence of cationic ammonium-modified chitosan as the meso-template. Through a subsequent solid-gas reaction between highly dealuminated mesoporous Beta zeolite and SnCl4 steam at an elevated temperature, mesoporous Sn-Beta has been facilely obtained. It was revealed that the addition of cationic chitosan induced the nanocrystal aggregation to particle sizes of ∼300 nm, giving rise to the intercrystalline/interparticle mesoporosity. In the Sn-implanting procedure, Sn species were demonstrated to be doped into the framework of the resulting mesoporous Beta zeolite in a tetrahedral environment without structural collapse. Due to the micro/mesoporous structures, both mesoporous Beta and Sn-Beta exhibited superior performances in α-pinene isomerization, Baeyer-Villiger oxidation of 2-adamantanone by hydrogen peroxide and the isomerization of glucose in water, respectively.

  20. 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

    2016-10-01

    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. PMID:27554196

  1. 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

  2. Using mesoporous carbon electrodes for brackish water desalination.

    PubMed

    Zou, Linda; Li, Lixia; Song, Huaihe; Morris, Gayle

    2008-04-01

    Electrosorptive deionisation is an alternative process to remove salt ions from the brackish water. The porous carbon materials are used as electrodes. When charged in low voltage electric fields, they possess a highly charged surface that induces adsorption of salt ions on the surface. This process is reversible, so the adsorbed salt ions can be desorbed and the electrode can be reused. In the study, an ordered mesoporous carbon (OMC) electrode was developed for electrosorptive desalination. The effects of pore arrangement pattern (ordered and random) and pore size distribution (mesopores and micropores) on the desalination performance was investigated by comparing OMC and activated carbon (AC). It were revealed from X-ray diffraction and N(2) sorption measurements that AC has both micropores and mesopores, whereas ordered mesopores are dominant in OMC. Their performance as potential electrodes to remove salt was evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests at a range of electrolyte concentrations and sweep rates. It is deduced that under the same electrochemical condition the specific capacitance values of OMC electrode (i.e. 133 F/g obtained from CV at a sweep rate of 1 mV/s in 0.1M NaCl solution) are larger than those of AC electrode (107 F/g), suggesting that the former has a higher desalting capacity than the latter. Furthermore, the OMC electrode shows a better rate capacity than the AC electrode. In addition, the desalination capacities were quantified by the batch-mode experiment at low voltage of 1.2V in 25 ppm NaCl solution (50 micros/cm conductivity). It was found that the adsorbed ion amounts of OMC and AC electrodes were 11.6 and 4.3 micromol/g, respectively. The excellent electrosorptive desalination performance of OMC electrode might be not only due to the suitable pore size (average of 3.3 nm) for the propagation of the salt ions, but also due to the ordered mesoporous structure that facilitates desorption of the

  3. Using mesoporous carbon electrodes for brackish water desalination.

    PubMed

    Zou, Linda; Li, Lixia; Song, Huaihe; Morris, Gayle

    2008-04-01

    Electrosorptive deionisation is an alternative process to remove salt ions from the brackish water. The porous carbon materials are used as electrodes. When charged in low voltage electric fields, they possess a highly charged surface that induces adsorption of salt ions on the surface. This process is reversible, so the adsorbed salt ions can be desorbed and the electrode can be reused. In the study, an ordered mesoporous carbon (OMC) electrode was developed for electrosorptive desalination. The effects of pore arrangement pattern (ordered and random) and pore size distribution (mesopores and micropores) on the desalination performance was investigated by comparing OMC and activated carbon (AC). It were revealed from X-ray diffraction and N(2) sorption measurements that AC has both micropores and mesopores, whereas ordered mesopores are dominant in OMC. Their performance as potential electrodes to remove salt was evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests at a range of electrolyte concentrations and sweep rates. It is deduced that under the same electrochemical condition the specific capacitance values of OMC electrode (i.e. 133 F/g obtained from CV at a sweep rate of 1 mV/s in 0.1M NaCl solution) are larger than those of AC electrode (107 F/g), suggesting that the former has a higher desalting capacity than the latter. Furthermore, the OMC electrode shows a better rate capacity than the AC electrode. In addition, the desalination capacities were quantified by the batch-mode experiment at low voltage of 1.2V in 25 ppm NaCl solution (50 micros/cm conductivity). It was found that the adsorbed ion amounts of OMC and AC electrodes were 11.6 and 4.3 micromol/g, respectively. The excellent electrosorptive desalination performance of OMC electrode might be not only due to the suitable pore size (average of 3.3 nm) for the propagation of the salt ions, but also due to the ordered mesoporous structure that facilitates desorption of the

  4. Highly enhanced capacitance of MgO-templated mesoporous carbons in low temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Kado, Yuya; Imoto, Kiyoaki; Soneda, Yasushi; Yoshizawa, Noriko

    2014-12-01

    MgO-templated mesoporous carbons with high specific surface areas were employed for the electrode materials of electric double layer capacitors (EDLCs) in low temperature ionic liquids. The mesoporous carbons exhibit strongly enhanced capacitance in ionic liquids at 20 to -40 °C compared to conventional activated carbons. Mesopores in the carbon electrodes provide a smooth pathway for the ions, and minimize the temperature influence on the diffusion resistance of the ions. Thus, this paper confirms that mesoporous carbons work as electrode materials to achieve highly enhanced capacitances below 0 °C in ionic liquids, which leads to wide ranging applications of EDLC devices.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. Preparation and characterization of well ordered mesoporous diopside nanobiomaterial.

    PubMed

    Wei, Jie; Lu, Jingxiong; Yan, Yonggang; Li, Hong; Ma, Jian; Wu, Xiaohui; Dai, Chenglong; Liu, Changsheng

    2011-12-01

    Well ordered mesoporous diopside (OMD) nanobiomaterial was synthesized by a sol-gel process. The in vitro bioactivity of the OMD was evaluated by investigating the apatite-forming ability in simulated body fluid (SBF), and the hemostatic activity of the OMD was determined by measuring the activated partial thromboplastin time (APTT) and prothrombin time (PT) in vitro. The results suggested that the OMD exhibited excellent in vitro bioactivity, with surface apatite formation for OMD exceeding that of non-mesoporous diopside (n-MD) at 7 days. Moreover, the OMD with high surface area possessed good hemostatic property because it could absorb a large number of water from the blood. In conclusion, the prepared OMD had excellent bioactivity and hemostatic activity, which can not only be applied as bone repair biomaterial for bone regeneration, but also as hemostatic agent for surgery hemostasis. PMID:22408987

  11. Impact of Surface Chemistry on Copper Deposition in Mesoporous Silicon.

    PubMed

    Darwich, Walid; Garron, Anthony; Bockowski, Piotr; Santini, Catherine; Gaillard, Frédéric; Haumesser, Paul-Henri

    2016-08-01

    An easy, efficient, and safe process is developed to metallize mesoporous silicon (PSi) with Cu from the decomposition of a solution of mesitylcopper (CuMes) in an imidazolium-based ionic liquid (IL), [C1C4Im][NTf2]. The impregnation of a solution of CuMes in IL affords the deposition of metallic islands not only on the surface but also deep within the pores of a mesoporous Si layer with small pores below 10 nm. Therefore, this process is well suited to efficiently and completely metallize PSi layers. An in-depth mechanistic study shows that metal deposition is due to the reduction of CuMes by surface silane groups rather than by Si oxidation as observed in aqueous or water-containing media. This could open a new route to the chemical metallization of PSi by less-noble metals difficult to attain by a conventional displacement reaction.

  12. 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.

  13. 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.

  14. Impact of Surface Chemistry on Copper Deposition in Mesoporous Silicon.

    PubMed

    Darwich, Walid; Garron, Anthony; Bockowski, Piotr; Santini, Catherine; Gaillard, Frédéric; Haumesser, Paul-Henri

    2016-08-01

    An easy, efficient, and safe process is developed to metallize mesoporous silicon (PSi) with Cu from the decomposition of a solution of mesitylcopper (CuMes) in an imidazolium-based ionic liquid (IL), [C1C4Im][NTf2]. The impregnation of a solution of CuMes in IL affords the deposition of metallic islands not only on the surface but also deep within the pores of a mesoporous Si layer with small pores below 10 nm. Therefore, this process is well suited to efficiently and completely metallize PSi layers. An in-depth mechanistic study shows that metal deposition is due to the reduction of CuMes by surface silane groups rather than by Si oxidation as observed in aqueous or water-containing media. This could open a new route to the chemical metallization of PSi by less-noble metals difficult to attain by a conventional displacement reaction. PMID:27368422

  15. 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. PMID:25872710

  16. Catalytic conversion of cellulose over mesoporous Y zeolite.

    PubMed

    Park, Young-Kwon; Jun, Bo Ram; Park, Sung Hoon; Jeon, Jong-Ki; Lee, See Hoon; Kim, Seong-Soo; Jeong, Kwang-Eun

    2014-07-01

    Mesoporous Y zeolite (Meso-Y) was applied, for the first time, to the catalytic pyrolysis of cellulose which is a major constituent of lignocellulosic biomass, to produce high-quality bio-oil. A representative mesoporous catalyst Al-MCM-41 was also used to compare its catalytic activity with that of Meso-Y. Pyrolysis-gas chromatography/mass spectrometry was used for the experiments. Meso-Y, with higher acidity, led to larger yields of aromatics and furans with high value-added than Al-MCM-41, resulting in the production of bio-oil with higher quality. The effect of temperature on the catalytic pyrolysis was not significant within the range of 400-500 degrees C. When the Meso-Y to cellulose ratio was increased from 1/1 via 2/1 to 3/1, the deoxygenation efficiency increased, leading to increased yield of aromatics. PMID:24757989

  17. 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.

  18. 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.

  19. 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

  20. Is there any microporosity in ordered mesoporous silicas?

    PubMed

    Silvestre-Alberto, A; Jardim, E O; Bruijn, E; Meynen, V; Cool, P; Sepulveda-Escribano, A; Silvestre-Alberto, J; Rodriguez-Reinoso, F

    2009-01-20

    The porous structure of nanostructured silicas MCM-41 and SBA-15 has been characterized using N2 adsorption at 77 K, before and after n-nonane preadsorption, together with immersion calorimetry into liquids of different molecular dimensions. Selective blocking of the microporosity with n-nonane proves experimentally that MCM-41 is exclusively mesoporous while SBA-15 exhibits both micro- and mesopores. Additionally, N2 adsorption experiments on the preadsorbed samples show that the microporosity on SBA-15 is located in intrawall positions, the micropore volume accounting for only approximately 7-8 % of the total pore volume. Calorimetric measurements into n-hexane (0.43 nm), 2-methylpentane (0.49 nm), and 2,2-dimethylbutane (0.56 nm) estimate the size of these micropores to be < or = 0.56 nm.

  1. Ordered micro/mesoporous composite prepared as thin films.

    PubMed

    Petkov, N; Hölzl, M; Metzger, T H; Mintova, S; Bein, T

    2005-03-17

    A new synthesis method for preparation of thin films and powders consisting of zeolite beta nanocrystals embedded in ordered mesoporous silica matrix is described. The final structures possessing bimodal porosity, i.e., high degree of mesophase order and spatially defined microporous zeolite nanocrystals are obtained via simultaneous solvent evaporation of preformed silica/surfactant/ethanol/nanosized zeolite beta assemblies. The films were characterized with grazing-incident diffraction (GID), nitrogen sorption based on gravimetric measurements with quartz crystal microbalance (QCM) devices, and transmission electron microscopy (TEM). It is shown that the incorporation of beta nanocrystals in the mesoporous silica matrix and the mesophase order itself can be controlled through the variation of the fractional amounts of the zeolite nanoparticles and silica/surfactant solutions. The HR-TEM measurements showed that the nanosized Beta microporous crystals are separated and at the same time connected through an ordered mesostructured matrix.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. From polymeric "plasticine" to shape-controlled mesoporous carbon.

    PubMed

    Qian, Xu-Fang; Wang, Zheng; Wan, Ying

    2009-07-15

    A soft-phase intercalating process to synthesize mesostructured plasticine by using amphiphilic triblock copolymer F127 as a structure-directing agent, reverse triblock copolymer 25R4 as an intercalating soft matter, and soluble phenolic resin as a carbon source is demonstrated. The "plasticine" has interlayer organic-organic hybrid structure, which is emplastic, sticky, and able to be easily shaped at will. After template removal at 350 degrees C and further carbonization at 600 degrees C, highly ordered mesoporous polymers and carbons can be successively obtained with the maintenance of the original shape. The self-supported, shape-controlled, ordered mesoporous carbon products possess high surface areas (495-777 m(2)/g), large pore volumes (0.32-0.47 cm(3)/g), uniform pore sizes (2.5-4.3 nm) in the nanoscale and hollow tremella-like morphology in the micronscale which may facilitate mass transportation. PMID:19406429

  7. Mesoporous material Al-MCM-41 from natural halloysite

    NASA Astrophysics Data System (ADS)

    Xie, Yaling; Zhang, Yi; Ouyang, Jing; Yang, Huaming

    2014-07-01

    Aluminum-containing hexagonally ordered mesoporous silica (Al-MCM-41) with specific surface area of 509.4 m2/g was first synthesized using natural halloysite as source material by hydrothermal treatment, without addition of silica or aluminum regents. The samples were characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption measurements, and Fourier transform infrared spectra techniques. The results indicate that process parameters, including calcination temperature, pH value, n(SiO2)/ n(CTAB)/ n(H2O) ratio, and hydrothermal reaction time, show moderate effects on the preparation of Al-MCM-41. SiO2/Al2O3 molar ratio could be effectively modulated by the calcination temperature for halloysite. Furthermore, we first clarified the structural evolution from natural halloysite to mesoporous material Al-MCM-41 at the atomic level.

  8. 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.

  9. 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.

  10. 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. PMID:24245279

  11. 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.

  12. 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

  13. Packaging biological cargoes in mesoporous materials: opportunities for drug delivery

    PubMed Central

    Siefker, Justin; Karande, Pankaj; Coppens, Marc-Olivier

    2014-01-01

    Introduction: 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. Areas covered: 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. Expert opinion: 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. PMID:25016923

  14. 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.

  15. Synthesis and characterization of nanocrystalline and mesoporous zeolites

    NASA Astrophysics Data System (ADS)

    Petushkov, Anton

    2011-12-01

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

  16. Rapid removal of bisphenol A on highly ordered mesoporous carbon.

    PubMed

    Sui, Qian; Huang, Jun; Liu, Yousong; Chang, Xiaofeng; Ji, Guangbin; Deng, Shubo; Xie, Tao; Yu, Gang

    2011-01-01

    Bisphenol A (BPA) is of global concern due to its disruption of endocrine systems and ubiquity in the aquatic environment. It is important, therefore, that efforts are made to remove it from the aqueous phase. A novel adsorbent, mesoporous carbon CMK-3, prepared from hexagonal SBA-15 mesoporous silica was studied for BPA removal from aqueous phase, and compared with conventional powdered activated carbon (PAC). Characterization of CMK-3 by transmission electron microscopy (TEM), X-ray diffraction, and nitrogen adsorption indicated that prepared CMK-3 had an ordered mesoporous structure with a high specific surface area of 920 m2/g and a pore-size of about 4.9 nm. The adsorption of BPA on CMK-3 followed a pseudo second-order kinetic model. The kinetic constant was 0.00049 g/(mg x min), much higher than the adsorption of BPA on PAC. The adsorption isotherm fitted slightly better with the Freundlich model than the Langmuir model, and adsorption capacity decreased as temperature increased from 10 to 40 degrees C. No significant influence of pH on adsorption was observed at pH 3 to 9; however, adsorption capacity decreased dramatically from pH 9 to 13. PMID:21516989

  17. 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.

  18. Transformation of layered polyoxometallate cluster salts into mesoporous materials

    SciTech Connect

    Holland, B.T.; Isbester, P.K.; Munson, E.J.; Stein, A. . Dept. of Chemistry)

    1999-02-01

    A new approach to the formation of mesoporous materials has been developed, based on a two-step salt-gel'' synthesis, in which mesoporous aluminophosphates, galloaluminophosphates, and aluminosilicates have been created. The first step involves pre-organizing charged inorganic clusters (MO[sub 4]Al[sub 12](OH)[sub 24](H[sub 2]O)[sub 12][sup 7+], M = Al or Ga) into a layered mesoscopic material with oppositely charged organic surfactant molecules. In the second step, phosphate or silicate linker molecules are added, which diffuse through the cluster/surfactant salt, react with the clusters, and transform the layered precursor into a non-lamellar mesostructured material. Removal of the surfactant from the alumino- and galloaluminophosphates by anion-exchange and from the aluminosilicates by calcination results in mesoporous materials with BET surface areas up to 630, 455, and 431 m[sup 2]/g, respectively. Direct condensation by calcination of polyoxoaluminate cluster salts without additional linkers produces nanometer-sized one-dimensional strings.

  19. 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

  20. Selective Response of Mesoporous Silicon to Adsorbants with Nitro Groups

    SciTech Connect

    McLeod, John A.; Kurmaev, Ernst Z.; Sushko, Petr V.; Boyko, Teak D.; Levitsky, Igor A.; Moewes, Alexander

    2012-01-30

    We demonstrate that the electronic structure of mesoporous silicon is affected by adsorption of nitrobased explosive molecules in a compound-selective manner. This selective response is demonstrated by probing the adsorption of two nitro-based molecular explosives (trinitrotoluene and cyclotrimethylenetrinitramine) and a nonexplosive nitro-based aromatic molecule (nitrotoluene) on mesoporous silicon using soft X-ray spectroscopy. The Si atoms strongly interact with adsorbed molecules to form Si-O and Si-N bonds, as evident from the large shifts in emission energy present in the Si L2,3 X-ray emission spectroscopy (XES) measurements. Furthermore, we find that the energy gap (band gap) of mesoporous silicon changes depending on the adsorbant, as estimated from the Si L2,3 XES and 2p X-ray absorption spectroscopy (XAS) measurements. Our ab initio molecular dynamics calculations of model compounds suggest that these changes are due to spontaneous breaking of the nitro groups upon contacting surface Si atoms. This compound-selective change in electronic structure may provide a powerful tool for the detection and identification of trace quantities of airborne explosive molecules.

  1. 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. PMID:23394515

  2. 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.

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

    PubMed

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

    2015-01-01

    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

  4. Mesoporous hexagonal Co3O4 for high performance lithium ion batteries

    PubMed Central

    Su, Dawei; Xie, Xiuqiang; Munroe, Paul; Dou, Shixue; Wang, Guoxiu

    2014-01-01

    Mesoporous Co3O4 nanoplates were successfully prepared by the conversion of hexagonal β-Co(OH)2 nanoplates. TEM, HRTEM and N2 sorption analysis confirmed the facet crystal structure and inner mesoporous architecture. When applied as anode materials for lithium storage in lithium ion batteries, mesoporous Co3O4 nanocrystals delivered a high specific capacity. At 10 C current rate, as-prepared mesoporous Co3O4 nanoplates delivered a specific capacity of 1203 mAh/g at first cycle and after 200 cycles it can still maintain a satisfied value (330 mAh/g). From ex-situ TEM, SAED and FESEM observation, it was found that mesoporous Co3O4 nanoplates were reduced to Li2O and Co during the discharge process and re-oxidised without losing the mesoporous structure during charge process. Even after 100 cycles, mesoporous Co3O4 crystals still preserved their pristine hexagonal shape and mesoporous nanostructure. PMID:25283174

  5. Preparation of activated mesoporous carbons for electrosorption of ions from aqueous solutions

    SciTech Connect

    Dai, Sheng; Lee, Jeseung; Tsouris, Costas; DePaoli, David W; Wang, Xiqing

    2010-01-01

    Mesoporous carbon with a narrow pore size distribution centered at about 9 nm, which was prepared by self assembly of block copolymer and phloroglucinol-formaldehyde resin via the soft-template method, was activated by CO{sub 2} and potassium hydroxide (KOH). The effects of activation conditions, such as the temperature, activation time, and mass ratio of KOH/C, on the textural properties of the resulting activated mesoporous carbons were investigated. Activated mesoporous carbons exhibit high BET specific surface areas (up to {approx} 2000 m{sup 2} g{sup -1}) and large pore volumes (up to {approx} 1.6 cm{sup 3} g{sup -1}), but still maintain a highly mesoporous structure. Heat treatment of mesoporous carbons by CO{sub 2} generally requires a moderate to high extent of activation in order to increase its BET surface area by 2-3 times, while KOH activation needs a much smaller degree of activation than the former to reach an identical surface area, ensuring high yields of activated mesoporous carbons. In addition, KOH activation allows a controllable degree of activation by adjusting the mass ratio of KOH/C (2-8), as evidenced by the fact that surface area and pore volume increase with the mass ratio of KOH/C. The electrosorption properties of activated mesoporous carbons were investigated by cyclic voltammetry in 0.1 M NaCl aqueous solutions. Upon activation, the electrosorption capacitance of activated mesoporous carbons was greatly enhanced.

  6. 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. PMID:26695263

  7. Surfactant-free synthesis of mesoporous and hollow silica nanoparticles with an inorganic template.

    PubMed

    Baù, Luca; Bártová, Barbora; Arduini, Maria; Mancin, Fabrizio

    2009-12-28

    A surfactant-free synthesis of mesoporous and hollow silica nanoparticles is reported in which boron acts as the templating agent. Using such a simple and mild procedure as a treatment with water, the boron-rich phase is selectively removed, affording mesoporous pure silica nanoparticles with wormhole-like pores or, depending on the synthetic conditions, silica nanoshells.

  8. 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.

  9. Hollow mesoporous aluminosilica spheres with perpendicular pore channels as catalytic nanoreactors.

    PubMed

    Fang, Xiaoliang; Liu, Zhaohui; Hsieh, Ming-Feng; Chen, Mei; Liu, Pengxin; Chen, Cheng; Zheng, Nanfeng

    2012-05-22

    The design and synthesis of hollow/yolk-shell mesoporous structures with catalytically active ordered mesoporous shells can infuse new vitality into the applications of these attractive structures. In this study, we report that hollow/yolk-shell structures with catalytically active ordered mesoporous aluminosilica shells can be easily prepared by using silica spheres as the silica precursors. By simply treating with a hot alkaline solution in the presence of sodium aluminate (NaAlO(2)) and cetyltrimethylammonium bromide (CTAB), solid silica spheres can be directly converted into high-quality hollow mesoporous aluminosilica spheres with perpendicular pore channels. On the basis of the proposed formation mechanism of etching followed by co-assembly, the synthesis strategy developed in this work can be extended as a general strategy to prepare ordered mesoporous yolk-shell structures with diverse compositions and morphologies simply by replacing solid silica spheres with silica-coated nanocomposites. The reduction of 4-nitrophenol with yolk-shell structured Au@ordered mesoporous aluminosilica as the catalyst has clearly demonstrated that the highly permeable perpendicular pore channels of mesoporous aluminosilica can effectively prevent the catalytically active yolk from aggregating. Furthermore, with accessible acidity, the yolk-shell structured ordered mesoporous aluminosilica spheres containing Pd yolk exhibit high catalytic activity and recyclability in a one-pot two-step synthesis involving an acid catalysis and subsequent catalytic hydrogenation for desired benzimidazole derivative, which makes the proposed hollow ordered aluminosilica spheres a versatile and practicable scaffold for advanced catalytic nanoreactor systems.

  10. Hollow mesoporous ceria nanoreactors with enhanced activity and stability for catalytic application.

    PubMed

    Liu, Baocang; Yu, Shengli; Wang, Qin; Hu, Wenting; Jing, Peng; Liu, Yang; Jia, Wenjing; Liu, Yongxin; Liu, Lixia; Zhang, Jun

    2013-05-01

    Novel hollow mesoporous @M/CeO(2) (M = Au, Pd, and Au-Pd) nanospheres are created. The nanospheres can be used as effective nanoreactors with superior catalytic activity and stability for reduction of 4-nitrophenol due to their hollow mesoporous structural features.

  11. 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.

  12. 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.

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

    PubMed

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

    2010-01-01

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

  14. 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.

  15. Preparation of TiO2 nanotubes/mesoporous calcium silicate composites with controllable drug release.

    PubMed

    Xie, Chunling; Li, Ping; Liu, Yan; Luo, Fei; Xiao, Xiufeng

    2016-10-01

    Nanotube structures such as TiO2 nanotube (TNT) arrays produced by self-ordering electrochemical anodization have been extensively explored for drug delivery applications. In this study, we presented a new implantable drug delivery system that combined mesoporous calcium silicate coating with nanotube structures to achieve a controllable drug release of water soluble and antiphlogistic drug loxoprofen sodium. The results showed that the TiO2 nanotubes/mesoporous calcium silicate composites were successfully fabricated by a simple template method and the deposition of mesoporous calcium silicate increased with the soaking time. Moreover, the rate of deposition of biological mesoporous calcium silicate on amorphous TNTs was better than that on anatase TNTs. Further, zinc-incorporated mesoporous calcium silicate coating, produced by adding a certain concentration of zinc nitrate into the soaking system, displayed improved chemical stability. A significant improvement in the drug release characteristics with reduced burst release and sustained release was demonstrated.

  16. Micro-mesoporous materials obtained by zeolite recrystallization: synthesis, characterization and catalytic applications.

    PubMed

    Ivanova, Irina I; Knyazeva, Elena E

    2013-05-01

    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.

  17. Preparation of TiO2 nanotubes/mesoporous calcium silicate composites with controllable drug release.

    PubMed

    Xie, Chunling; Li, Ping; Liu, Yan; Luo, Fei; Xiao, Xiufeng

    2016-10-01

    Nanotube structures such as TiO2 nanotube (TNT) arrays produced by self-ordering electrochemical anodization have been extensively explored for drug delivery applications. In this study, we presented a new implantable drug delivery system that combined mesoporous calcium silicate coating with nanotube structures to achieve a controllable drug release of water soluble and antiphlogistic drug loxoprofen sodium. The results showed that the TiO2 nanotubes/mesoporous calcium silicate composites were successfully fabricated by a simple template method and the deposition of mesoporous calcium silicate increased with the soaking time. Moreover, the rate of deposition of biological mesoporous calcium silicate on amorphous TNTs was better than that on anatase TNTs. Further, zinc-incorporated mesoporous calcium silicate coating, produced by adding a certain concentration of zinc nitrate into the soaking system, displayed improved chemical stability. A significant improvement in the drug release characteristics with reduced burst release and sustained release was demonstrated. PMID:27287140

  18. Large Enhancement in Electrorheological Activity of Mesoporous Cerium-Doped TIO2 from High Surface Area and Robust Pore Walls

    NASA Astrophysics Data System (ADS)

    Yin, Jianbo; Zhao, Xiaopeng

    Considering the importance of large interfacial or surface polarization to strong electrorheological (ER) effect, we developed a high surface area mesoporous doped TiO2 ER material by using block-copolymer. By comparing the ER experiments between samples with mesopore and without mesopore, we demonstrate a very large enhancement in ER activity of mesoporous ER material and its yield stress is 100 times that of the pure TiO2 ER material and 5-8 times that of single doped TiO2 without mesoporous structure. We give a preliminary discussion about the improvement in ER activity based on previous dielectric analysis.

  19. Bimodal mesoporous carbon synthesized from large organic precursor and amphiphilic tri-block copolymer by self assembly

    SciTech Connect

    Saha, Dipendu; Contescu, Cristian I; Gallego, Nidia C

    2012-01-01

    Owing to several disadvantages of traditional hard template based synthesis, soft-template or self-assembly was adopted to synthesize mesoporous carbon. In this work, we have introduced hexaphenol as a new and large organic precursor for the synthesis of mesoporous carbon by self-assembly with pluronic P123 as structure dictating agent. The resultant mesoporous carbon is bimodal in nature with median pore widths of 29 and 45 and BET surface area of 312 m2/g. Unlike previously synthesized mesoporous carbon, this carbon possesses negligible micropore volume. This mesoporous carbon is very suitable candidate for several applications including membrane separation, chemical sensor or selective sorption of larger molecules.

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. Multiplexed immunoassay using the stabilized enzymes in mesoporous silica.

    PubMed

    Piao, Yunxian; Lee, Dohoon; Lee, Jinwoo; Hyeon, Taeghwan; Kim, Jungbae; Kim, Hak-Sung

    2009-12-15

    Multiplexed immunoassay system was developed using the enzyme-immobilized mesoporous silica in a form of nanoscale enzyme reactors (NERs), which improve the enzyme loading, activity, and stability. Glucose oxidase (GO) and trypsin (TR) were adsorbed into mesoporous silica and further crosslinked for the construction of NERs, and antibody-conjugated NERs were employed for the analysis of target antigens in a sandwich-type magnetic bead-based immunoassay. This approach, called as NER-LISA (NER-linked immunosorbent assay), generated signals out of enzyme reactions that correlated well with the concentration of target antigens. The detection limit of NER-LISA using NER-GO and anti-human IgG was 67pM human IgG, and the sensitivity was 20 times higher than that of the conventional ELISA using anti-human IgG conjugated GO. Antibody-conjugated NER-GO and NER-TR were successfully employed for the simultaneous detection of two target antigens (human IgG and chicken IgG) in a solution by taking advantage of signals at different wavelengths (absorbances at 570nm and 410nm, respectively) from the assays of GO and TR activities, demonstrating the potential of NER-LISA in multiplexed immunoassay. The NER-LISA approach also enabled the successful use of a protease (trypsin), because the NER approach can effectively retain the protease molecules within the mesoporous silica and prevent the digestion of antibodies and enzymes during the whole process of NER-LISA.

  6. 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)

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Industrial water treatment, by adsorption, using organized mesoporous materials

    NASA Astrophysics Data System (ADS)

    Koubaissy, Bachar; Toufaily, Joumana; Kafrouny, Lina; Joly, Guy; Magnoux, Patrick; Hamieh, Tayssir

    In this work, pure silica SBA-15 was synthesized by a sol-gel method and in-situ functionalized by a series of organosilane. These mesoporous materials are used to absorb polluants from wastewater. We studied the influence of functional groups on adsorption of phenol drifts. The carboxylic acid groups and substituted chlorine on phenol have been studied. There is a sharp increase of adsorption (more than double compared to phenol) which is very encouraging. Furthermore we note that the percentage of grafted ligands also plays an important role in adsorption. Finally, the adsorption capacity also depends on the nature and percentage of ligands present.

  12. 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

  13. Functioning of nanovalves on polymer coated mesoporous silica Nanoparticles

    NASA Astrophysics Data System (ADS)

    Dong, Juyao; Xue, Min; Zink, Jeffrey I.

    2013-10-01

    Nanomachines activated by a pH change can be combined with polymer coatings on mesoporous silica nanoparticles to produce a new generation of nanoparticles for drug delivery that exhibits properties of both components. The nanovalves can trap cargos inside the mesoporous silica nanoparticles without premature release and only respond to specific stimuli, resulting in a high local concentration of drugs at the site of release. The polymer surface coatings can increase the cellular uptake, avoid the reticuloendothelial uptake, provide protected space for storing siRNA, and enhance the biodistribution of nanoparticles. Two nanovalve-polymer systems are designed and their successful assembly is confirmed by solid state NMR and thermogravimetric analysis. The fluorescence spectroscopy results demonstrate that the controlled release functions of the nanomachines in both of the systems are not hindered by the polymer surface coatings. These new multifunctional nanoparticles combining stimulated molecule release together with the functionality provided by the polymers produce enhanced biological properties and multi-task drug delivery applications.Nanomachines activated by a pH change can be combined with polymer coatings on mesoporous silica nanoparticles to produce a new generation of nanoparticles for drug delivery that exhibits properties of both components. The nanovalves can trap cargos inside the mesoporous silica nanoparticles without premature release and only respond to specific stimuli, resulting in a high local concentration of drugs at the site of release. The polymer surface coatings can increase the cellular uptake, avoid the reticuloendothelial uptake, provide protected space for storing siRNA, and enhance the biodistribution of nanoparticles. Two nanovalve-polymer systems are designed and their successful assembly is confirmed by solid state NMR and thermogravimetric analysis. The fluorescence spectroscopy results demonstrate that the controlled release

  14. 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.

  15. Studies on supercapacitor electrode material from activated lignin-derived mesoporous carbon.

    PubMed

    Saha, Dipendu; Li, Yunchao; Bi, Zhonghe; Chen, Jihua; Keum, Jong K; Hensley, Dale K; Grappe, Hippolyte A; Meyer, Harry M; Dai, Sheng; Paranthaman, M Parans; Naskar, A K

    2014-01-28

    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 Brunauer-Emmett-Teller (BET) specific surface area of 1148 m(2)/g and a pore volume of 1.0 cm(3)/g. Both physical and chemical activation enhanced the mesoporosity along with significant microporosity. 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 a range of surface-area-based capacitance similar to that of other known carbon-based supercapacitors, activation decreased the surface-area-based specific capacitance and enhanced the gravimetric specific capacitance of the mesoporous carbons. A vertical tail in the lower-frequency domain of the Nyquist plot provided additional evidence of good supercapacitor behavior for the activated mesoporous carbons. We have modeled the equivalent circuit of the Nyquist plot with the help of two constant phase elements (CPE). Our work demonstrated that biomass-derived mesoporous carbon materials continue to show potential for use in specific electrochemical applications.

  16. 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.

  17. Post-treatment and characterization of novel luminescent hybrid bimodal mesoporous silicas

    SciTech Connect

    Li Yuzhen; Sun Jihong; Wu Xia; Lin Li; Gao Lin

    2010-08-15

    A novel luminescent hybrid bimodal mesoporous silicas (LHBMS) were synthesized via grafting 1,8-Naphthalic anhydride into the pore channels of bimodal mesoporous silicas (BMMs) for the first time. The resulting samples were characterized by powder X-ray diffraction (XRD), N{sub 2} adsorption/desorption measurement, Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM), UV-vis absorption spectroscopy, and Photoluminescence spectroscopy (PL). The results show that 1,8-Naphthalic anhydride organic groups have been successfully introduced into the mesopores of the BMMs and the hybrid silicas are of bimodal mesoporous structure with the ordered small mesopores of around 3 nm and the large mesopores of uniform intra-nanoparticle. The excellent photoluminescent performance of LHBMS has a blue shift compared to that of 2-[3-(triethoxysilyl) propyl-1 H-Benz [de]isoquinoline-1, 3(2 H)-dione, suggesting the existence of the quantum confinement effectiveness. - Graphical abstract: A novel luminescent hybrid bimodal mesoporous silicas was synthesized via modification and then grafting with 1, 8-Naphthalic anhydride, which would be strong potential application in the photoluminescent fields.

  18. "Bricks and mortar" self-assembly approach to graphitic mesoporous carbon nanocomposites

    SciTech Connect

    Fulvio, P. F.; Mayes, R.; Wang, X. Q.; Mahurin, S., M.; Bauer, J. C.; Presser, V.; McDonough, J.; Gogotsi, Y.; Dai, S.

    2011-04-20

    Mesoporous carbon materials do not have sufficient ordering at the atomic scale to exhibit good electronic conductivity. To date, mesoporous carbons having uniform mesopores and high surface areas have been prepared from partially-graphitizable precursors in the presence of templates. High temperature thermal treatments above 2000 °C, which are usually required to increase conductivity, result in a partial or total collapse of the mesoporous structures and reduced surface areas induced by growth of graphitic domains, limiting their applications in electric double layer capacitors and lithium-ion batteries. In this work, we successfully implemented a “brick-and-mortar” approach to obtain ordered graphitic mesoporous carbon nanocomposites with tunable mesopore sizes below 850 °C without using graphitization catalysts or high temperature thermal treatments. Phenolic resin-based mesoporous carbons act as mortar to highly conductive carbon blacks and carbon onions (bricks). The capacitance and resistivity of final materials can be tailored by changing the mortar to brick ratios.

  19. Shape-Enhanced Photocatalytic Activities of Thoroughly Mesoporous ZnO Nanofibers.

    PubMed

    Ren, Xiaolong; Hou, Huilin; Liu, Zhixiong; Gao, Fengmei; Zheng, Jinju; Wang, Lin; Li, Wenge; Ying, Pengzhan; Yang, Weiyou; Wu, Tom

    2016-08-01

    1D mesoporous materials have attracted extensive interest recently, owning to their fascinating properties and versatile applications. However, it remains as a grand challenge to develop a simple and efficient technique to produce oxide nanofibers with mesoporous architectures, controlled morphologies, large surface areas, and optimal performances. In this work, a facile foaming-assisted electrospinning strategy with foaming agent of tea saponin is used to produce thoroughly mesoporous ZnO nanofibers with high purity and controlled morphology. Interestingly, mesoporous fibers with elliptical cross-section exhibit the significantly enhanced photocatalytic activity for hydrogen production, as compared to the counterparts with circular and rectangular cross-sections, and they also perform better than the commercial ZnO nanopowders. The unexpected shape dependence of photocatalytic activities is attributed to the different stacking modes of the mesoporous fibers, and a geometrical model is developed to account for the shape dependence. This work represents an important step toward producing thoroughly mesoporous ZnO nanofibers with tailored morphologies, and the discovery that fibers with elliptical cross-section render the best performance provides a valuable guideline for improving the photocatalytic performance of such mesoporous nanomaterials. PMID:27337544

  20. Mesoporous ZnS–NiS Nanocomposites for Nonenzymatic Electrochemical Glucose Sensors

    PubMed Central

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

    2015-01-01

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

  1. 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.

  2. 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.

  3. Hollow mesoporous carbon spheres with magnetic cores and their performance as separable bilirubin adsorbents.

    PubMed

    Guo, Limin; Cui, Xiangzhi; Li, Yongsheng; He, Qianjun; Zhang, Lingxia; Bu, Wenbo; Shi, Jianlin

    2009-09-01

    Hollow mesoporous carbon spheres with magnetic cores are directly replicated from hollow mesoporous aluminosilicate spheres with hematite cores by a simple incipient-wetness impregnation technique. The amount of magnetic cores and the saturation magnetization value can be easily tuned by changing the concentration of iron nitrate solution used in the synthesis procedure. As-prepared hollow mesoporous carbon spheres with magnetic cores are used as separable bilirubin adsorbents and show very good adsorptive properties. The characteristics of as-prepared composites are examined by XRD, N(2) sorption, TEM, vibrating-sample magnetometry, and UV/Vis spectroscopy. PMID:19582733

  4. 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.

  5. Enhanced capacitive deionization of graphene/mesoporous carbon composites.

    PubMed

    Zhang, Dengsong; Wen, Xiaoru; Shi, Liyi; Yan, Tingting; Zhang, Jianping

    2012-09-01

    Capacitive deionization (CDI) with low-energy consumption and no secondary waste is emerging as a novel desalination technology. Graphene/mesoporous carbon (GE/MC) composites have been prepared via a direct triblock-copolymer-templating method and used as CDI electrodes for the first time. The influences of GE content on the textural properties and electrochemical performance were studied. The transmission electron microscopy and nitrogen adsorption-desorption analysis indicate that mesoporous structures are well retained and the composites display improved specific surface area and pore size distribution, as well as pore volume. Well dispersed GE nanosheets are deduced to be beneficial for enhanced electrical conductivity. The electrochemical performance of electrodes in an NaCl aqueous solution was characterized by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy measurements. The composite electrodes perform better on the capacitance values, conductive behaviour, rate performance and cyclic stability. The desalination capacity of the electrodes was evaluated by a batch mode electrosorptive experiment and the amount of adsorbed ions can reach 731 μg g⁻¹ for the GE/MC composite electrode with a GE content of 5 wt%, which is much higher than that of MC alone (590 μg g⁻¹). The enhanced CDI performance of the composite electrodes can be attributed to the better conductive behaviour and higher specific surface area.

  6. 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.

  7. Facile fabrication and supercapacitive properties of mesoporous zinc cobaltite microspheres

    NASA Astrophysics Data System (ADS)

    Wang, Qinghong; Du, Jialu; Zhu, Yuxuan; Yang, Jiaqin; Chen, Juan; Wang, Chao; Li, Liang; Jiao, Lifang

    2015-06-01

    Mesoporous zinc cobaltite (ZnCo2O4) microspheres have been successfully prepared by a facile solvothermal method followed by an annealing process. The as-prepared ZnCo2O4 displays uniform sphere-like morphology composed of interconnected ZnCo2O4 nanoparticles. The Brunauer-Emmett-Teller (BET) surface area of mesoporous ZnCo2O4 microspheres is about 51.4 m2 g-1 with dominant pore diameter of 7.5 nm. The novel ZnCo2O4 material exhibits high specific capacitance of 953.2 F g-1 and 768.5 F g-1 at discharge current densities of 4 A g-1 and 30 A g-1, respectively. The energy density can be estimated to be 26.68 Wh kg-1 at a power density of 8 kW kg-1. The specific capacitance retention is 97.8% after 3000 cycles, suggesting its excellent cycling stability. The superior electrochemical performance is mainly attributed to the uniformity of the surface structure and the porosity of the microspheres, which benefit electrons and ions transportation, provide large electrode-electrolyte contact area, and meanwhile reduce volume change during the charge-discharge process. This method of constructing porous microspheres is very effective, yet simple, and it could be applied in other high-performance metal oxide electrode materials for electrochemical capacitors, as well as in Li-ion batteries.

  8. 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.

  9. 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.

  10. Mesoporous aluminosilicate ropes with improved stability from protozeolitic nanoclusters

    SciTech Connect

    Zheng Junlin; Kong Dejin; Yang Weimin; Xie Zaiku; Wu Dong; Sun Yuhan

    2007-02-15

    Mesoporous aluminosilicate ropes with improved hydrothermal stability have been prepared through S{sup +}X{sup -}I{sup +} route via self-assembly of protozeolitic nanoclusters with cetyltrimethylammonium bromides (CTAB) template micelles in HNO{sub 3} solution. SEM observation confirmed that high-yield aluminosilicate ropes could be produced under proper HNO{sub 3} concentration. NO{sub 3} {sup -} ions had strong binding strength to the CTA{sup +} ions and tended to form more elongated surfactant micelles, thus fibrous products were fabricated under the direction of these long rod micelles in shearing flow. At the same time, the NO{sub 3} {sup -} ions combining with CTA{sup +} ions generated more active (CTA{sup +}NO{sub 3} {sup -}) assembly, which effectively catalysed the polymerization of protozeolitic nanoclusters with large volume into highly ordered mesostructures. Compared with normal MCM-41 silica synthesized through S{sup +}X{sup -}I{sup +} route in acidic media, the hydrothermal stability was improved considerably. These protozeolitic nanoclusters survived strongly acidic media and entered into mesostructured framework, which contributed to the improvement of hydrothermal stability. - Graphical abstract: Mesoporous aluminosilicate ropes with enhanced hydrothermal stability were fabricated from protozeolitic nanoclusters through S{sup +}X{sup -}I{sup +} route in HNO{sub 3} solution under the direction of CTAB templates.

  11. 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. PMID:26673796

  12. 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.

  13. Mesoporous Zirconium Phenylenesiliconate-phosphonate Hybrids with Ordered Lamellar Nanostructures.

    PubMed

    Maeda, Kazuyuki; Kobayashi, Hiroki; Oguro, Kaku; Otsu, Masato; Kondo, Atsushi; Maki, Tei

    2015-11-16

    Novel ordered lamellar mesostructure pZrPS-2 was hydrothermally prepared by using zirconium propoxide and 4-(EtO)2OPC6H4Si(OEt)3 (pPPS-E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of Cn TAB and TMAOH. The pZrPS-2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer-chain surfactant (n = 12-18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS-2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia-based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS-2. A possible schematic model to elucidate these results is also proposed. PMID:26427615

  14. Optical detection of E. coli bacteria by mesoporous silicon biosensors.

    PubMed

    Massad-Ivanir, Naama; Shtenberg, Giorgi; Segal, Ester

    2013-01-01

    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.

  15. 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

  16. 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.

  17. 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.

  18. Periodic mesoporous organosilica with a hexagonally pillared lamellar structure.

    PubMed

    Lee, Hyung Ik; Kim, Ji Man; Stucky, Galen D

    2009-10-14

    Ordered mesoporous materials (OMMs) with well-defined pore sizes (>2 nm) and pore geometries are important in various applications that require fast mass transfer or deal with large molecules. Extensive research has resulted in the discovery of OMMs with three types of mesostructures: (i) bi- or multicontinuous, (ii) columnar, and (iii) discontinuous (cagelike). However, another type, the pillared lamellar structure, which has long been sought and has been mathematically computed and known to exist in the research fields of surfactant and multiblock-copolymer mesophases, still remains a mesostructure that has not been observed in real OMMs for any specific symmetry. Herein, we report an unprecedented type of ordered mesoporous material with a hexagonally pillared lamellar (HPL) structure (P6(3)/mmc) that can be synthesized via a phase transformation from a lamellar mesophase by hydrothermal reaction in the presence of an organosilica precursor and a high concentration of a designed Gemini surfactant (Gem(16-3-16)) that has a large g value. The present GMO-HPL, which has an unique three-dimensional periodic structure with two-dimensionally connected pore channels running between the framework layers, provides a fascinating topological link between the lamellar and columnar (2D hexagonal) mesophases. It is unique in its application potential by making possible selective 2D diffusion in different directions.

  19. 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

  20. Template-free fabrication of mesoporous carbons from carbon quantum dots and their catalytic application to the selective oxidation of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Zhou, Lei; Liu, Juan; Zhang, Xing; Liu, Ruihua; Huang, Hui; Liu, Yang; Kang, Zhenhui

    2014-05-01

    Mesoporous carbons (pore size 5 nm) were successfully synthesized without templates from carbon quantum dots. As catalysts, both mesoporous carbons and Cu nanoparticles on mesoporous carbons show superior catalytic activity and stability for the selective oxidation of cyclooctene.Mesoporous carbons (pore size 5 nm) were successfully synthesized without templates from carbon quantum dots. As catalysts, both mesoporous carbons and Cu nanoparticles on mesoporous carbons show superior catalytic activity and stability for the selective oxidation of cyclooctene. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00716f

  1. 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.

  2. Improved catalytic capability of mesoporous TiO2 microspheres and photodecomposition of toluene.

    PubMed

    Feng, Yinchang; Li, Lei; Ge, Ming; Guo, Changsheng; Wang, Junfeng; Liu, Lu

    2010-11-01

    A series of mesoporous titanium dioxide microspheres were calcined at various temperatures to improve their photocatalytic activity. The prepared catalysts were characterized by XRD, SEM, TEM, TG-DTA, UV-vis, and N(2) adsorption-desorption measurements, and their photocatalytic performances were investigated by photooxidation of gaseous toluene. As the results revealed, calcination temperatures obviously influenced the surface morphology and photocatalytic activity of the mesoporous TiO(2) microspheres. The noncalcined samples had a mesoporous structure of the anatase phase. The sample calcined at 400 °C showed a superior photocatalytic performance, which had a reaction rate constant 2-fold higher than that of P(25). The enhanced photoreactivity is possibly due to the synergetic effects of the mesoporous structure and light-transmittance ability of the catalysts. Two new reaction intermediates were discovered as well, and a tentative degradation pathway was proposed. PMID:20968291

  3. Nucleic acid-mesoporous silica nanoparticle conjugates for keypad lock security operation.

    PubMed

    Pu, Fang; Liu, Zhen; Ren, Jinsong; Qu, Xiaogang

    2013-03-21

    We fabricated a keypad lock system based on mesoporous silica nanoparticle (MSN)-nucleic acid conjugates. DNA strand displacement triggered the release of guest molecules entrapped within the pores of MSNs through logic-based control.

  4. Alcohols solubilization in a nonionic fluorinated surfactant based system: effects on the characteristics of mesoporous silica.

    PubMed

    Blin, J L; Du, N; Stébé, M J

    2012-05-01

    In this study, we have used hydrogenated alcohols with different chain lengths and one fluorinated alcohol as additives to determine their effect on the characteristics of mesoporous materials prepared from fluorinated micelles.

  5. 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. PMID:24335918

  6. Self-Assembly and Compartmentalization of Nanozymes in Mesoporous Silica-Based Nanoreactors.

    PubMed

    Huang, Yanyan; Lin, Youhui; Ran, Xiang; Ren, Jinsong; Qu, Xiaogang

    2016-04-11

    Herein, to mimic complex natural system, polyelectrolyte multilayer (PEM)-coated mesoporous silica nanoreactors were used to compartmentalize two different artificial enzymes. PEMs coated on the surface of mesoporous silica could serve as a permeable membrane to control the flow of molecules. When assembling hemin on the surface of mesoporous silica, the hemin-based mesoporous silica system possessed remarkable peroxidase-like activity, especially at physiological pH, and could be recycled more easily than traditional graphene-hemin nanocompounds. The hope is that these new findings may pave the way for exploring novel nanoreactors to achieve compartmentalization of nanozymes and applying artificial cascade catalytic systems to mimic cell organelles or important biochemical transformations.

  7. 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.

  8. Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica.

    PubMed

    Ji, Yazhou; Caskey, Christopher; Richards, Ryan M

    2015-01-01

    As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

  9. Mesoporous graphitic carbon nanodisks fabricated via catalytic carbonization of coordination polymers.

    PubMed

    Su, Panpan; Jiang, Liang; Zhao, Jiao; Yan, Jingwang; Li, Can; Yang, Qihua

    2012-09-11

    Mesoporous graphitic carbon nanodisks with hierarchical porous structure, facilely fabricated by catalytic carbonization of iron-based coordination polymer nanodisks, exhibit high capacitance even at high scan rates as electrode materials for electrochemical double layer capacitors.

  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. Biocatalytic approach for polymer synthesis and polymer encapsulation in mesoporous materials

    NASA Astrophysics Data System (ADS)

    Ford, Christy

    The goal of this research is to encapsulate enzymatically synthesized polymers within the pores of mesoporous silica. In order to fully understand the effect of polymer incorporation on mesoporous silica structure, the effect of dopant and polymer on micelle shape, the effect of dopant on the final mesoporous silica structure, and the effect of incorporating polymer within mesoporous silica are investigated. Direct entrapment of aromatic molecules within cationic micelles to ultimately fabricate tailored, functional mesoporous silica/polymer composites is investigated. Specifically, the influence of 4-ethylphenol and aniline on the shape of cetyltrimethylammonium bromide (CTAB) micelles and on the structure of mesoporous silica synthesized via the micellar templating is investigated. Small angle neutron scattering indicates that the dopant affects the micellar size, micellar arrangement, and the domain size over which the arrangement extends. Cryo-TEM offers further insight into the micellar shape. The effect of the dopant-to-surfactant molar ratio on the structure of surfactant-templated mesoporous silica is characterized by x-ray diffraction, transmission electron microscopy, and nitrogen sorption techniques. The mesoporous silica undergoes a transition from hexagonal to lamellar with increasing dopant-to-surfactant molar ratio for both 4-ethylphenol and 2-naphthol, suggesting a possible change in the template morphology. A better understanding of the relation between dopant, micellar shape, and mesoporous structure plays a critical role in the development of polymer-ceramic nanocomposites with novel electrooptical, conductive, and fluorescent properties. A novel method for encapsulating polymers in mesoporous silica is presented. The method involves enzymatic synthesis of polyphenols and polyaromatic amines in micellar aggregates, and subsequently condensing silica at the surfactant-water interface. Thus, poly(4-ethylphenol), poly(2-naphthol), and polyaniline

  12. Development of nanoaptamers using a mesoporous silica model labeled with (99m)tc for cancer targeting.

    PubMed

    Sá, Lucas Torres Miranda; Pessoa, Claudia; Meira, Assuero Silva; da Silva, Maria Isabel Pais; Missailidis, Sotiris; Santos-Oliveira, Ralph

    2012-01-01

    The use of mesoporous silica in targeted cancer therapy is increasing daily. The combination of a rigid model of nanoparticles like mesoporous silica and biological compounds with an affinity for oncological diseases is the most promising drug-targeting system nowadays. In this study, we used the mesoporous silica SBA-15 combined with aptamer (functionalized for tumor with MUC1). The results obtained were of interest and showed the formation of the silica mesoporous structure. The impregnation methodology of mesoporous silica with the aptamer was also confirmed. Cytotoxicity results demonstrated that the particle associated with the aptamer has no cytotoxicity. We conclude that although further studies are required, the mesoporous silica nanoparticle model loaded with aptamer is very functional and can be used for other applications, especially in nuclear medicine. PMID:22508189

  13. 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.

  14. The sonochemical synthesis and characterization of mesoporous chiral titania using a chiral inorganic precursor.

    PubMed

    Gabashvili, Alexandra; Major, Dan T; Perkas, Nina; Gedanken, Aharon

    2010-03-01

    The paper presents a successful sonochemical attempt to synthesize mesoporous chiral titania using a chiral inorganic precursor and dodecylamine, as the surfactant template. The resulting porous structure was characterized by nitrogen sorption experiments, transmission electron microscopy, and small-angle XRD. The enantioselectivity of this mesoporous titania after the extraction of the amine was examined by selective adsorption of enantiomers and racemic aqueous solution of camphor. The selective adsorption was measured by circular dichroism (CD) spectroscopy. PMID:19942471

  15. Mixed surfactants-directed the mesoporous silica materials with various morphologies and structures

    SciTech Connect

    Lin Huiming; Qu Fengyu; Wu Xiang; Xue Ming; Zhu Guangshan; Qiu Shilun

    2011-06-15

    A new mixed surfactants system using alkyl carboxylic acids and quaternized poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl] urea] (PEPU) as the co-template was used to synthesize mesoporous silica materials with various morphologies and structures, including flakes, regular spheres, nanoparticles, and tube-spheres. The cationic polymer connected the anionic surfactant micelle to the anionic polysilicate species to induce the synthesis of the mesoporous silica materials. The structure and property of the surfactant and the cationic polymer determined the formation of mesoporous silica, and also had a signification influence on the morphology and structure of the final materials. To further explore the possible formation mechanism of these mesoporous materials, zeta potential was utilized to evaluate the interaction between the anionic surfactant and the cationic co-template. In addition, the structure, morphology, and porosity of these materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N{sub 2} adsorption-desorption measurements. - Graphical abstract: A new mixed surfactants system using alkyl carboxylic acids and PEPU as the co-template was used to synthesize mesoporous silica materials with various morphologies and structures. Highlights: {yields}A new mixed surfactants system induced the mesoporous silica materials with various morphologies and structure. > It is a development of the type S{sup -}N{sup +}I{sup -} route of the mesoporous formation. > Zeta potential was utilized to evaluate the interaction between the anionic surfactant and the cationic co-template. > The property and amount of surfactant and polymer determined the formation of the mesoporous materials.

  16. 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

  17. Bifunctionalized mesoporous silica-supported gold nanoparticles: intrinsic oxidase and peroxidase catalytic activities for antibacterial applications.

    PubMed

    Tao, Yu; Ju, Enguo; Ren, Jinsong; Qu, Xiaogang

    2015-02-11

    Bifunctionalized mesoporous silica-supported gold nanoparticles as oxidase and peroxidase mimics for antibacterial applications are demonstrated. For the first time, these mesoporous silica-supported gold nanoparticles are applied as oxidase and peroxidase mimics. Taking advantage of their prominent enzyme activities, the MSN-AuNPs show excellent antibacterial properties against both Gram-negative and Gram-positive bacteria. Furthermore, MSN-AuNPs also exhibit outstanding performance in biofilm elimination . PMID:25655182

  18. Synthesis and Characterization of Mesoporous Silica Functionalized with Calix[4]arene Derivatives

    PubMed Central

    Alahmadi, Sana M.; Mohamad, Sharifah; Maah, Mohd Jamil

    2012-01-01

    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. PMID:23202977

  19. Membrane interactions of mesoporous silica nanoparticles as carriers of antimicrobial peptides.

    PubMed

    Braun, Katharina; Pochert, Alexander; Lindén, Mika; Davoudi, Mina; Schmidtchen, Artur; Nordström, Randi; Malmsten, Martin

    2016-08-01

    Membrane interactions are critical for the successful use of mesoporous silica nanoparticles as delivery systems for antimicrobial peptides (AMPs). In order to elucidate these, we here investigate effects of nanoparticle charge and porosity on AMP loading and release, as well as consequences of this for membrane interactions and antimicrobial effects. Anionic mesoporous silica particles were found to incorporate considerable amounts of the cationic AMP LLGDFFRKSKEKIGKEFKRIVQRIKDFLRNLVPRTES (LL-37), whereas loading is much lower for non-porous or positively charged silica nanoparticles. Due to preferential pore localization, anionic mesoporous particles, but not the other particles, protect LL-37 from degradation by infection-related proteases. For anionic mesoporous nanoparticles, membrane disruption is mediated almost exclusively by peptide release. In contrast, non-porous silica particles build up a resilient LL-37 surface coating due to their higher negative surface charge, and display largely particle-mediated membrane interactions and antimicrobial effects. For positively charged mesoporous silica nanoparticles, LL-37 incorporation promotes the membrane binding and disruption displayed by the particles in the absence of peptide, but also causes toxicity against human erythrocytes. Thus, the use of mesoporous silica nanoparticles as AMP delivery systems requires consideration of membrane interactions and selectivity of both free peptide and the peptide-loaded nanoparticles, the latter critically dependent on nanoparticle properties. PMID:27174622

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. Supported mesoporous carbon ultrafiltration membrane and process for making the same

    DOEpatents

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

    2004-04-13

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

  5. 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.

  6. 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. PMID:14968882

  7. Synthesis, characterization and magnetic performance of Co-incorporated ordered mesoporous carbons

    SciTech Connect

    Liu, Zhi; Song, Yan; Yang, Yuan; Mi, Junhua; Deng, Liping

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer A facile one-pot aqueous self-assembly strategy for the synthesis Co-incorporated ordered mesoporous carbons (Co-OMCs). Black-Right-Pointing-Pointer Co-OMCs exhibit typical ferromagnetic characteristics. Black-Right-Pointing-Pointer Saturation magnetization strength can be easily adjusted by changing the content of cobalt. Black-Right-Pointing-Pointer Carbonization temperatures have significant effects on the structure and magnetic properties of Co-OMCs. -- Abstract: Co-incorporated ordered mesoporous carbon (Co-OMC) with magnetic frameworks has been synthesized via a one-pot self-assembly strategy. The effects of cobalt loading on carbon matrix, adsorption properties and magnetic properties of the resultant mesostructured cobalt/carbon composites were investigated by nitrogen sorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG) and magnetometer measurements. The results show that the mesoporous composites with a high cobalt content (such as 18.0 wt%) possess an ordered and uniform mesoporous structure (5.3 nm), high surface areas (up to 687 m{sup 2}/g) and high pore volumes (up to 0.54 cm{sup 3}/g). Cobalt nanoparticles of size 4-9 nm are confined inside the mesopores or walls of the mesoporous carbon. These materials exhibit typical ferromagnetic characteristics. The saturation magnetization strength can be easily adjusted by changing the content of cobalt. The carbonization temperatures have significant effects on the structure and magnetic properties of Co-OMC also.

  8. 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.

  9. Effective enrichment and mass spectrometry analysis of phosphopeptides using mesoporous metal oxide nanomaterials.

    PubMed

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

    2010-09-01

    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 dioxide (ZrO(2)) nanomaterials for effective phosphopeptide enrichment. Here, we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO(2)), ZrO(2), and hafnium dioxide (HfO(2)) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO(2) and HfO(2) are demonstrated to be superior to TiO(2) 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 alpha-casein identified 21 out of 22 phosphorylation sites for alpha-casein. Moreover, the mesoporous ZrO(2) and HfO(2) can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO(2) and HfO(2) nanomaterials hold great promise for applications in MS-based phosphoproteomics.

  10. 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.

  11. Alkali oxide containing mesoporous bioactive glasses: synthesis, characterization and in vitro bioactivity.

    PubMed

    Vaid, Chitra; Murugavel, Sevi

    2013-03-01

    We report, for the first time, the synthesis of sodium oxide containing mesoporous bioactive quaternary glasses and compared with two different mesoporous ternary silicate systems by modified sol-gel process. With the aid of three different glass systems, a systematic analysis has been made on phosphorous-bearing (P-bearing) and phosphorous-free (P-free) mesoporous bioactive glasses to investigate the role of phosphorus on in vitro bioactivity of various silicate glasses with constant alkali oxide content. The combined use of multiple analytical techniques XRD, FTIR, SEM, nitrogen adsorption/desorption analysis before and after soaking in the SBF solution allowed us to establish strong correlation between composition, pore structure and bioactivity. We find that the P-bearing mesoporous glasses show the rapid hydroxycarbonate apatite (HCA) crystallization than P-free mesoporous glasses independent of calcium content. The present study reveals that the presence of phosphorous jointly with calcium in the bioactive glass system significantly enhances the rate of apatite formation as well as crystallization of apatite phase. Additionally, we find that a glass with sodium orthophosphate rich phase enhances the solubility when immersed in SBF and further accelerate the kinetics of apatite formation. The influences of the chemical composition and their superior textural properties on bioactivity are explained in terms of the unique structure of mesoporous bioactive glasses.

  12. High performance of phosphonate-functionalized mesoporous silica for U(VI) sorption from aqueous solution.

    PubMed

    Yuan, Li-Yong; Liu, Ya-Lan; Shi, Wei-Qun; Lv, Yu-Long; Lan, Jian-Hui; Zhao, Yu-Liang; Chai, Zhi-Fang

    2011-07-28

    The renaissance of nuclear energy promotes increasing basic research on the separation and enrichment of nuclear fuel associated radionuclides. Herein, we report the first study for developing mesoporous silica functionalized with phosphonate (NP10) as a sorbent for U(VI) sorption from aqueous solution. The mesoporous silica was synthesized by co-condensation of diethylphosphatoethyltriethoxysilane (DPTS) and tetraethoxysilane (TEOS), using cationic surfactant cetyltrimethylammonium bromide (CTAB) as the template. The synthesized silica nanoparticles were observed to possess a mesoporous structure with a uniform pore diameter of 2.7 nm, and to have good stability and high efficiency for U(VI) sorption from aqueous solution. A maximum sorption capacity of 303 mg g(-1) and fast equilibrium time of 30 min were achieved under near neutral conditions at room temperature. The adsorbed U(VI) can be easily desorbed by using 0.1 mol L(-1) HNO(3), and the reclaimed mesoporous silica can be reused with no decrease of sorption capacity. In addition, the preconcentration of U(VI) from a 100 mL aqueous solution using the functionalized mesoporous silica was also studied. The preconcentration factor was found to be as high as 100, suggesting the vast opportunities of this kind of mesoporous silica for the solid-phase extraction and enrichment of U(VI). PMID:21681327

  13. Hazardous dyes removal from aqueous solution over mesoporous aluminophosphate with textural porosity by adsorption.

    PubMed

    Kannan, Chellapandian; Muthuraja, Kumarasamy; Devi, Murugan R

    2013-01-15

    Dye pollution in aquatic nature produce serious environmental effects. In this investigation, mesoporous aluminophosphate molecular sieve synthesized and applied for the removal of hazardous dyes Malachite green (MG) and Methylene blue (MB). In the synthesis of mesoporous aluminophosphate (AlPO(4)) molecular sieve, the structure-directing agent, long-chain alkylbenzene has been used as a template. The template used for the synthesis of mesoporous material is environmentally biodegradable. The mesoporous AlPO(4) was synthesized by the absence of an organic base, tetramethyl ammonium hydroxide (TMAOH) which is necessary to maintain the pH for the conventional AlPO(4) synthesis methods. The synthesized mesoporous AlPO(4) has high thermal stability up to 1173K and large porosity nature (40 nm). It was confirmed by the characterization techniques such as low-angle XRD, FT-IR, TGA and BET surface area analysis. The morphology of the material was explained by using SEM and TEM. The hazardous dyes MG and MB removal studied under the various conditions like contact time, dye concentration, temperature, pH and adsorbent dosage to examine the adsorption characteristics of the newly synthesized mesoporous AlPO(4) molecular sieves.

  14. Membrane interactions of mesoporous silica nanoparticles as carriers of antimicrobial peptides.

    PubMed

    Braun, Katharina; Pochert, Alexander; Lindén, Mika; Davoudi, Mina; Schmidtchen, Artur; Nordström, Randi; Malmsten, Martin

    2016-08-01

    Membrane interactions are critical for the successful use of mesoporous silica nanoparticles as delivery systems for antimicrobial peptides (AMPs). In order to elucidate these, we here investigate effects of nanoparticle charge and porosity on AMP loading and release, as well as consequences of this for membrane interactions and antimicrobial effects. Anionic mesoporous silica particles were found to incorporate considerable amounts of the cationic AMP LLGDFFRKSKEKIGKEFKRIVQRIKDFLRNLVPRTES (LL-37), whereas loading is much lower for non-porous or positively charged silica nanoparticles. Due to preferential pore localization, anionic mesoporous particles, but not the other particles, protect LL-37 from degradation by infection-related proteases. For anionic mesoporous nanoparticles, membrane disruption is mediated almost exclusively by peptide release. In contrast, non-porous silica particles build up a resilient LL-37 surface coating due to their higher negative surface charge, and display largely particle-mediated membrane interactions and antimicrobial effects. For positively charged mesoporous silica nanoparticles, LL-37 incorporation promotes the membrane binding and disruption displayed by the particles in the absence of peptide, but also causes toxicity against human erythrocytes. Thus, the use of mesoporous silica nanoparticles as AMP delivery systems requires consideration of membrane interactions and selectivity of both free peptide and the peptide-loaded nanoparticles, the latter critically dependent on nanoparticle properties.

  15. Application of mesoporous carbon to counter electrode for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Guiqiang; Xing, Wei; Zhuo, Shuping

    The mesoporous carbons were prepared by the carbonation of the triblock copolymer F127/phloroglucinol-formaldehyde composite self-assembled in an acid medium and employed as the catalyst for triiodide reduction in dye-sensitized solar cells (DSCs). The characteristics of mesoporous carbon were analyzed by scanning electron microscopy, transmission electron microscopy, N 2 sorption measurement and X-ray diffraction. The mesoporous carbon with low crystallinity exhibited Brunauer-Emmett-Teller surface area of 400 m 2 g -1, pore diameter of 6.8 nm and pore volume of 0.63 cm 3 g -1. The photovoltaic performances of DSCs with mesoporous carbon counter electrode were improved by increasing the carbon loading on counter electrode due to the charge-transfer resistance of mesoporous carbon counter electrode decreasing with the increase of the carbon loading. However, further carbon loading increase has no obvious effect on the photovoltaic performance of DSCs with carbon electrode when carbon loading exceeds 300 μg cm -2. The overall conversion efficiency of 6.18% was obtained by DSCs composed of mesoporous carbon counter electrode with the carbon loading of 339 μg cm -2. This value is comparable to that of DSCs with conventional platinum counter electrode.

  16. 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.

  17. Carbon functionalized mesoporous silica-based gas sensors for indoor volatile organic compounds.

    PubMed

    Liu, Yupu; Chen, Junchen; Li, Wei; Shen, Dengke; Zhao, Yujuan; Pal, Manas; Yu, Haijun; Tu, Bo; Zhao, Dongyuan

    2016-09-01

    Indoor organic gaseous pollution is a global health problem, which seriously threats the health and life of human all over the world. Hence, it is important to fabricate new sensing materials with high sensitivity and efficiency for indoor volatile organic compounds. In this study, a series of ordered mesoporous silica-based nanocomposites with uniform carbon coatings on the internal surface of silica mesopore channels were synthesized through a simple template-carbonization strategy. The obtained mesoporous silica-carbon nanocomposites not only possess ordered mesostructures, high surface areas (up to ∼759m(2)g(-1)), large and tunable pore sizes (2.6-10.2nm), but also have the improved hydrophobicity and anti-interference capability to environmental humidity. The sensing performances of the mesoporous silica-carbon nanocomposites to volatile organic compounds, such as ethylbenzene, methylbenzene, benzene, methanol, acetone, formaldehyde, dichloromethane and tetrahydrofuran, were systematically investigated. The relationships between the sensing performances and their properties, including mesostructures, surface areas, pore sizes, carbon contents and surface hydrophilic/hydrophobic interactions, have been achieved. The mesoporous silica-carbon nanocomposites with hexagonal mesostructure exhibit outstanding performance at room temperature to benzene and acetone with high responses, short response (2-3s) and recovery (16-19s) time, strong anti-interference to environmental humidity, and long-term stability (less than ∼5% loss of the frequency shifts after 42days). Therefore, the obtained mesoporous silica-carbon nanocomposites have a hopeful prospect in the field of environmental air quality monitoring.

  18. 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

  19. Utilization of a By-product Produced from Oxidative Desulfurization Process over Cs-Mesoporous Silica Catalysts

    SciTech Connect

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

    2011-02-28

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

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

    PubMed

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

    2011-02-01

    We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process. PMID:21456272

  1. 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

  2. Enhanced capacitive deionization of graphene/mesoporous carbon composites

    NASA Astrophysics Data System (ADS)

    Zhang, Dengsong; Wen, Xiaoru; Shi, Liyi; Yan, Tingting; Zhang, Jianping

    2012-08-01

    Capacitive deionization (CDI) with low-energy consumption and no secondary waste is emerging as a novel desalination technology. Graphene/mesoporous carbon (GE/MC) composites have been prepared via a direct triblock-copolymer-templating method and used as CDI electrodes for the first time. The influences of GE content on the textural properties and electrochemical performance were studied. The transmission electron microscopy and nitrogen adsorption-desorption analysis indicate that mesoporous structures are well retained and the composites display improved specific surface area and pore size distribution, as well as pore volume. Well dispersed GE nanosheets are deduced to be beneficial for enhanced electrical conductivity. The electrochemical performance of electrodes in an NaCl aqueous solution was characterized by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy measurements. The composite electrodes perform better on the capacitance values, conductive behaviour, rate performance and cyclic stability. The desalination capacity of the electrodes was evaluated by a batch mode electrosorptive experiment and the amount of adsorbed ions can reach 731 μg g-1 for the GE/MC composite electrode with a GE content of 5 wt%, which is much higher than that of MC alone (590 μg g-1). The enhanced CDI performance of the composite electrodes can be attributed to the better conductive behaviour and higher specific surface area.Capacitive deionization (CDI) with low-energy consumption and no secondary waste is emerging as a novel desalination technology. Graphene/mesoporous carbon (GE/MC) composites have been prepared via a direct triblock-copolymer-templating method and used as CDI electrodes for the first time. The influences of GE content on the textural properties and electrochemical performance were studied. The transmission electron microscopy and nitrogen adsorption-desorption analysis indicate that mesoporous structures are

  3. Towards understanding of shape formation mechanism of mesoporous silica particles.

    PubMed

    Volkov, Dmytro O; Benson, James; Kievsky, Yaroslav Y; Sokolov, Igor

    2010-01-14

    Growth of even simple crystals is a rather hard problem to describe because of the non-equilibrium nature of the process. Meso(nano)porous silica particles, which are self-assembled in a sol-gel template synthesis, demonstrate an example of shapes of high complexity, similar to those observed in the biological world. Despite such complexity, here we present the evidence that at least a part of the formation of these shapes is an equilibrium process. We demonstrate it for an example of mesoporous fibers, one of the abundant shapes. We present a quantitative proof that the fiber free energy is described by the Boltzmann distribution, which is predicted by the equilibrium thermodynamics. This finding may open up new ground for a quantitative description of the morphogenesis of complex self-assembled shapes, including biological hierarchy.

  4. Breakable mesoporous silica nanoparticles for targeted drug delivery.

    PubMed

    Maggini, Laura; Cabrera, Ingrid; Ruiz-Carretero, Amparo; Prasetyanto, Eko A; Robinet, Eric; De Cola, Luisa

    2016-04-01

    "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.

  5. A High Temperature Capacitive Humidity Sensor Based on Mesoporous Silica

    PubMed Central

    Wagner, Thorsten; Krotzky, Sören; Weiß, Alexander; Sauerwald, Tilman; Kohl, Claus-Dieter; Roggenbuck, Jan; Tiemann, Michael

    2011-01-01

    Capacitive sensors are the most commonly used devices for the detection of humidity because they are inexpensive and the detection mechanism is very specific for humidity. However, especially for industrial processes, there is a lack of dielectrics that are stable at high temperature (>200 °C) and under harsh conditions. We present a capacitive sensor based on mesoporous silica as the dielectric in a simple sensor design based on pressed silica pellets. Investigation of the structural stability of the porous silica under simulated operating conditions as well as the influence of the pellet production will be shown. Impedance measurements demonstrate the utility of the sensor at both low (90 °C) and high (up to 210 °C) operating temperatures. PMID:22163790

  6. Far-infrared spectra of mesoporous ZnS nanoparticles

    NASA Astrophysics Data System (ADS)

    Trajić, J.; Romčević, M.; Romčević, N.; Babić, B.; Matović, B.; Baláž, P.

    2016-07-01

    ZnS nanoparticles were synthesized mechanochemically by high-energy milling, with three different milling times (5 min, 10 min and 20 min). Nitrogen adsorption method was used for examining specific surface area and texture of obtained powders. It was found that all samples are completely mesoporous. The optical properties were studied by far-infrared spectroscopy at room temperature in spectral region of 50-600 cm-1. The analysis of the far-infrared reflectivity spectra was made by the fitting procedure. The dielectric function of ZnS nanoparticles is modeled as a mixture of homogenous spherical inclusions in air by the Maxwell-Garnet formula. In the analysis of the far-infrared reflection spectra, appearance of combined plasmon-LO phonon modes (CPPMs) with high phonon damping are observed, which causes decrease of coupled plasmon-phonon frequencies.

  7. Selective functionalization of the mesopores of SBA-15

    DOE PAGESBeta

    Webb, Jonathan D.; Seki, Tomohiro; Goldston, Jennifer F.; Pruski, Marek; Crudden, Cathleen M.

    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

  8. Selective functionalization of the mesopores of SBA-15

    SciTech Connect

    Webb, Jonathan D.; Seki, Tomohiro; Goldston, Jennifer F.; Pruski, Marek; Crudden, Cathleen M.

    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 other 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.

  9. Breakable mesoporous silica nanoparticles for targeted drug delivery.

    PubMed

    Maggini, Laura; Cabrera, Ingrid; Ruiz-Carretero, Amparo; Prasetyanto, Eko A; Robinet, Eric; De Cola, Luisa

    2016-04-01

    "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. PMID:26974603

  10. Nanostructured poly(benzimidazole): from mesoporous networks to nanofibers.

    PubMed

    Weber, Jens

    2010-02-22

    Poly(benzimidazole)s (PBIs) are a class of high-performance polymers which have been receiving increasing interest during the last years due to their high potential as constituents of membrane materials in proton-exchange membrane fuel cells (PEMFCs). In addition to the importance of PBI in fuel-cell technology, there are a number of other applications (e.g., catalysis) that make use of the special properties of this material. The scope of this Minireview is to first give a short overview about the use of nanostructured, mesoporous PBI as a proton conductor. Secondly, the use of spirobifluorene derivatives as new monomers, which allow the synthesis of hierarchically structured PBI, is presented. Limitations of traditional synthetic methods will be discussed, and an ionothermal scheme towards PBI will be presented as a versatile tool for the synthesis of plain and spirobifluorene-based PBIs. Finally, the use of electrospinning as a powerful processing technique for PBI will be presented briefly.

  11. Intrusion and extrusion of water in hydrophobic mesopores

    NASA Astrophysics Data System (ADS)

    Lefevre, B.; Saugey, A.; Barrat, J. L.; Bocquet, L.; Charlaix, E.; Gobin, P. F.; Vigier, G.

    2004-03-01

    We present experimental and theoretical results on intrusion-extrusion cycles of water in hydrophobic mesoporous materials, characterized by independent cylindrical pores. The intrusion, which takes place above the bulk saturation pressure, can be well described using a macroscopic capillary model. Once the material is saturated with water, extrusion takes place upon reduction of the externally applied pressure. Our results for the extrusion pressure can only be understood by assuming that the limiting extrusion mechanism is the nucleation of a vapor bubble inside the pores. A comparison of calculated and experimental nucleation pressures shows that a proper inclusion of line tension effects is necessary to account for the observed values of nucleation barriers. Negative line tensions of order 10-11 J m-1 are found for our system, in reasonable agreement with other experimental estimates of this quantity.

  12. Recyclable Magnetic Mesoporous Nanocomposite with Improved Sensing Performance toward Nitrite.

    PubMed

    Zhang, Yihe; Su, Zisheng; Li, Bin; Zhang, Liming; Fan, Di; Ma, Heping

    2016-05-18

    A magnetic nanomaterial for nitrite ion detection was demonstrated in the present study. This nanomaterial was prepared by grafting a rhodamine 6G derivative (denoted as Rh 6G-OH) into the channels of core-shell magnetic mesoporous silica nanospheres. The nanocomposite (denoted as Fe3O4@Rh 6G) showed large surface area and improved fluorescent performance to accumulate and recognize NO2(-), and its superparamagnetic behavior played an important role in reusability. The fluorescent intensity decreased linearly along with the NO2(-) concentration in the range of 1-50 μM, and the detection limit was estimated to be 0.8 μM, which was much lower than the maximum limit of nitrite ion in drinking water (65 μM) recommended by World Health Organization. Importantly, Fe3O4@Rh 6G could be magnetically collected and effectively reutilized after six test cycles. PMID:27115527

  13. 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.

  14. A simple method to ordered mesoporous carbons containing nickel nanoparticles

    SciTech Connect

    Dai, Sheng; Wang, Xiqing

    2009-01-01

    A series of ordered mesoporous carbons containing magnetic Ni nanoparticles (Ni-OMCs) with a variety of Ni loadings was made by a simple one-pot synthetic procedure through carbonization of phenolic resin-Pluronic block copolymer composites containing various amount of nickel nitrate. Such composite materials were characterized by N{sub 2} sorption, XRD, and STEM. Ni-OMCs exhibited high BET surface area, uniform pore size, and large pore volume without obvious pore blockage with a Ni loading as high as 15 wt%. Ni nanoparticles were crystalline with a face-center-cubic phase and observed mainly in the carbon matrix and on the outer surface as well. The average particle size of Ni nanoparticles was dependent on the preparation (carbonization) temperature and Ni loading; the higher the temperature was used and the more the Ni was incorporated, the larger the Ni nanoparticles were observed. One of the applications of Ni-OMCs was demonstrated as magnetically separable adsorbents.

  15. Desalination of Basal Water by Mesoporous Carbons Nanocomposite Membrane.

    PubMed

    Choi, Jeongdong; Ahn, Youngho; Gamal El-Din, Mohamed; Kim, Eun-Sik

    2016-02-01

    The hydro-transportation process used to obtain bitumen from the Alberta oil sands produces large volume of basal depressurization water (BDW), which contains high salt concentrations. In this research, thin-film nanocomposite (TFN) membrane technology applied to treat BDW in lab-scale, and evaluated water properties before and after the treatment. The average rejection ratios of ionic species were 95.2% and 92.8% by TFN membrane (with ordered mesoporous carbons (OMCs)) and thin-film composite (TFC) (without OMCs) membrane, respectively. The turbidity and total dissolved solids (TDS) were completely rejected in all treatment conditions. Interestingly, the water flux of TFN membrane was dramatically increased compared to TFC membrane. The increase of water flux was believed to be caused by the increased membrane surface hydrophilicity and nano-pore effects by the OMCs. PMID:27433734

  16. Externally Controlled Nanomachines on Mesoporous Silica Nanoparticles for Biomedical Applications.

    PubMed

    Rühle, Bastian; Saint-Cricq, Philippe; Zink, Jeffrey I

    2016-06-17

    Many machines (including nanomachines) consist of a solid support with moving parts that can undergo large amplitude motion to carry out specific tasks. In this Minireview, we will describe nanomachines that are supported on mesoporous silica nanoparticles that are typically 50-100 nanometers in diameter and have an array of open, readily accessible pores with an average width of a few nanometers. For triggering a large amplitude motion of the moving parts, we will focus primarily on external stimuli such as heat or light. As for the specific task the machines are carrying out, this Minireview will focus on the controlled release of pharmaceutically active agents in biomedical applications. We will discuss examples of how nanomachines can be used for remotely controlled cargo release and how existing machines that were originally designed to respond to internal physiological stimuli could be reconfigured to respond to external stimuli instead.

  17. Porous thin films of functionalized mesoporous silica nanoparticles.

    PubMed

    Kobler, Johannes; Bein, Thomas

    2008-11-25

    The synthesis of extremely small mesoporous silica nanoparticles via a specific co-condensation process with phenyl groups is demonstrated. The suspensions are ideally suited for the production of nanoscale thin films by spin-coating. Thanks to the small particle size and the resulting low surface roughness, the films show excellent optical qualities and exhibit good diffusion properties and a highly accessible pore system. The availability of such homogeneous porous thin films made it possible to use ellipsometric porosimetry (EP) as a convenient method to determine the effective porosity of the films on their original support without destroying it. It was possible to record sorption isotherms of the thin films with ellipsometry and to correlate the data with nitrogen sorption data of dried powders of the same material. The thin films showed very low refractive indices of around 1.2. PMID:19206399

  18. Mesoporous aluminosilicate ropes with improved stability from protozeolitic nanoclusters

    NASA Astrophysics Data System (ADS)

    Zheng, Junlin; Kong, Dejin; Yang, Weimin; Xie, Zaiku; Wu, Dong; Sun, Yuhan

    2007-02-01

    Mesoporous aluminosilicate ropes with improved hydrothermal stability have been prepared through S +X -I + route via self-assembly of protozeolitic nanoclusters with cetyltrimethylammonium bromides (CTAB) template micelles in HNO 3 solution. SEM observation confirmed that high-yield aluminosilicate ropes could be produced under proper HNO 3 concentration. NO 3- ions had strong binding strength to the CTA + ions and tended to form more elongated surfactant micelles, thus fibrous products were fabricated under the direction of these long rod micelles in shearing flow. At the same time, the NO 3- ions combining with CTA + ions generated more active (CTA +NO 3-) assembly, which effectively catalysed the polymerization of protozeolitic nanoclusters with large volume into highly ordered mesostructures. Compared with normal MCM-41 silica synthesized through S +X -I + route in acidic media, the hydrothermal stability was improved considerably. These protozeolitic nanoclusters survived strongly acidic media and entered into mesostructured framework, which contributed to the improvement of hydrothermal stability.

  19. Thrombin-Responsive Gated Silica Mesoporous Nanoparticles As Coagulation Regulators.

    PubMed

    Bhat, Ravishankar; Ribes, Àngela; Mas, Núria; Aznar, Elena; Sancenón, Félix; Marcos, M Dolores; Murguía, Jose R; Venkataraman, Abbaraju; Martínez-Máñez, Ramón

    2016-02-01

    The possibility of achieving sophisticated actions in complex biological environments using gated nanoparticles is an exciting prospect with much potential. We herein describe new gated mesoporous silica nanoparticles (MSN) loaded with an anticoagulant drug and capped with a peptide containing a thrombin-specific cleavage site. When the coagulation cascade was triggered, active thrombin degraded the capping peptidic sequence and induced the release of anticoagulant drugs to delay the clotting process. The thrombin-dependent response was assessed and a significant increase in coagulation time in plasma from 2.6 min to 5 min was found. This work broadens the application of gated silica nanoparticles and demonstrates their ability to act as controllers in a complex scenario such as hemostasis. PMID:26794474

  20. Photonic patterns printed in chiral nematic mesoporous resins.

    PubMed

    Khan, Mostofa K; Bsoul, Anas; Walus, Konrad; Hamad, Wadood Y; MacLachlan, Mark J

    2015-03-27

    Chiral nematic mesoporous phenol-formaldehyde resins, which were prepared using cellulose nanocrystals as a template, can be used as a substrate to produce latent photonic images. These resins undergo swelling, which changes their reflected color. By writing on the films with chemical inks, the density of methylol groups in the resin changes, subsequently affecting their degree of swelling and, consequently, their color. Writing on the films gives latent images that are revealed only upon swelling of the films. Using inkjet printing, it is possible to make higher resolution photonic patterns both as text and images that can be visualized by swelling and erased by drying. This novel approach to printing photonic patterns in resin films may be applied to anti-counterfeit tags, signage, and decorative applications. PMID:25682748

  1. Sol-gel synthesis and characterization of mesoporous manganese oxide

    SciTech Connect

    Hong Xinlin; Zhang Gaoyong; Zhu Yinyan; Yang Hengquan

    2003-10-30

    Mesoporous manganese oxide (MPMO) from reduction of KMnO{sub 4} with maleic acid, was obtained and characterized in detail. The characterization of the material was confirmed by high-resolution transmission electron microscopy (HRTEM), X-ray powder diffractometry (XRD) and N{sub 2} sorptometry. The results showed that MPMO is a pseudo-crystalline material with complex network pore structure, of which BET specific surface area is 297 m{sup 2}/g and pore size distribution is approximately in the range of 0.7-6.0 nm. The MPMO material turns to cryptomelane when the calcinating temperature rises to 400 deg. C. The optimum sol-gel reaction conditions are KMnO{sub 4}/C{sub 4}H{sub 4}O{sub 4} molar ratio=3, pH=7 and gelation time>6 h.

  2. Mesoporous nano/micro noble metal particles: synthesis and applications.

    PubMed

    Yang, Shengchun; Luo, Xiao

    2014-05-01

    The morphology, size and composition often govern the physical and chemical properties of noble metal units with a size in the nano or micro scale. Thus, the controlled growth of noble metal crystals would help to tailor their unique properties and this would be followed by their practical application. Mesoporous nano/micro noble metal units are types of nanostructured material that have fascinating properties that can generate great potential for various applications. This review presents a general view on the growth mechanisms of porous noble metal units and is focused on recent progresses in their synthetic approaches. Then, their potential applications in the field of drug delivery, cell imaging and SERS substrates, as well as fuel cell catalysts are overviewed.

  3. Magnetic Mesoporous Palladium Catalyzed Selective Hydrogenation of Sunflower Oil.

    PubMed

    Liu, Wei; Tian, Fei; Yu, Jingjing; Bi, Yanlan

    2016-05-01

    In this paper, a novel magnetic mesoporous Pd catalyst is used to catalyse selective hydrogenation of sunflower oil at a mild temperature of 50°C. Effects of reaction temperature, stirring speed, time, catalyst loading and hydrogen pressure on the reaction activity, trans fatty acid (TFA) and stearic acid formation were studied. Under the condition of 3.2 mg Pd/100 g oil, 50°C, 1300 rpm stirring speed and 19.0 atm of H2, the lowest amount of TFA generated during the reaction (IV = 80) was 14.9 ± 0.4% while 11.4 ± 0.4% of stearic acid was produced. And this magnetic Pd-catalyst can be reused easily for at least six times without significant catalyst deactivation, the amount of TFA almost remained unchanged. Moreover, this Pd-catalyst shows a good magnetic separation, which provides a potential method for the facile oil modification. PMID:27086993

  4. Desalination of Basal Water by Mesoporous Carbons Nanocomposite Membrane.

    PubMed

    Choi, Jeongdong; Ahn, Youngho; Gamal El-Din, Mohamed; Kim, Eun-Sik

    2016-02-01

    The hydro-transportation process used to obtain bitumen from the Alberta oil sands produces large volume of basal depressurization water (BDW), which contains high salt concentrations. In this research, thin-film nanocomposite (TFN) membrane technology applied to treat BDW in lab-scale, and evaluated water properties before and after the treatment. The average rejection ratios of ionic species were 95.2% and 92.8% by TFN membrane (with ordered mesoporous carbons (OMCs)) and thin-film composite (TFC) (without OMCs) membrane, respectively. The turbidity and total dissolved solids (TDS) were completely rejected in all treatment conditions. Interestingly, the water flux of TFN membrane was dramatically increased compared to TFC membrane. The increase of water flux was believed to be caused by the increased membrane surface hydrophilicity and nano-pore effects by the OMCs.

  5. Gated proton transport in aligned mesoporous silica films

    NASA Astrophysics Data System (ADS)

    Fan, Rong; Huh, Seong; Yan, Ruoxue; Arnold, John; Yang, Peidong

    2008-04-01

    Modulated proton transport plays significant roles in biological processes such as ATP synthesis as well as in technologically important applications including, for example, hydrogen fuel cells. The state-of-the-art proton-exchange membrane is the sulphonated tetrafluoroethylene copolymer Nafion developed by DuPont in the late 1960s, with a high proton conductivity. However, actively switchable proton conduction, a functional mimic of the ion transport within a cell membrane, has yet to be realized. Herein, we report the electrostatic gating of proton transport within aligned mesoporous silica thin film. It is observed that surface-charge-mediated transport is dominant at low proton concentrations. We have further demonstrated that the proton conduction can be actively modulated by two-fourfold with a gate voltage as low as 1V. Such artificial gatable ion transport media could have potential applications in nanofluidic chemical processors, biomolecular separation and electrochemical energy conversion.

  6. Rapid pathogen detection with bacterial-assembled magnetic mesoporous silica.

    PubMed

    Lee, Soo Youn; Lee, Jiho; Lee, Hye Sun; Chang, Jeong Ho

    2014-03-15

    We report rapid and accurate pathogen detection by coupling with high efficiency magnetic separation of pathogen by Ni(2+)-heterogeneous magnetic mesoporous silica (Ni-HMMS) and real time-polymerase chain reaction (RT-PCR) technique. Ni-HMMS was developed with a significant incorporation of Fe particles within the silica mesopores by programmed thermal hydrogen reaction and functionalized with Ni(2+) ion on the surface by the wet impregnation process. High abundant Ni(2+) ions on the Ni-HMMS surface were able to assemble with cell wall component protein NikA (nickel-binding membrane protein), which contains several pathogenic bacteria including Escherichia coli O157:H7. NikA protein expression experiment showed the outstanding separation rate of the nikA gene-overexpressed E. coli (pSY-Nik) when comparing with wild-type E. coli (44.5 ± 13%) or not over-expressed E. coli (pSY-Nik) (53.2 ± 2.7%). Moreover, Ni-HMMS showed lower obstacle effect by large reaction volume (10 mL) than spherical core/shell-type silica magnetic nanoparticles functionalized with Ni(2+) (ca. 40 nm-diameters). Finally, the Ni-HMMS was successfully assessed to separate pathogenic E. coli O157:H7 and applied to direct and rapid RT-PCR to quantitative detection at ultralow concentration (1 Log10 cfu mL(-1)) in the real samples (milk and Staphylococcus aureus culture broth) without bacterial amplification and DNA extraction step.

  7. Breakable mesoporous silica nanoparticles for targeted drug delivery

    NASA Astrophysics Data System (ADS)

    Maggini, Laura; Cabrera, Ingrid; Ruiz-Carretero, Amparo; Prasetyanto, Eko A.; Robinet, Eric; de Cola, Luisa

    2016-03-01

    ``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.``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. Electronic supplementary information (ESI) available: Full experimental procedures, additional SEM and TEM images of particles, complete UV-Vis and PL-monitored characterization of the breakdown of

  8. Synthesis and structural evolution of mesoporous silica silver nanocomposites

    NASA Astrophysics Data System (ADS)

    Armelao, L.; Bottaro, G.; Campostrini, R.; Gialanella, S.; Ischia, M.; Poli, F.; Tondello, E.

    2007-04-01

    Mesoporous silica materials were prepared by a sol-gel procedure using Si(OCH2CH3)4 (TEOS) as the silica source and the non-ionic alkyl-poly(ethyleneoxide) oligomer Brij76 as the structure-directing agent. Pure inorganic hexagonal-like mesostructured SiO2 powders were obtained after annealing, performed in air between 400 and 600 °C. Upon calcination, the organic template was removed and silica networks with a different amount of Si-OH groups as well as porous features were prepared. Ag-SiO2 nanocomposites were obtained by metallation of the mesoporous silica powders with aqueous solutions of silver acetate. Ag+ ions were chemically grafted on the silica pores by taking advantage of the basic character of acetate anions and the acidic properties of Si-OH groups. Different silver concentrations were achieved on the mesostructured silica powders, depending on their former annealing treatment. For all samples the formation of silver nanoclusters occurred spontaneously at room temperature. Monodispersed, spherical Ag crystallites, with an average diameter of a few nanometres, were obtained starting from the 400 °C-treated silica, whereas clusters with different sizes (3-20 nm) and irregular shapes were grown for metallation of the 600 °C-heated SiO2 matrix. The sample's chemical composition was studied by x-ray photoelectron spectroscopy (XPS) and x-ray excited Auger electron spectroscopy (XE-AES), whereas the porous features were investigated by N2 BET adsorption. Information concerning structure and microstructure was obtained by x-ray diffraction (XRD) and transmission electron microscopy (TEM).

  9. Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

    NASA Astrophysics Data System (ADS)

    Lee, Min-Hong

    The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

  10. Functionalized mesoporous materials for adsorption and release of different drug molecules: A comparative study

    SciTech Connect

    Wang Gang; Otuonye, Amy N.; Blair, Elizabeth A.; Denton, Kelley; Tao Zhimin; Asefa, Tewodros

    2009-07-15

    The adsorption capacity and release properties of mesoporous materials for drug molecules can be improved by functionalizing their surfaces with judiciously chosen organic groups. Functionalized ordered mesoporous materials containing various types of organic groups via a co-condensation synthetic method from 15% organosilane and by post-grafting organosilanes onto a pre-made mesoporous silica were synthesized. Comparative studies of their adsorption and release properties for various model drug molecules were then conducted. Functional groups including 3-aminopropyl, 3-mercaptopropyl, vinyl, and secondary amine groups were used to functionalize the mesoporous materials while rhodamine 6G and ibuprofen were utilized to investigate the materials' relative adsorption and release properties. The self-assembly of the mesoporous materials was carried out in the presence of cetyltrimethylammonium bromide (CTAB) surfactant, which produced MCM-41 type materials with pore diameters of {approx}2.7-3.3 nm and moderate to high surface areas up to {approx}1000 m{sup 2}/g. The different functional groups introduced into the materials dictated their adsorption capacity and release properties. While mercaptopropyl and vinyl functionalized samples showed high adsorption capacity for rhodamine 6G, amine functionalized samples exhibited higher adsorption capacity for ibuprofen. While the diffusional release of ibuprofen was fitted on the Fickian diffusion model, the release of rhodamine 6G followed Super Case-II transport model. - Graphical abstract: The adsorption capacity and release properties of mesoporous materials for various drug molecules are tuned by functionalizing the surfaces of the materials with judiciously chosen organic groups. This work reports comparative studies of the adsorption and release properties of functionalized ordered mesoporous materials containing different hydrophobic and hydrophilic groups that are synthesized via a co-condensation and post

  11. Enhancing pseudocapacitive charge storage in polymer templated mesoporous materials.

    PubMed

    Rauda, Iris E; Augustyn, Veronica; Dunn, Bruce; Tolbert, Sarah H

    2013-05-21

    Growing global energy demands coupled with environmental concerns have increased the need for renewable energy sources. For intermittent renewable sources like solar and wind to become available on demand will require the use of energy storage devices. Batteries and supercapacitors, also known as electrochemical capacitors (ECs), represent the most widely used energy storage devices. Supercapacitors are frequently overlooked as an energy storage technology, however, despite the fact that these devices provide greater power, much faster response times, and longer cycle life than batteries. Their limitation is that the energy density of ECs is significantly lower than that of batteries, and this has limited their potential applications. This Account reviews our recent work on improving pseudocapacitive energy storage performance by tailoring the electrode architecture. We report our studies of mesoporous transition metal oxide architectures that store charge through surface or near-surface redox reactions, a phenomenon termed pseudocapacitance. The faradaic nature of pseudocapacitance leads to significant increases in energy density and thus represents an exciting future direction for ECs. We show that both the choice of material and electrode architecture is important for producing the ideal pseudocapacitor device. Here we first briefly review the current state of electrode architectures for pseudocapacitors, from slurry electrodes to carbon/metal oxide composites. We then describe the synthesis of mesoporous films made with amphiphilic diblock copolymer templating agents, specifically those optimized for pseudocapacitive charge storage. These include films synthesized from nanoparticle building blocks and films made from traditional battery materials. In the case of more traditional battery materials, we focus on using flexible architectures to minimize the strain associated with lithium intercalation, that is, the accumulation of lithium ions or atoms between the

  12. Surface functionalized mesoporous silica nanoparticles for intracellular drug delivery

    NASA Astrophysics Data System (ADS)

    Vivero-Escoto, Juan Luis

    Mesoporous silica nanoparticles (MSNs) are a highly promising platform for intracellular controlled release of drugs and biomolecules. Despite that the application of MSNs in the field of intracellular drug delivery is still at its infancy very exciting breakthroughs have been achieved in the last years. A general review of the most recent progress in this area of research is presented, including a description of the latest findings on the pathways of entry into live mammalian cells together with the intracellular trafficking, a summary on the contribution of MSNs to the development of site-specific drug delivery systems, a report on the biocompatibility of this material in vitro andin vivo, and a discussion on the most recent breakthroughs in the synthesis and application of stimuli-responsive mesoporous silica-based delivery vehicles. A gold nanoparticles (AuNPs)-capped MSNs-based intracellular photoinduced drug delivery system (PR-AuNPs-MSNs) for the controlled release of anticancer drug inside of human fibroblast and liver cells was synthesized and characterized. We found that the mesoporous channels of MSNs could be efficiently capped by the photoresponsive AuNPs without leaking the toxic drug, paclitaxel, inside of human cells. Furthermore, we demonstrated that the cargo-release property of this PR-AuNPs-MSNs system could be easily photo-controlled under mild and biocompatible conditions in vitro. In collaboration with Renato Mortera (a visiting student from Italy), a MSNs based intracellular delivery system for controlled release of cell membrane impermeable cysteine was developed. A large amount of cysteine molecules were covalently attached to the silica surface of MSNs through cleavable disulfide linkers. These cysteine-containing nanoparticles were efficiently endocytosed by human cervical cancer cells HeLa. These materials exhibit 450 times higher cell growth inhibition capability than that of the conventional N-acetylcysteine prodrug. The ability to

  13. Mesoporous Carbon-based Materials for Alternative Energy Applications

    NASA Astrophysics Data System (ADS)

    Cross, Kimberly Michelle

    Increasing concerns for the escalating issues activated by the effect of carbon dioxide emissions on the global climate from extensive use of fossil fuels and the limited amount of fossil resources has led to an in-depth search for alternative energy systems, primarily based on nuclear or renewable energy sources. Recent innovations in the production of more efficient devices for energy harvesting, storage, and conversion are based on the incorporation of nanostructured materials into electrochemical systems. The aforementioned nano-electrochemical energy systems hold particular promise for alternative energy transportation related technologies including fuel cells, hydrogen storage, and electrochemical supercapacitors. In each of these devices, nanostructured materials can be used to increase the surface area where the critical chemical reactions occur within the same volume and mass, thereby increasing the energy density, power density, electrical efficiency, and physical robustness of the system. Durable corrosion resistant carbon support materials for fuel cells have been designed by adding conductive low cost carbon materials with chemically robust ceramic materials. Since a strict control of the pore size is mandatory to optimize properties for improved performance, chemical activation agents have been utilized as porogens to tune surface areas, pore size distributions, and composition of carbon-based mesoporous materials. Through the use of evaporative self-assembly methods, both randomly disordered and surfactant-templated, ordered carbon-silica nanocomposites have been synthesized with controlled surface area, pore volume, and pore size ranging from 50-800 m2/g, 0.025-0.75 cm3/g, and 2-10 nm, respectively. Multi-walled carbon nanotubes (MWNTs) ranging from 0.05-1.0 wt. % were added to the aforementioned carbon-silica nanocomposites, which provided an additional increase in surface area and improved conductivity. Initially, a conductivity value of 0.0667 S

  14. Novel hollow mesoporous 1D TiO2 nanofibers as photovoltaic and photocatalytic materials.

    PubMed

    Zhang, Xiang; Thavasi, Velmurugan; Mhaisalkar, S G; Ramakrishna, Seeram

    2012-03-01

    Hollow mesoporous one dimensional (1D) TiO(2) nanofibers are successfully prepared by co-axial electrospinning of a titanium tetraisopropoxide (TTIP) solution with two immiscible polymers; polyethylene oxide (PEO) and polyvinylpyrrolidone (PVP) using a core-shell spinneret, followed by annealing at 450 °C. The annealed mesoporous TiO(2) nanofibers are found to having a hollow structure with an average diameter of 130 nm. Measurements using the Brunauer-Emmett-Teller (BET) method reveal that hollow mesoporous TiO(2) nanofibers possess a high surface area of 118 m(2) g(-1) with two types of mesopores; 3.2 nm and 5.4 nm that resulted from gaseous removal of PEO and PVP respectively during annealing. With hollow mesoporous TiO(2) nanofibers as the photoelectrode in dye sensitized solar cells (DSSC), the solar-to-current conversion efficiency (η) and short circuit current (J(sc)) are measured as 5.6% and 10.38 mA cm(-2) respectively, which are higher than those of DSSC made using regular TiO(2) nanofibers under identical conditions (η = 4.2%, J(sc) = 8.99 mA cm(-2)). The improvement in the conversion efficiency is mainly attributed to the higher surface area and mesoporous TiO(2) nanostructure. It facilitates the adsorption of more dye molecules and also promotes the incident photon to electron conversion. Hollow mesoporous TiO(2) nanofibers with close packing of grains and crystals intergrown with each other demonstrate faster electron diffusion, and longer electron recombination time than regular TiO(2) nanofibers as well as P25 nanoparticles. The surface effect of hollow mesoporous TiO(2) nanofibers as a photocatalyst for the degradation of rhodamine dye was also investigated. The kinetic study shows that the hollow mesoporous surface of the TiO(2) nanofibers influenced its interactions with the dye, and resulted in an increased catalytic activity over P25 TiO(2) nanocatalysts. PMID:22315140

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

    SciTech Connect

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

    2010-02-15

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

  16. Ordered mesoporous carbons obtained by a simple soft template method as sulfur immobilizers for lithium-sulfur cells.

    PubMed

    Moreno, Noelia; Caballero, Alvaro; Hernán, Lourdes; Morales, Julián; Canales-Vázquez, Jesús

    2014-08-28

    Carbon materials with ordered mesoporous structures were synthesized using soft template methods and then activated by CO2 treatment. Sulfur was incorporated in these carbons via a simple chemical deposition method in aqueous solutions and the resulting composites were tested as electrodes in Li-S cells. The electrochemical results showed that well-ordered mesoporous carbons perform better than those with a random mesopore arrangement (wormhole-like mesoporous structure). The mesopore ordering yields a framework of well-connected empty sites that results in an enhancement of both the charge carrier mobility and the reversibility of the electrochemical reaction. Although the activation with CO2 partially destroys the mesopore arrangement, which adversely affects the electrode performance, it notably increases the surface area and the micropore content which improves the connectivity between the mesopores. The final observation was an irrelevant effect of the activation process at low current densities. However, at higher rates the activated carbon composite delivered higher capacities. The hierarchical pore structure formed by micro- and mesopores should guarantee the required fast mobility of the Li(+).

  17. Phosphonate-functionalized large pore 3-D cubic mesoporous (KIT-6) hybrid as highly efficient actinide extracting agent.

    PubMed

    Lebed, Pablo J; de Souza, Kellen; Bilodeau, François; Larivière, Dominic; Kleitz, Freddy

    2011-11-01

    A new type of radionuclide extraction material is reported based on phosphonate functionalities covalently anchored on the mesopore surface of 3-D cubic mesoporous silica (KIT-6). The easily prepared nanoporous hybrid shows largely superior performance in selective sorption of uranium and thorium as compared to the U/TEVA commercial resin and 2-D hexagonal SBA-15 equivalent.

  18. Ion current behaviors of mesoporous zeolite-polymer composite nanochannels prepared by water-assisted self-assembly.

    PubMed

    Zhang, Wenjuan; Meng, Zheyi; Zhai, Jin; Heng, Liping

    2014-04-01

    Inspired by the asymmetry of biological ion channels in structure and composition, we designed a novel type of artificial asymmetric nanochannels based on mesoporous zeolite (MCM-41) and polyimide (PI) by water-assisted self-assembly. Meanwhile, we studied ionic current behaviors and rectifying characteristics of the mesoporous zeolite-polymer composite nanochannels. PMID:24394328

  19. Periodic mesoporous hydridosilica--synthesis of an "impossible" material and its thermal transformation into brightly photoluminescent periodic mesoporous nanocrystal silicon-silica composite.

    PubMed

    Xie, Zhuoying; Henderson, Eric J; Dag, Ömer; Wang, Wendong; Lofgreen, Jennifer E; Kübel, Christian; Scherer, Torsten; Brodersen, Peter M; Gu, Zhong-Ze; Ozin, Geoffrey A

    2011-04-01

    There has always been a fascination with "impossible" compounds, ones that do not break any rules of chemical bonding or valence but whose structures are unstable and do not exist. This instability can usually be rationalized in terms of chemical or physical restrictions associated with valence electron shells, multiple bonding, oxidation states, catenation, and the inert pair effect. In the pursuit of these "impossible" materials, appropriate conditions have sometimes been found to overcome these instabilities and synthesize missing compounds, yet for others these tricks have yet to be uncovered and the materials remain elusive. In the scientifically and technologically important field of periodic mesoporous silicas (PMS), one such "impossible" material is periodic mesoporous hydridosilica (meso-HSiO(1.5)). It is the archetype of a completely interrupted silica open framework material: its pore walls are comprised of a three-connected three-dimensional network that should be so thermodynamically unstable that any mesopores present would immediately collapse upon removal of the mesopore template. In this study we show that meso-HSiO(1.5) can be synthesized by template-directed self-assembly of HSi(OEt)(3) under aqueous acid-catalyzed conditions and after template extraction remains stable to 300 °C. Above this temperature, bond redistribution reactions initiate a metamorphic transformation which eventually yields periodic mesoporous nanocrystalline silicon-silica, meso-ncSi/SiO(2), a nanocomposite material in which brightly photoluminescent silicon nanocrystallites are embedded within a silica matrix throughout the mesostructure. The integration of the properties of silicon nanocrystallinity with silica mesoporosity provides a wealth of new opportunities for emerging nanotechnologies.

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

    PubMed

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

    2016-01-01

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

  1. Interleaved mesoporous copper for the anode catalysis in direct ammonium borane fuel cells.

    PubMed

    Auxilia, Francis M; Tanabe, Toyokazu; Ishihara, Shinsuke; Saravanan, Govindachetty; Ramesh, Gubbala V; Matsumoto, Futoshi; Ya, Xu; Ariga, Katsuhiko; Dakshanamoorthy, Arivuoli; Abe, Hideki

    2014-06-01

    Mesoporous materials with tailored microstructures are of increasing importance in practical applications particularly for energy generation and/or storage. Here we report a mesoporous copper material (MS-Cu) can be prepared in a hierarchical microstructure and exhibit high catalytic performance for the half-cell reaction of direct ammonium borane (NH3BH3) fuel cells (DABFs). Hierarchical copper oxide (CuO) nanoplates (CuO Npls) were first synthesized in a hydrothermal condition. CuO Npls were then reduced at room temperature using water solution of sodium borohydride (NaBH4) to yield the desired mesoporous copper material, MS-Cu, consisting of interleaved nanoplates with a high density of mesopores. The surface of MS-Cu comprised high-index facets, whereas a macroporous copper material (MC-Cu), which was prepared from CuO Npls at elevated temperatures in a hydrogen stream, was surrounded by low-index facets with a low density of active sites. MS-Cu exhibited a lower onset potential and improved durability for the electro-oxidation of NH3BH3 than MC-Cu or copper particles because of the catalytically active mesopores on the interleaved nanoplates.

  2. Comprehensive Mechanism Analysis of Mesoporous-Silica-Nanoparticle-Induced Cancer Immunotherapy.

    PubMed

    Wang, Xiupeng; Li, Xia; Yoshiyuki, Kazuko; Watanabe, Yohei; Sogo, Yu; Ohno, Tadao; Tsuji, Noriko M; Ito, Atsuo

    2016-05-01

    A plain mesoporous silica nanoparticle without any immunomodulatory molecules significantly enhances anticancer immunity in vivo. Comprehensive mechanism of mesoporous-silica-nanoparticle-induced cancer immunotherapy is analyzed in this paper. The mesoporous silica nanoparticle promotes both Th1 and Th2 immune responses, as it accelerates lymphocytes proliferation, stimulates IFN-γ, IL-2, IL-4, and IL-10 cytokine secretion by lymphocytes ex vivo, and increases IgG, IgG1, IgG2a, IgM, and IgA antibody titers in mice serum compared with those of alum and adjuvant-free groups. Moreover, the mesoporous silica nanoparticle enhances effector memory CD4(+) and CD8(+) T cell populations in three most important immune organs (bone marrow, lymph node, and spleen) of mice compared with those of alum and adjuvant-free groups three months after adjuvant injection. The present study paves the way for the application of mesoporous silica nanoparticle as immunoadjuvant for cancer immunotherapy. PMID:26987867

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

    PubMed Central

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

    2016-01-01

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

  4. Chemical Insight into the Adsorption of Chromium(III) on Iron Oxide/Mesoporous Silica Nanocomposites.

    PubMed

    Egodawatte, Shani; Datt, Ashish; Burns, Eric A; Larsen, Sarah C

    2015-07-14

    Magnetic iron oxide/mesoporous silica nanocomposites consisting of iron oxide nanoparticles embedded within mesoporous silica (MCM-41) and modified with aminopropyl functional groups were prepared for application to Cr(III) adsorption followed by magnetic recovery of the nanocomposite materials from aqueous solution. The composite materials were extensively characterized using physicochemical techniques, such as powder X-ray diffraction, thermogravimetric and elemental analysis, nitrogen adsorption, and zeta potential measurements. For aqueous Cr(III) at pH 5.4, the iron oxide/mesoporous silica nanocomposite exhibited a superior equilibrium adsorption capacity of 0.71 mmol/g, relative to 0.17 mmol/g for unmodified mesoporous silica. The aminopropyl-functionalized iron oxide/mesoporous silica nanocomposites displayed an equilibrium adsorption capacity of 2.08 mmol/g, the highest adsorption capacity for Cr(III) of all the materials evaluated in this study. Energy-dispersive spectroscopy (EDS) with transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) experiments provided insight into the chemical nature of the adsorbed chromium species.

  5. Comprehensive Mechanism Analysis of Mesoporous-Silica-Nanoparticle-Induced Cancer Immunotherapy.

    PubMed

    Wang, Xiupeng; Li, Xia; Yoshiyuki, Kazuko; Watanabe, Yohei; Sogo, Yu; Ohno, Tadao; Tsuji, Noriko M; Ito, Atsuo

    2016-05-01

    A plain mesoporous silica nanoparticle without any immunomodulatory molecules significantly enhances anticancer immunity in vivo. Comprehensive mechanism of mesoporous-silica-nanoparticle-induced cancer immunotherapy is analyzed in this paper. The mesoporous silica nanoparticle promotes both Th1 and Th2 immune responses, as it accelerates lymphocytes proliferation, stimulates IFN-γ, IL-2, IL-4, and IL-10 cytokine secretion by lymphocytes ex vivo, and increases IgG, IgG1, IgG2a, IgM, and IgA antibody titers in mice serum compared with those of alum and adjuvant-free groups. Moreover, the mesoporous silica nanoparticle enhances effector memory CD4(+) and CD8(+) T cell populations in three most important immune organs (bone marrow, lymph node, and spleen) of mice compared with those of alum and adjuvant-free groups three months after adjuvant injection. The present study paves the way for the application of mesoporous silica nanoparticle as immunoadjuvant for cancer immunotherapy.

  6. Hierarchically ordered mesoporous Co3O4 materials for high performance Li-ion batteries.

    PubMed

    Sun, Shijiao; Zhao, Xiangyu; Yang, Meng; Wu, Linlin; Wen, Zhaoyin; Shen, Xiaodong

    2016-01-01

    Highly ordered mesoporous Co3O4 materials have been prepared via a nanocasting route with three-dimensional KIT-6 and two-dimensional SBA-15 ordered mesoporous silicas as templates and Co(NO3)2 · 6H2O as precursor. Through changing the hydrothermal treating temperature of the silica template, ordered mesoporous Co3O4 materials with hierarchical structures have been developed. The larger pores around 10 nm provide an efficient transport for Li ions, while the smaller pores between 3-5 nm offer large electrochemically active areas. Electrochemical impedance analysis proves that the hierarchical structure contributes to a lower charge transfer resistance in the mesoporous Co3O4 electrode than the mono-sized structure. High reversible capacities around 1141 mAh g(-1) of the hierarchically mesoporous Co3O4 materials are obtained, implying their potential applications for high performance Li-ion batteries. PMID:26781265

  7. Interleaved mesoporous copper for the anode catalysis in direct ammonium borane fuel cells.

    PubMed

    Auxilia, Francis M; Tanabe, Toyokazu; Ishihara, Shinsuke; Saravanan, Govindachetty; Ramesh, Gubbala V; Matsumoto, Futoshi; Ya, Xu; Ariga, Katsuhiko; Dakshanamoorthy, Arivuoli; Abe, Hideki

    2014-06-01

    Mesoporous materials with tailored microstructures are of increasing importance in practical applications particularly for energy generation and/or storage. Here we report a mesoporous copper material (MS-Cu) can be prepared in a hierarchical microstructure and exhibit high catalytic performance for the half-cell reaction of direct ammonium borane (NH3BH3) fuel cells (DABFs). Hierarchical copper oxide (CuO) nanoplates (CuO Npls) were first synthesized in a hydrothermal condition. CuO Npls were then reduced at room temperature using water solution of sodium borohydride (NaBH4) to yield the desired mesoporous copper material, MS-Cu, consisting of interleaved nanoplates with a high density of mesopores. The surface of MS-Cu comprised high-index facets, whereas a macroporous copper material (MC-Cu), which was prepared from CuO Npls at elevated temperatures in a hydrogen stream, was surrounded by low-index facets with a low density of active sites. MS-Cu exhibited a lower onset potential and improved durability for the electro-oxidation of NH3BH3 than MC-Cu or copper particles because of the catalytically active mesopores on the interleaved nanoplates. PMID:24738410

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  9. Graphitic Mesoporous Carbon Loaded with Iron-Nickel Hydroxide for Superior Oxygen Evolution Reactivity.

    PubMed

    Wang, Ling; Huang, Xiaolei; Xue, Junmin

    2016-07-21

    Earth-abundant transition metal oxides and hydroxides have been intensively investigated as promising catalysts for the oxygen evolution reaction (OER). However, the overall OER performance of the transition metal oxides/hydroxides is largely jeopardized by their inherent low electrical conductivity. Mesoporous carbon has been a commonly used as a carrier material for these oxides/hydroxides to promote the electrical conductivity and provide a large specific surface area. However, most of the available mesoporous carbon carriers are amorphous. It has been very challenging to synthesize graphitic mesoporous carbon owing to the extremely high graphitization temperature. In this work, we report a new strategy used to prepare graphitic mesoporous carbon (GMC) by employing Fe metal as the graphitization catalyst. The graphitic carbon was obtained at 1000 °C, at which it retained its mesoporous structure. The conductivity of the obtained GMC was approximately 550 S m(-1) , which was almost ten times higher than that of amorphous carbon. The GMC was further loaded with Fe-Ni hydroxide to fabricate the OER catalyst. The obtained catalyst showed good OER activity with an overpotential of 320 mV at a current density of 10 mA cm(-2) and a low Tafel slope of 57 mV dec(-1) . The synthesized catalyst also possessed excellent stability, with almost no current drop even after 2000 cycles and at a constant voltage for 2 h. PMID:27312811

  10. Nickel Nanofoam/Different Phases of Ordered Mesoporous Carbon Composite Electrodes for Superior Capacitive Energy Storage.

    PubMed

    Lee, Kangsuk; Song, Haeni; Lee, Kwang Hoon; Choi, Soo Hyung; Jang, Jong Hyun; Char, Kookheon; Son, Jeong Gon

    2016-08-31

    Electrochemical energy storage devices based on electric double layer capacitors (EDLCs) have received considerable attention due to their high power density and potential for obtaining improved energy density in comparison to the lithium ion battery. Ordered mesoporous carbon (OMC) is a promising candidate for use as an EDLC electrode because it has a high specific surface area (SSA), providing a wider charge storage space and size-controllable mesopore structure with a long-range order, suppling high accessibility to the electrolyte ions. However, OMCs fabricated using conventional methods have several drawbacks including low electronic conductivity and long ionic diffusion paths in mesopores. We used nickel nanofoam, which has a relatively small pore (sub-100 nm to subμm) network structure, as a current collector. This provides a significantly shortened electronic/ionic current paths and plentiful surface area, enabling stable and close attachment of OMCs without the use of binders. Thus, we present hierarchical binder-free electrode structures based on OMC/Ni nanofoams. These structures give rise to enhanced specific capacitance and a superior rate capability. We also investigated the mesopore structural effect of OMCs on electrolyte transport by comparing the capacitive performances of collapsed lamellar, cylindrical, and spherical mesopore electrodes. The highly ordered and straightly aligned cylindrical OMCs exhibited the highest specific capacitance and the best rate capability. PMID:27490161

  11. Chemistry of Mesoporous Organosilica in Nanotechnology: Molecularly Organic-Inorganic Hybridization into Frameworks.

    PubMed

    Chen, Yu; Shi, Jianlin

    2016-05-01

    Organic-inorganic hybrid materials aiming to combine the individual advantages of organic and inorganic components while overcoming their intrinsic drawbacks have shown great potential for future applications in broad fields. In particular, the integration of functional organic fragments into the framework of mesoporous silica to fabricate mesoporous organosilica materials has attracted great attention in the scientific community for decades. The development of such mesoporous organosilica materials has shifted from bulk materials to nanosized mesoporous organosilica nanoparticles (designated as MONs, in comparison with traditional mesoporous silica nanoparticles (MSNs)) and corresponding applications in nanoscience and nanotechnology. In this comprehensive review, the state-of-art progress of this important hybrid nanomaterial family is summarized, focusing on the structure/composition-performance relationship of MONs of well-defined morphology, nanostructure, and nanoparticulate dimension. The synthetic strategies and the corresponding mechanisms for the design and construction of MONs with varied morphologies, compositions, nanostructures, and functionalities are overviewed initially. Then, the following part specifically concentrates on their broad spectrum of applications in nanotechnology, mainly in nanomedicine, nanocatalysis, and nanofabrication. Finally, some critical issues, presenting challenges and the future development of MONs regarding the rational synthesis and applications in nanotechnology are summarized and discussed. It is highly expected that such a unique molecularly organic-inorganic nanohybrid family will find practical applications in nanotechnology, and promote the advances of this discipline regarding hybrid chemistry and materials.

  12. Mesoporous CLEAs-silica composite microparticles with high activity and enhanced stability

    PubMed Central

    Cui, Jiandong; Jia, Shiru; Liang, Longhao; Zhao, Yamin; Feng, Yuxiao

    2015-01-01

    A novel enzyme immobilization approach was used to generate mesoporous enzymes-silica composite microparticles by co-entrapping gelatinized starch and cross-linked phenylalanine ammonia lyase (PAL) aggregates (CLEAs) containing gelatinized starch into biomemitic silica and subsequently removing the starch by α-amylase treatment. During the preparation process, the gelatinzed starch served as a pore-forming agent to create pores in CLEAs and biomimetic silica. The resulting mesoporous CLEAs-silica composite microparticles exhibited higher activity and stability than native PAL, conventional CLEAs, and PAL encapsulated in biomimetic silica. Furthermore, the mesoporous CLEAs-silica composite microparticles displayed good reusability due to its suitable size and mechanical properties, and had excellent stability for storage. The superior catalytic performances were attributed to the combinational unique structure from the intra-cross-linking among enzyme aggregates and hard mesoporous silica shell, which not only decreased the enzyme-support negative interaction and mass-transfer limitations, but also improved the mechanical properties and monodispersity. This approach will be highly beneficial for preparing various bioactive mesoporous composites with excellent catalytic performance. PMID:26374188

  13. Adsorption on Mesoporous Metal-Organic Frameworks in Solution: Aromatic and Heterocyclic Compounds.

    PubMed

    Samokhvalov, Alexander

    2015-11-16

    Adsorption and desorption play major roles in separations, purification of water, waste streams, liquid fuels, catalysis, biomedicine and chromatography. Mesoporous metal-organic frameworks (MOFs) with pore sizes 2-50 nm are particularly suitable for adsorption of organic compounds in solution. Tens of thousands of aromatic and heterocyclic compounds are major components of liquid fuels, feedstock for industrial synthesis, solvents, dyestuffs, agricultural chemicals, medicinal drugs, food additives, and so forth. This Review provides a systematization and analysis of studies on adsorption/desorption on mesoporous MOFs in solution and their underlying chemical mechanisms. The (in)stability of mesoporous MOFs in water is critically discussed. Adsorption capacity and selectivity are covered for organic dyes, medicinal drugs, major components of liquid fuels, and miscellaneous industrial chemicals. Ionic interactions, Brønsted acid-base interactions, hydrogen bonding, coordination bonding, π-π interactions, and non-specific interactions are covered amongst adsorption mechanisms. The effects of post-synthetic modifications of mesoporous MOFs on their stability, adsorption capacity, selectivity, and mechanisms of adsorption and desorption are analyzed. To encourage research in this quickly growing field, we identify "niches" for which no application-oriented and/or mechanistic studies were reported. Perspectives and limitations of a wide use of mesoporous MOFs as industrial sorbents are discussed.

  14. Hierarchically ordered mesoporous Co3O4 materials for high performance Li-ion batteries

    PubMed Central

    Sun, Shijiao; Zhao, Xiangyu; Yang, Meng; Wu, Linlin; Wen, Zhaoyin; Shen, Xiaodong

    2016-01-01

    Highly ordered mesoporous Co3O4 materials have been prepared via a nanocasting route with three-dimensional KIT-6 and two-dimensional SBA-15 ordered mesoporous silicas as templates and Co(NO3)2 · 6H2O as precursor. Through changing the hydrothermal treating temperature of the silica template, ordered mesoporous Co3O4 materials with hierarchical structures have been developed. The larger pores around 10 nm provide an efficient transport for Li ions, while the smaller pores between 3–5 nm offer large electrochemically active areas. Electrochemical impedance analysis proves that the hierarchical structure contributes to a lower charge transfer resistance in the mesoporous Co3O4 electrode than the mono-sized structure. High reversible capacities around 1141 mAh g−1 of the hierarchically mesoporous Co3O4 materials are obtained, implying their potential applications for high performance Li-ion batteries. PMID:26781265

  15. The characterizations and electrochemical properties of lignosulfonate templates based mesoporous NiO

    NASA Astrophysics Data System (ADS)

    Chen, Feng; Yao, Hongfei; Fan, Ping; Yang, Jintao; Zhong, Mingqiang

    2013-06-01

    Environmentally recycled liginsulfonate were successfully employed for the facile synthesis of mesoporous NiO materials. The XRD, SEM, TEM and N2 adsorption-desorption analysis were performed for characterizing the structure and surface properties of resultant NiO. The proximate globular structure of lignin macromolecules played an templating role in the formation of mesoporous framework of NiO. The fabricated NiO nanostructures had high specific surface area (193.8 m2/g), large pore volume (0.42 cm3/g), and narrow pore size distribution making them ideal candidates for supercapacitor applications. CV, ESI and galvanostatic constant-current charge/discharge tests showed that the fabricated mesoporous NiO had high specific capacitance (342 Fṡg-1) and good circulatory stability. Furthermore, the mesoporous NiO showed a good rate capability, which is due to that the ordered mesopores did not limit the ion motion within the pores. The results suggest that resultant NiO mesostructures are a promising supercapacitor electrode material.

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

    SciTech Connect

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

    2015-01-15

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

  17. A reversible light-operated nanovalve on mesoporous silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Tarn, Derrick; Ferris, Daniel P.; Barnes, Jonathan C.; Ambrogio, Michael W.; Stoddart, J. Fraser; Zink, Jeffrey I.

    2014-02-01

    Two azobenzene α-cyclodextrin based nanovalves are designed, synthesized and assembled on mesoporous silica nanoparticles. Under aqueous conditions, the cyclodextrin cap is tightly bound to the azobenzene moiety and capable of holding back loaded cargo molecules. Upon irradiation with a near-UV light laser, trans to cis-photoisomerization of azobenzene initiates a dethreading process, which causes the cyclodextrin cap to unbind followed by the release of cargo. The addition of a bulky stopper to the end of the stalk allows this design to be reversible; complete dethreading of cyclodextrin as a result of unbinding with azobenzene is prevented as a consequence of steric interference. As a result, thermal relaxation of cis- to trans-azobenzene allows for the rebinding of cyclodextrin and resealing of the nanopores, a process which entraps the remaining cargo. Two stalks were designed with different lengths and tested with alizarin red S and propidium iodide. No cargo release was observed prior to light irradiation, and the system was capable of multiuse. On/off control was also demonstrated by monitoring the release of cargo when the light stimulus was applied and removed, respectively.Two azobenzene α-cyclodextrin based nanovalves are designed, synthesized and assembled on mesoporous silica nanoparticles. Under aqueous conditions, the cyclodextrin cap is tightly bound to the azobenzene moiety and capable of holding back loaded cargo molecules. Upon irradiation with a near-UV light laser, trans to cis-photoisomerization of azobenzene initiates a dethreading process, which causes the cyclodextrin cap to unbind followed by the release of cargo. The addition of a bulky stopper to the end of the stalk allows this design to be reversible; complete dethreading of cyclodextrin as a result of unbinding with azobenzene is prevented as a consequence of steric interference. As a result, thermal relaxation of cis- to trans-azobenzene allows for the rebinding of cyclodextrin and

  18. Gated silica mesoporous supports for controlled release and signaling applications.

    PubMed

    Coll, Carmen; Bernardos, Andrea; Martínez-Máñez, Ramón; Sancenón, Félix

    2013-02-19

    Blending molecular and supramolecular advances with materials science has resulted in recent years in the development of new organic-inorganic hybrid materials displaying innovative functionalities. One appealing concept in this field is the development of gated nanodevices. These materials are prepared by grafting molecular or supramolecular caps onto the external surface of mesoporous inorganic scaffolds loaded with a particular cargo. The caps or "gates" can then be opened and the cargo delivered at will upon the application of a given stimulus. In this Account, we report some of the recent advances we have made in designing such materials for drug delivery and as new chromo-fluorogenic probes. For controlled release applications, we have prepared capped hybrid mesoporous supports capable of being selectively opened by applying certain physical and chemical stimuli. We report examples of gated materials opened by changes in pH (using polyamines as caps), light (employing spiropyran derivatives or gold nanoparticles), and temperature (using selected paraffins). We also report gated materials opened by enzymes that cleave capping molecules based on lactose, hydrolyzed starch, and peptides. The use of enzymes is especially appealing because molecular caps built of enzyme-specific sequences made of peptides or other cleavable molecules could allow on-command delivery of drugs and biomolecules in specialized contexts. In the second part of the manuscript, we revisit the possibility of using hybrid gated nanomaterials as sensory systems. In such systems, when target analytes interact with the cap, their presence triggers the transport of a dye from pores to the solution, resulting in a chromo-fluorogenic signal that allows their detection. Two approaches are possible. In the first one, pores remain open and the dye can diffuse into the solution, until the presence of a target analyte binds to receptors in the caps and closes the gate. In the second approach, the caps

  19. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    PubMed Central

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-01-01

    Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant. PMID:27220563

  20. Preparation of mesoporous CdS-containing TiO{sub 2} film and enhanced visible light photocatalytic property

    SciTech Connect

    Zhu, Yanmei; Wang, Renliang Zhang, Wenping; Ge, Haiyan; Wang, Xiaopeng; Li, Li

    2015-01-15

    Highlights: • Well-dispersed distribution of CdS nanoparticles inside of TiO{sub 2} mesoporous structures was fabricated. • The sensitization of CdS nanoparticles significantly extends the response of TiO{sub 2} mesoporous film in the visible region. • An improved visible light photocatalytic activity was observed by the CdS–MTF. - Abstract: Mesoporous TiO{sub 2} films containing CdS nanocrystals were successfully fabricated by a two-step process of successive ionic layer adsorption and reaction (SILAR) technique and a solvothermal method followed by annealing. The distribution of CdS nanoparticles in the inner structures of the TiO{sub 2} mesoporous films is confirmed by field emission scanning electron microscope. The CdS modification of the mesoporous films results in an increase in the visible light adsorption, and exhibits more excellent photocatalytic degradation of methyl orange (MO) under visible light irradiation.

  1. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    NASA Astrophysics Data System (ADS)

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-05-01

    Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant.

  2. Synthesis and textural evolution of alumina particles with mesoporous structures

    NASA Astrophysics Data System (ADS)

    Liu, Xun; Peng, Tianyou; Yao, Jinchun; Lv, Hongjin; Huang, Cheng

    2010-06-01

    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 γ-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 - 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 γ-Al 2O 3 particles with mesostructures after further calcination at 1173 K, whereas coexisting SO 42- can promote above morphology evolution and then transformed into γ-Al 2O 3 nanofibers after calcination at 1173 K. Moreover nearly all materials retain relatively high specific surface areas larger than 100 m 2 g -1 even after calcinations at 1173 K.

  3. Synthesis of mesoporous zeolite single crystals with cheap porogens

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

  4. Mesoporous nanocomposite coatings for photonic devices: sol-gel approach

    NASA Astrophysics Data System (ADS)

    Islam, Shumaila; Bidin, Noriah; Riaz, Saira; Suan, Lau Pik; Naseem, Shahzad; Sanagi, Mohd. Marsin

    2016-10-01

    Thermally stable, optically active inorganic nanocomposites, i.e., aluminum-silicate (AS) and silica-titania (ST), are synthesized via acid-catalyzed low-temperature sol-gel method in order to get stable, crack-free coating material for photonic devices. The samples are characterized by atomic force microscope, field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett--Teller (BET) surface area, Barrett-Joyner-Halenda (BJH) pore size distribution surface analysis and UV-Vis spectroscopy. Microscopic results show good incorporation of ST and AS particles as composites with grain size within range of 12-17 and 62-109 nm, respectively. EDX analysis substantiated the stoichiometric formation of homogeneous nanocomposites. XRD of the films reveals primary polycrystalline anatase titania phase and mullite phase of ST and AS nanocomposites. FTIR confirms the heterogeneous bond linkage between titania, silica and alumina species. Furthermore, the fabricated samples have mesoporous nature with high surface area, large pore volume and diameter. The tunable refractive index of 1.33-1.35 with high transparency is obtained for synthesized nanocomposites. The experimental findings show that these physically modified and thermally stable alumina- and titania-doped silica-based composite coatings are promising for photonic devices modification.

  5. Mesoporous Cladophora cellulose separators for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pan, Ruijun; Cheung, Ocean; Wang, Zhaohui; Tammela, Petter; Huo, Jinxing; Lindh, Jonas; Edström, Kristina; Strømme, Maria; Nyholm, Leif

    2016-07-01

    Much effort is currently made to develop inexpensive and renewable materials which can replace the polyolefin microporous separators conventionally used in contemporary lithium-ion batteries. In the present work, it is demonstrated that mesoporous Cladophora cellulose (CC) separators constitute very promising alternatives based on their high crystallinity, good thermal stability and straightforward manufacturing. The CC separators, which are fabricated using an undemanding paper-making like process involving vacuum filtration, have a typical thickness of about 35 μm, an average pore size of about 20 nm, a Young's modulus of 5.9 GPa and also exhibit an ionic conductivity of 0.4 mS cm-1 after soaking with 1 M LiPF6 EC: DEC (1/1, v/v) electrolyte. The CC separators are demonstrated to be thermally stable at 150 °C and electrochemically inert in the potential range between 0 and 5 V vs. Li+/Li. A LiFePO4/Li cell containing a CC separator showed good cycling stability with 99.5% discharge capacity retention after 50 cycles at a rate of 0.2 C. These results indicate that the renewable CC separators are well-suited for use in high-performance lithium-ion batteries.

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

    PubMed

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

    2014-07-14

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

  7. Controlled release of alendronate from nitrogen-doped mesoporous carbon

    DOE PAGESBeta

    Saha, Dipendu; Spurri, Amanda; Chen, Jihua; Hensley, Dale K.

    2016-04-13

    With this study, we have synthesized a nitrogen doped mesoporous carbon with the BET surface area of 1066 m2/g, total pore volume 0.6 cm3/g and nitrogen content of 0.5%. Total alendronate adsorption in this carbon was ~5%. The release experiments were designed in four different media with sequential pH values of 1.2, 4.5, 6.8 and 7.4 for 3, 1, 3 and 5 h, respectively and at 37 °C to imitate the physiological conditions of stomach, duodenum, small intestine and colon, respectively. Release of the drug demonstrated a controlled fashion; only 20% of the drug was released in the media withmore » pH = 1.2, whereas 64% of the drug was released in pH = 7.4. This is in contrary to pure alendronate that was completely dissolved within 30 min in the first release media (pH = 1.2) only. The relatively larger uptake of alendronate in this carbon and its sustained fashion of release can be attributed to the hydrogen bonding between the drug and the nitrogen functionalities on carbon surface. Based on this result, it can be inferred that this formulation may lower the side effects of oral delivery of alendronate.« less

  8. Protective effect of mesoporous silica particles on encapsulated folates.

    PubMed

    Ruiz-Rico, María; Daubenschüz, Hanna; Pérez-Esteve, Édgar; Marcos, María D; Amorós, Pedro; Martínez-Máñez, Ramón; Barat, José M

    2016-08-01

    Mesoporous silica particles (MSPs) are considered suitable supports to design gated materials for the encapsulation of bioactive molecules. Folates are essential micronutrients which are sensitive to external agents that provoke nutritional deficiencies. Folates encapsulation in MSPs to prevent degradation and to allow their controlled delivery is a promising strategy. Nevertheless, no information exists about the protective effect of MSPs encapsulation to prevent their degradation. In this work, 5-formyltetrahydrofolate (FO) and folic acid (FA) were entrapped in MSPs functionalized with polyamines, which acted as pH-dependent molecular gates. The stability of free and entrapped vitamins after acidic pH, high temperature and light exposure was studied. The results showed the degradation of FO after high temperature and acidic pH, whereas entrapped FO displayed enhanced stability. Free FA was degraded by light, but MSPs stabilized the vitamin. The obtained results point toward the potential use of MSPs as candidates to enhance stability and to improve the bioavailability of functional biomolecules. PMID:27235728

  9. Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

    PubMed

    Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

    2016-02-29

    Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation.

  10. Stabilization of RNA through absorption by functionalized mesoporous silicate nanospheres.

    PubMed

    Johnson, Brandy J; Melde, Brian J; Dinderman, Michael A; Lin, Baochuan

    2012-01-01

    The potential for encapsulating RNA within tunable, semi-permeable structures for storage and transportation purposes offers an interesting approach to the reduction of stringent storage requirements that often hamper the field application of genetic analysis methods. In this study, we assessed the potential for application of functionalized, porous silicate sorbents in maintaining nucleic acid integrity. Mesoporous silica nanoparticles (MSNs) with and without incorporated stabilizing reagents were used to encapsulate triosephosphate isomerase mRNA of Arabidopsis thaliana. The absorption, elution, and the long-term stability of the RNA were monitored by using quantitative real-time RT-PCR. The results indicate that adsorbed RNA can be eluted from the sorbents using simple buffers and employed directly for downstream molecular diagnostic assays without any further processing. RNA integrity can be maintained for extended time periods under refrigeration temperatures in the presence of covalently immobilized stabilizing compounds. This study provides initial evidence of the potential for application of MSNs in transportation and storage. They may also have utility in sample collection and processing in restrictive environments.

  11. Protective effect of mesoporous silica particles on encapsulated folates.

    PubMed

    Ruiz-Rico, María; Daubenschüz, Hanna; Pérez-Esteve, Édgar; Marcos, María D; Amorós, Pedro; Martínez-Máñez, Ramón; Barat, José M

    2016-08-01

    Mesoporous silica particles (MSPs) are considered suitable supports to design gated materials for the encapsulation of bioactive molecules. Folates are essential micronutrients which are sensitive to external agents that provoke nutritional deficiencies. Folates encapsulation in MSPs to prevent degradation and to allow their controlled delivery is a promising strategy. Nevertheless, no information exists about the protective effect of MSPs encapsulation to prevent their degradation. In this work, 5-formyltetrahydrofolate (FO) and folic acid (FA) were entrapped in MSPs functionalized with polyamines, which acted as pH-dependent molecular gates. The stability of free and entrapped vitamins after acidic pH, high temperature and light exposure was studied. The results showed the degradation of FO after high temperature and acidic pH, whereas entrapped FO displayed enhanced stability. Free FA was degraded by light, but MSPs stabilized the vitamin. The obtained results point toward the potential use of MSPs as candidates to enhance stability and to improve the bioavailability of functional biomolecules.

  12. Mechanical Stability of Templated Mesoporous Silica Thin Films

    SciTech Connect

    Williford, Rick E.; Li, Xiaohong S.; Addleman, Raymond S.; Fryxell, Glen E.; Baskaran, Suresh; Birnbaum, Jerome C.; Coyle, Christopher A.; Zemanian, Thomas S.; Wang, Chong M.; Courtney, Andrea R.

    2005-11-07

    Mesoporous silica thin films about 1 micron thick were prepared by spin casting using several organic templates that provide a range of pore structures from disordered (sponge-like) to more ordered (honeycomb-like) 2D hexagonal arrays. Nanoindentation measurements indicate that the elastic modulus (E), and thus the density, of the pore wall material are substantially lower than for fused silica. The corresponding lower dielectric constant for pore walls was used to calculate film porosities (P) with recent correlations from the literature. Curve fits to the standard modulus vs. porosity correlation, E/Eporewall=(1-P)n, for the films gave lower n=2.2 for the honeycomb-like film with higher E, but higher n=2.5 for the sponge-like film with lower E, in contrast to theoretical expectations (n=2 for sponge-like and n=3 for honeycomb-like). Although the dielectric constant depends primarily on first-order structural information (P), the elastic modulus of these structurally imperfect films required second-order (pore wall thickness/diameter ratio) and third-order (pore connectivity) parameters to resolve the data. The power law exponent n can vary continuously, depending on the details of the mesostructure, and should not be assumed a' priori unless justified by detailed structural information

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

    SciTech Connect

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

    2011-07-01

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

  14. Magnetic mesoporous silica nanoparticles: fabrication and their laccase immobilization performance.

    PubMed

    Wang, Feng; Guo, Chen; Yang, Liang-rong; Liu, Chun-Zhao

    2010-12-01

    Newly large-pore magnetic mesoporous silica nanoparticles (MMSNPs) with wormhole framework structures were synthesized for the first time by using tetraethyl orthosilicate as the silica source and amine-terminated Jeffamine surfactants as template. Iminodiacerate was attached on these MMSNPs through a silane-coupling agent and chelated with Cu(2+). The Cu(2+)-chelated MMSNPs (MMSNPs-CPTS-IDA-Cu(2+)) showed higher adsorption capacity of 98.1 mg g(-1)-particles and activity recovery of 92.5% for laccase via metal affinity adsorption in comparison with MMSNPs via physical adsorption. The Michaelis constant (K(m)) and catalytic constant (k(cat)) of laccase immobilized on the MMSNPs-CPTS-IDA-Cu(2+) were 3.28 mM and 155.4 min(-1), respectively. Storage stability and temperature endurance of the immobilized laccase on MMSNPs-CPTS-IDA-Cu(2+) increased significantly, and the immobilized laccase retained 86.6% of its initial activity after 10 successive batch reactions operated with magnetic separation.

  15. Functionalization of mesoporous materials for lanthanide and actinide extraction.

    PubMed

    Florek, Justyna; Giret, Simon; Juère, Estelle; Larivière, Dominic; Kleitz, Freddy

    2016-10-14

    Among the energy sources currently available that could address our insatiable appetite for energy and minimize our CO2 emission, solar, wind, and nuclear energy currently occupy an increasing portion of our energy portfolio. The energy associated with these sources can however only be harnessed after mineral resources containing valuable constituents such as actinides (Ac) and rare earth elements (REEs) are extracted, purified and transformed into components necessary for the conversion of energy into electricity. Unfortunately, the environmental impacts resulting from their manufacture including the generation of undesirable and, sometimes, radioactive wastes and the non-renewable nature of the mineral resources, to name a few, have emerged as challenges that should be addressed by the scientific community. In this perspective, the recent development of functionalized solid materials dedicated to selective elemental separation/pre-concentration could provide answers to several of the above-mentioned challenges. This review focuses on recent advances in the field of mesoporous solid-phase (SP) sorbents designed for REEs and Ac liquid-solid extraction. Particular attention will be devoted to silica and carbon sorbents functionalized with commonly known ligands, such as phosphorus or amide-containing functionalities. The extraction performances of these new systems are discussed in terms of sorption capacity and selectivity. In order to support potential industrial applications of the silica and carbon-based sorbents, their main drawbacks and advantages are highlighted and discussed. PMID:27240525

  16. Biosynthesis of amorphous mesoporous aluminophosphates using yeast cells as templates

    SciTech Connect

    Sifontes, Ángela B.; González, Gema; Tovar, Leidy M.; Méndez, Franklin J.; Gomes, Maria E.; Cañizales, Edgar; Niño-Vega, Gustavo; Villalobos, Hector; Brito, Joaquin L.

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Amorphous aluminophosphates can take place using yeast as template. ► A mesoporous material was obtained. ► The specific surface area after calcinations ranged between 176 and 214 m{sup 2} g{sup −1}. -- Abstract: In this study aluminophosphates have been synthesized from aluminum isopropoxide and phosphoric acid solutions using yeast cells as template. The physicochemical characterization was carried out by thermogravimetric analysis; X-ray diffraction; Fourier transform infrared; N{sub 2} adsorption–desorption isotherms; scanning electron microscopy; transmission electron microscopy and potentiometric titration with N-butylamine for determination of: thermal stability; crystalline structure; textural properties; morphology and surface acidity, respectively. The calcined powders consisted of an intimate mixture of amorphous and crystallized AlPO particles with sizes between 23 and 30 nm. The average pore size observed is 13–16 nm and the specific surface area after calcinations (at 650 °C) ranged between 176 and 214 m{sup 2} g{sup −1}.

  17. Hollow Mesoporous Plasmonic Nanoshells for Enhanced Solar Vapor Generation.

    PubMed

    Zielinski, Marcin S; Choi, Jae-Woo; La Grange, Thomas; Modestino, Miguel; Hashemi, Seyyed Mohammad Hosseini; Pu, Ye; Birkhold, Susanne; Hubbell, Jeffrey A; Psaltis, Demetri

    2016-04-13

    In the past decade, nanomaterials have made their way into a variety of technologies in solar energy, enhancing the performance by taking advantage of the phenomena inherent to the nanoscale. Recent examples exploit plasmonic core/shell nanoparticles to achieve efficient direct steam generation, showing great promise of such nanoparticles as a useful material for solar applications. In this paper, we demonstrate a novel technique for fabricating bimetallic hollow mesoporous plasmonic nanoshells that yield a higher solar vapor generation rate compared with their solid-core counterparts. On the basis of a combination of nanomasking and incomplete galvanic replacement, the hollow plasmonic nanoshells can be fabricated with tunable absorption and minimized scattering. When exposed to sun light, each hollow nanoshell generates vapor bubbles simultaneously from the interior and exterior. The vapor nucleating from the interior expands and diffuses through the pores and combines with the bubbles formed on the outer wall. The lack of a solid core significantly accelerates the initial vapor nucleation and the overall steam generation dynamics. More importantly, because the density of the hollow porous nanoshells is essentially equal to the surrounding host medium these particles are much less prone to sedimentation, a problem that greatly limits the performance and implementation of standard nanoparticle dispersions.

  18. Functionalization of mesoporous materials for lanthanide and actinide extraction.

    PubMed

    Florek, Justyna; Giret, Simon; Juère, Estelle; Larivière, Dominic; Kleitz, Freddy

    2016-10-14

    Among the energy sources currently available that could address our insatiable appetite for energy and minimize our CO2 emission, solar, wind, and nuclear energy currently occupy an increasing portion of our energy portfolio. The energy associated with these sources can however only be harnessed after mineral resources containing valuable constituents such as actinides (Ac) and rare earth elements (REEs) are extracted, purified and transformed into components necessary for the conversion of energy into electricity. Unfortunately, the environmental impacts resulting from their manufacture including the generation of undesirable and, sometimes, radioactive wastes and the non-renewable nature of the mineral resources, to name a few, have emerged as challenges that should be addressed by the scientific community. In this perspective, the recent development of functionalized solid materials dedicated to selective elemental separation/pre-concentration could provide answers to several of the above-mentioned challenges. This review focuses on recent advances in the field of mesoporous solid-phase (SP) sorbents designed for REEs and Ac liquid-solid extraction. Particular attention will be devoted to silica and carbon sorbents functionalized with commonly known ligands, such as phosphorus or amide-containing functionalities. The extraction performances of these new systems are discussed in terms of sorption capacity and selectivity. In order to support potential industrial applications of the silica and carbon-based sorbents, their main drawbacks and advantages are highlighted and discussed.

  19. Direct imaging Au nanoparticle migration inside mesoporous silica channels.

    PubMed

    Liu, Zhengwang; Che, Renchao; Elzatahry, Ahmed A; Zhao, Dongyuan

    2014-10-28

    Supported metal nanoparticle (NP) catalysts have been widely used in many industry processes and catalytic reactions. Catalyst deactivation is mainly caused by the sintering of supported metal NPs. Hence, understanding the metal NPs' sintering behaviors has great significance in preventing catalyst deactivation. Here we report the metal particle migration inside/between mesochannels by scanning transmission electron microscopy and electron energy loss spectroscopy via an in situ TEM heating technique. A sintering process is proposed that particle migration predominates, driven by the difference of gravitational potential from the height of the uneven internal surface of the mesopores; when the distance of the gold nanoparticles with a size of about 3 and 5 nm becomes short after migration, the coalescence process is completed, which is driven by an "octopus-claw-like" expansion of a conduction electron cloud outside the Au NPs. The supports containing an abundance of micropores help to suppress particle migration and coalescence. Our findings provide the understanding toward the rational design of supported industrial catalysts and other nanocomposites with enhanced activity and stability for applications such as batteries, catalysis, drug delivery, gas sensors, and solar cells.

  20. Neutron imaging of ion transport in mesoporous carbon materials.

    PubMed

    Sharma, Ketki; Bilheux, Hassina Z; Walker, Lakeisha M H; Voisin, Sophie; Mayes, Richard T; Kiggans, Jim O; Yiacoumi, Sotira; DePaoli, David W; Dai, Sheng; Tsouris, Costas

    2013-07-28

    Neutron imaging is presented as a tool for quantifying the diffusion of ions inside porous materials, such as carbon electrodes used in the desalination process via capacitive deionization and in electrochemical energy-storage devices. Monolithic mesoporous carbon electrodes of ∼10 nm pore size were synthesized based on a soft-template method. The electrodes were used with an aqueous solution of gadolinium nitrate in an electrochemical flow-through cell designed for neutron imaging studies. Sequences of neutron images were obtained under various conditions of applied potential between the electrodes. The images revealed information on the direction and magnitude of ion transport within the electrodes. From the time-dependent concentration profiles inside the electrodes, the average value of the effective diffusion coefficient for gadolinium ions was estimated to be 2.09 ± 0.17 × 10(-11) m(2) s(-1) at 0 V and 1.42 ± 0.06 × 10(-10) m(2) s(-1) at 1.2 V. The values of the effective diffusion coefficient obtained from neutron imaging experiments can be used to evaluate model predictions of the ion transport rate in capacitive deionization and electrochemical energy-storage devices.

  1. Quaternary ammonium borohydride adsorption in mesoporous silicate MCM-48

    SciTech Connect

    Wolverton, Michael J; Daemen, Luke L; Hartl, Monika A

    2010-01-01

    Inorganic borohydrides have a high gravimetric hydrogen density but release H2 only under energetically unfavorable conditions. Surface chemistry may help in lowering thermodynamic barriers, but inclusion of inorganic borohydrides in porous silica materials has proved hitherto difficult or impossible. We show that borohydrides with a large organic cation are readily adsorbed inside mesoporous silicates, particularly after surface treatment. Thermal analysis reveals that the decomposition thermodynamics of tetraalkylammonium borohydrides are substantially affected by inclusion in MCM-48. Inelastic neutron scattering (INS) data show that the compounds adsorb on the silica surface. Evidence of pore loading is supplemented by DSC/TGA, XRD, FTIR, and BET isotherm measurements. Mass spectrometry shows significant hydrogen release at lower temperature from adsorbed borohydrides in comparison with the bulk borohydrides. INS data measured for partially decomposed samples indicates that the decomposition of the cation and anion is likely simultaneous. Additionally, these data confirm the formation of Si-H bonds on the silica surface upon decomposition of adsorbed tetramethylammonium borohydride.

  2. Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

    PubMed

    Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

    2016-02-29

    Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation. PMID:26732521

  3. Functionalized mesoporous bioactive glass scaffolds for enhanced bone tissue regeneration

    PubMed Central

    Zhang, Xingdi; Zeng, Deliang; Li, Nan; Wen, Jin; Jiang, Xinquan; Liu, Changsheng; Li, Yongsheng

    2016-01-01

    Mesoporous bioactive glass (MBG), which possesses excellent bioactivity, biocompatibility and osteoconductivity, has played an important role in bone tissue regeneration. However, it is difficult to prepare MBG scaffolds with high compressive strength for applications in bone regeneration; this difficulty has greatly hindered its development and use. To solve this problem, a simple powder processing technique has been successfully developed to fabricate a novel type of MBG scaffold (MBGS). Furthermore, amino or carboxylic groups could be successfully grafted onto MBGSs (denoted as N-MBGS and C-MBGS, respectively) through a post-grafting process. It was revealed that both MBGS and the functionalized MBGSs could significantly promote the proliferation and osteogenic differentiation of bMSCs. Due to its positively charged surface, N-MBGS presented the highest in vitro osteogenic capability of the three samples. Moreover, in vivo testing results demonstrated that N-MBGS could promote higher levels of bone regeneration compared with MBGS and C-MBGS. In addition to its surface characteristics, it is believed that the decreased degradation rate of N-MBGS plays a vital role in promoting bone regeneration. These findings indicate that MBGSs are promising materials with potential practical applications in bone regeneration, which can be successfully fabricated by combining a powder processing technique and post-grafting process. PMID:26763311

  4. Scaling Dimensions of Nitrogen Adsorption Characteristics in Modulated Mesoporous Aluminophosphates

    PubMed

    Petrakis; Pasxalidis; Theocharis; Hudson; Pomonis

    1997-01-01

    Mesoporous alumina-aluminophosphates (MAAP) of the general formula Al100PXM20 (M = Al, Fe, Cr, and Ni and X = 0, 4.5, 9, 18, 36, 72, and 144) were tested for their pore size distribution by nitrogen adsorption. The distribution of pore size can be modified by the addition of phosphorus. The scaling or fractal dimensions (DS) of the adsorption characteristics in the pores, calculated from the plots of the log of the corresponding cumulative BJH desorption pores surface area versus the log of the corresponding pore size, indicate that for low values of P/P0, the adsorption proceeds in a two-dimensional manner, independently of the pore size distribution (p.s.d.). However, at high P/P0 values and narrow p.s.d. DS >/= 3, while at wide p.s.d. DS > 3. At medium P/P0 values the DS values obtained were found as high as 10 for narrow pore size distribution and decrease as the p.s.d. becomes wide by the addition of phosphorus. These phenomena are related to the supercritical condensation of nitrogen in the pores of MAAP.

  5. Mesoporous Carbon for Capacitive Deionization of Saline Water

    SciTech Connect

    Tsouris, Costas; Mayes, Richard T; Kiggans, Jim; Sharma, Ms. Ketki; Yiacoumi, Sotira; DePaoli, David W; Dai, Sheng

    2011-01-01

    Self-assembled mesoporous carbon (MC) materials have been synthesized and tested for application in capacitive deionization (CDI) of saline water. MC was prepared by self-assembly of a triblock copolymer with hydrogen-bonded chains via a phenolic resin, such as resorcinol or phloroglucinol in acidic conditions, followed by carbonization and, in some cases, activation by KOH. Carbon synthesized in this way was ground into powder, from which activated MC sheets were produced. In a variation of this process, after the reaction of triblock copolymer with resorcinol or phloroglucinol, the gel that was formed was used to coat a graphite plate and then carbonized. The coated graphite plate in this case was not activated and was tested to serve as current collector during the CDI process. The performance of these MC materials was compared to that of carbon aerogel for salt concentrations ranging between 1000 ppm and 35,000 ppm. Resorcinol-based MC removed up to 15.2 mg salt per gram of carbon, while carbon aerogel removed 5.8 mg salt per gram of carbon. Phloroglucinol-based MC-coated graphite exhibited the highest ion removal capacity at 21 mg of salt per gram of carbon for 35,000 ppm salt concentration.

  6. Supersaturation of poorly soluble drugs induced by mesoporous magnesium carbonate.

    PubMed

    Zhang, Peng; Zardán Gómez de la Torre, Teresa; Welch, Ken; Bergström, Christel; Strømme, Maria

    2016-10-10

    This work investigates whether the solubility of poorly soluble compounds can be improved by using mesoporous magnesium carbonate (MMC) as the drug delivery system. A solvent evaporation method was used to load structurally diverse model drugs (celecoxib, cinnarizine and griseofulvin) into the pores of MMC. The drug-loaded carrier system was then characterized in terms of porosity, crystallinity, and release profiles by a variety of experimental techniques, including X-ray diffraction, nitrogen adsorption analysis, differential scanning calorimetry, infrared spectroscopy, UV absorption spectroscopy, and thermogravimetric analysis. All three drugs were in a non-crystalline state after loading into the pores of MMC. The concentrations of the drugs in solution over time (a measure of the release rates from loaded MMC) were higher than the corresponding concentrations (dissolution rates) of equal amounts of the crystalline drugs. The release rates were five (celecoxib), three (cinnarizine) and two times (griseofulvin) higher than the dissolution rates of their crystalline counterparts. Supersaturation release profiles were also observed; the areas under the concentration-time curves (0-240min) were 25- (celecoxib), 5- (cinnarizine) and 2-fold (griseofulvin) greater than those of the crystalline drugs. Hence, MMC shows promise as a general drug delivery vehicle for increasing the bioavailability of compounds with dissolution rate- or solubility-limited absorption. PMID:27590126

  7. Mesoporous NiO crystals with dominantly exposed {110} reactive facets for ultrafast lithium storage

    PubMed Central

    Su, Dawei; Ford, Mike; Wang, Guoxiu

    2012-01-01

    Faceted crystals with exposed highly reactive planes have attracted intensive investigations for applications such as hydrogen production, enhanced catalytic activity, and electrochemical energy storage and conversion. Herein, we report the synthesis of mesoporous NiO crystals with dominantly exposed {110} reactive facets by the thermal conversion of hexagonal Ni(OH)2 nanoplatelets. When applied as anode materials in lithium-ion batteries, mesoporous NiO crystals exhibit a high reversible lithium storage capacity of 700 mAh g−1 at 1 C rate in 100 cycles and an excellent cyclability. In particular, the dominantly exposed {110} reactive facets and mesoporous nanostructure of NiO crystals lead to ultrafast lithium storage, which mimics the high power delivery of supercapacitors. PMID:23226591

  8. Mesoporous platinum electrodes for amperometric determination of sugars with anion exchange chromatography.

    PubMed

    Han, Jee Hoon; Choi, Han Nim; Park, Sejin; Chung, Taek Dong; Lee, Won-Yong

    2010-01-01

    A simple amperometric detection (AD) method based on mesoporous platinum (Pt) electrodes has been developed for the determination of sugars (glucose, fructose, and sucrose) with high-performance anion-exchange chromatography (HPAEC). The amperometric detection is based on the direct oxidation of sugars on mesoporous Pt films formed on a gold electrode. The mesoporous Pt electrode (roughness factor of 243) sensitively responded to glucose, fructose, and sucrose in 80 mM sodium hydroxide solution as an alkaline mobile-phase for HPAEC. Under the optimum conditions, the limits of detection (S/N = 3) in these sugars were 0.24, 0.29, and 1.8 mM, for glucose, fructose, and sucrose, respectively. The reproducibility (relative standard deviation) of the measurements was less than 3.5%. The present method was applied to the determination of sugars in apple juice. The recoveries for all sugars ranged from 97 to 99%.

  9. A highly sensitive ethanol sensor based on mesoporous ZnO–SnO2 nanofibers

    PubMed Central

    Song, Xiaofeng; Wang, Zhaojie; Liu, Yongben; Wang, Ce; Li, Lijuan

    2009-01-01

    A facile and versatile method for the large-scale synthesis of sensitive mesoporous ZnO–SnO2 (m-Z–S) nanofibers through a combination of surfactant-directed assembly and an electrospinning approach is reported. The morphology and the structure were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), and nitrogen adsorption–desorption isotherm analysis. The results showed that the diameters of fibers ranged from 100 to 150 nm with mixed structures of wurtzite (ZnO) and rutile (SnO2), and a mesoporous structure was observed in the m-Z–S nanofibers. The sensor performance of the prepared m-Z–S nanofibers was measured for ethanol. It is found that the mesoporous fiber film obtained exhibited excellent ethanol sensing properties, such as high sensitivity, quick response and recovery, good reproducibility, and linearity in the range 3–500 ppm. PMID:19417420

  10. Nanoconfinement in activated mesoporous carbon of calcium borohydride for improved reversible hydrogen storage.

    PubMed

    Comănescu, Cezar; Capurso, Giovanni; Maddalena, Amedeo

    2012-09-28

    Mesoporous carbon frameworks were synthesized using the soft-template method. Ca(BH(4))(2) was incorporated into activated mesoporous carbon by the incipient wetness method. The activation of mesoporous carbon was necessary to optimize the surface area and pore size. Thermal programmed absorption measurements showed that the confinement of this borohydride into carbon nanoscaffolds improved its reversible capacity (relative to the reactive portion) and performance of hydrogen storage compared to unsupported borohydride. Hydrogen release from the supported hydride started at a temperature as low as 100 °C and the dehydrogenation rate was fast compared to the bulk borohydride. In addition, the hydrogen pressure necessary to regenerate the borohydride from the dehydrogenation products was reduced. PMID:22948563

  11. Hyaluronic acid modified mesoporous carbon nanoparticles for targeted drug delivery to CD44-overexpressing cancer cells

    NASA Astrophysics Data System (ADS)

    Wan, Long; Jiao, Jian; Cui, Yu; Guo, Jingwen; Han, Ning; Di, Donghua; Chang, Di; Wang, Pu; Jiang, Tongying; Wang, Siling

    2016-04-01

    In this paper, hyaluronic acid (HA) functionalized uniform mesoporous carbon spheres (UMCS) were synthesized for targeted enzyme responsive drug delivery using a facile electrostatic attraction strategy. This HA modification ensured stable drug encapsulation in mesoporous carbon nanoparticles in an extracellular environment while increasing colloidal stability, biocompatibility, cell-targeting ability, and controlled cargo release. The cellular uptake experiments of fluorescently labeled mesoporous carbon nanoparticles, with or without HA functionalization, demonstrated that HA-UMCS are able to specifically target cancer cells overexpressing CD44 receptors. Moreover, the cargo loaded doxorubicin (DOX) and verapamil (VER) exhibited a dual pH and hyaluronidase-1 responsive release in the tumor microenvironment. In addition, VER/DOX/HA-UMCS exhibited a superior therapeutic effect on an in vivo HCT-116 tumor in BALB/c nude mice. In summary, it is expected that HA-UMCS will offer a new method for targeted co-delivery of drugs to tumors overexpressing CD44 receptors.

  12. Synthesis, characterization and enhanced photoconductivity from a mesoporous titania on dye doping.

    PubMed

    Pal, Nabanita; Paul, Manidipa; Bera, Ashoke; Basak, Durga; Bhaumik, Asim

    2010-07-26

    New wormhole-like mesoporous TiO(2) material has been synthesized through a convenient sol-gel method in the presence of a Schiff base secondary amine hexadecyl-2-pyrrole-methylamine (HPMA) containing chelating donor sites as template or structure directing agent (SDA). SDA molecules can be easily removed from the composite to generate mesoporosity and upon removal of the SDA molecule, this mesoporous TiO(2) material showed very high surface area (480+/-10 m(2)/g) with an average pore diameter of 2.57+/-0.05 nm. When Rose Bengal dye is entrapped inside the nanopores of this material, it showed a drastic enhancement (ca. 40-folds) in the photoconductivity vis-à-vis mesoporous TiO(2) alone under white light illumination.

  13. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-03-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures.

  14. Cantilever bending based on humidity-actuated mesoporous silica/silicon bilayers

    PubMed Central

    Ganser, Christian; Fritz-Popovski, Gerhard; Morak, Roland; Sharifi, Parvin; Marmiroli, Benedetta; Sartori, Barbara; Amenitsch, Heinz; Griesser, Thomas; Teichert, Christian

    2016-01-01

    Summary We use a soft templating approach in combination with evaporation induced self-assembly to prepare mesoporous films containing cylindrical pores with elliptical cross-section on an ordered pore lattice. The film is deposited on silicon-based commercial atomic force microscope (AFM) cantilevers using dip coating. This bilayer cantilever is mounted in a humidity controlled AFM, and its deflection is measured as a function of relative humidity. We also investigate a similar film on bulk silicon substrate using grazing-incidence small-angle X-ray scattering (GISAXS), in order to determine nanostructural parameters of the film as well as the water-sorption-induced deformation of the ordered mesopore lattice. The strain of the mesoporous layer is related to the cantilever deflection using simple bilayer bending theory. We also develop a simple quantitative model for cantilever deflection which only requires cantilever geometry and nanostructural parameters of the porous layer as input parameters. PMID:27335753

  15. Hierarchical mesoporous/microporous carbon with graphitized frameworks for high-performance lithium-ion batteries

    SciTech Connect

    Lv, Yingying; Fang, Yin; Qian, Xufang; Tu, Bo; Wu, Zhangxiong; Asiri, Abdullah M.; Zhao, Dongyuan

    2014-11-01

    A hierarchical meso-/micro-porous graphitized carbon with uniform mesopores and ordered micropores, graphitized frameworks, and extra-high surface area of ∼2200 m{sup 2}/g, was successfully synthesized through a simple one-step chemical vapor deposition process. The commercial mesoporous zeolite Y was utilized as a meso-/ micro-porous template, and the small-molecule methane was employed as a carbon precursor. The as-prepared hierarchical meso-/micro-porous carbons have homogeneously distributed mesopores as a host for electrolyte, which facilitate Li{sup +} ions transport to the large-area micropores, resulting a high reversible lithium ion storage of 1000 mA h/g and a high columbic efficiency of 65% at the first cycle.

  16. Cantilever bending based on humidity-actuated mesoporous silica/silicon bilayers.

    PubMed

    Ganser, Christian; Fritz-Popovski, Gerhard; Morak, Roland; Sharifi, Parvin; Marmiroli, Benedetta; Sartori, Barbara; Amenitsch, Heinz; Griesser, Thomas; Teichert, Christian; Paris, Oskar

    2016-01-01

    We use a soft templating approach in combination with evaporation induced self-assembly to prepare mesoporous films containing cylindrical pores with elliptical cross-section on an ordered pore lattice. The film is deposited on silicon-based commercial atomic force microscope (AFM) cantilevers using dip coating. This bilayer cantilever is mounted in a humidity controlled AFM, and its deflection is measured as a function of relative humidity. We also investigate a similar film on bulk silicon substrate using grazing-incidence small-angle X-ray scattering (GISAXS), in order to determine nanostructural parameters of the film as well as the water-sorption-induced deformation of the ordered mesopore lattice. The strain of the mesoporous layer is related to the cantilever deflection using simple bilayer bending theory. We also develop a simple quantitative model for cantilever deflection which only requires cantilever geometry and nanostructural parameters of the porous layer as input parameters. PMID:27335753

  17. Electrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties.

    PubMed

    Li, Cuiling; Dag, Ömer; Dao, Thang Duy; Nagao, Tadaaki; Sakamoto, Yasuhiro; Kimura, Tatsuo; Terasaki, Osamu; Yamauchi, Yusuke

    2015-01-01

    Mesoporous gold (Au) films with tunable pores are expected to provide fascinating optical properties stimulated by the mesospaces, but they have not been realized yet because of the difficulty of controlling the Au crystal growth. Here, we report a reliable soft-templating method to fabricate mesoporous Au films using stable micelles of diblock copolymers, with electrochemical deposition advantageous for precise control of Au crystal growth. Strong field enhancement takes place around the center of the uniform mesopores as well as on the walls between the pores, leading to the enhanced light scattering as well as surface-enhanced Raman scattering (SERS), which is understandable, for example, from Babinet principles applied for the reverse system of nanoparticle ensembles.

  18. A photostable bi-luminophore pressure-sensitive paint measurement system developed with mesoporous silica nanoparticles.

    PubMed

    Mochizuki, Dai; Tamura, Shinichi; Yasutake, Hiroaki; Kataoka, Tomoharu; Mitsuo, Kazunori; Wada, Yuji

    2013-04-01

    The accurate and high-resolution measurement of surface pressure is achieved by a pressure/ temperature-sensitive composite paint (bi-PSP), whereas the pressure-sensitive dye photodegraded the temperature sensitive dye in close arrangement of both dyes. In the present study, an attempt was made to synthesize a homogeneous bi-PSP membrane without light-induced degradation of the dye using mesoporous silica. Mesoporous silica as a molecular sieve was the separation of pressure- and temperature-sensitive dyes. Both achievement of control of photodegradation in temperature-sensitive paints with molecule-screening capacity and macroscopically uniform placement of insoluble pigments in the respective solvent, was accomplished using the mesoporous silica nanoparticles in a compound PSP.

  19. Electrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties

    PubMed Central

    Li, Cuiling; Dag, Ömer; Dao, Thang Duy; Nagao, Tadaaki; Sakamoto, Yasuhiro; Kimura, Tatsuo; Terasaki, Osamu; Yamauchi, Yusuke

    2015-01-01

    Mesoporous gold (Au) films with tunable pores are expected to provide fascinating optical properties stimulated by the mesospaces, but they have not been realized yet because of the difficulty of controlling the Au crystal growth. Here, we report a reliable soft-templating method to fabricate mesoporous Au films using stable micelles of diblock copolymers, with electrochemical deposition advantageous for precise control of Au crystal growth. Strong field enhancement takes place around the center of the uniform mesopores as well as on the walls between the pores, leading to the enhanced light scattering as well as surface-enhanced Raman scattering (SERS), which is understandable, for example, from Babinet principles applied for the reverse system of nanoparticle ensembles. PMID:25799072

  20. Soft-Templating Synthesis and Properties of Mesoporous Alumina-Titania

    SciTech Connect

    Morris, Stacy M; Horton, Jr, Joe A; Jaroniec, Mietek

    2010-01-01

    Mesoporous alumina-titania materials, having various molar compositions of aluminum and titanium, were synthesized via cooperative self-assembly of the corresponding metal alkoxides and Pluronic P123 triblock copolymer (soft template) in ethanolic solution under acidic conditions. The resulting mixed metal oxides possess ordered mesopores at low to equal molar compositions of titanium in relation to aluminum (up to 50%) and worm-like mesostructures at higher molar compositions of titanium (50-75%). In addition, these mesoporous oxides exhibit high BET surface areas (up to 438 m2/g), large pore widths (from 7.37 to 18.55 nm) and pore volumes (from 0.16 to 0.64 cm3/g), narrow pore size distributions, crystalline pore walls and high thermal stability.

  1. Preparation of bicontinuous mesoporous silica and organosilica materials containing gold nanoparticles by co-synthesis method

    SciTech Connect

    Lee, Byunghwan; Zhu, Haoguo; Zhang, Zongtao; Overbury, Steven {Steve} H; Dai, Sheng

    2004-01-01

    Catalytic activities of gold strongly depend on its particle size. It is necessary to have homogeneous distributions of small gold nanoparticles with diameters between 2 and 5 nm for excellent catalytic activities. In this study, gold-containing mesoporous silica materials were prepared by a co-synthesis method. The essence of this sol-gel co-synthesis method is to combine together neutral surfactant template synthesis of mesoporous silica materials with the introduction of metal ions via bifunctional silane ligands, so that the formation of mesostructures and metal-ion doping occur simultaneously. The formation of gold nanoparticles with size less than 5 nm inside mesoporous materials (HMS, MSU, and PMO) has been achieved by this co-synthesis sol-gel process. In addition, the effects of post-treatments, such as calcination and reduction, on pore structures and nanoparticle size distributions were also investigated.

  2. Hollow mesoporous raspberry-like colloids with removable caps as photoresponsive nanocontainers.

    PubMed

    Hu, Chi; West, Kevin R; Scherman, Oren A

    2016-04-21

    The fabrication, characterisation and controlled cargo release of hollow mesoporous raspberry-like colloids (HMRCs), which are assembled by utilising host-guest complexation of cucurbit[8]uril (CB[8]) are described. CB[8] is employed as a supramolecular linker to 'stick' the viologen functionalised paramagnetic iron oxide nanoparticles onto an azobenzene functionalised hollow mesoporous silica core. The formed HMRCs are photoresponsive and can be reversibly disassembled upon light irradiation, endowing them with an ability to release loaded cargo under photocontrol. While the assembled HMRCs retain cargo inside their cavity, disassembled particles with their iron oxide nanoparticle 'caps' removed will release the loaded cargo through the mesoporous shell of the hollow silica colloids. A model system using a boronic acid derivative as the cargo in the HMRCs and Alizarin Red salt as a sensor for the released boronic acid is demonstrated. PMID:27010833

  3. Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

    NASA Astrophysics Data System (ADS)

    Pal, Nabanita; Bhaumik, Asim

    2012-05-01

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

  4. Hollow mesoporous raspberry-like colloids with removable caps as photoresponsive nanocontainers.

    PubMed

    Hu, Chi; West, Kevin R; Scherman, Oren A

    2016-04-21

    The fabrication, characterisation and controlled cargo release of hollow mesoporous raspberry-like colloids (HMRCs), which are assembled by utilising host-guest complexation of cucurbit[8]uril (CB[8]) are described. CB[8] is employed as a supramolecular linker to 'stick' the viologen functionalised paramagnetic iron oxide nanoparticles onto an azobenzene functionalised hollow mesoporous silica core. The formed HMRCs are photoresponsive and can be reversibly disassembled upon light irradiation, endowing them with an ability to release loaded cargo under photocontrol. While the assembled HMRCs retain cargo inside their cavity, disassembled particles with their iron oxide nanoparticle 'caps' removed will release the loaded cargo through the mesoporous shell of the hollow silica colloids. A model system using a boronic acid derivative as the cargo in the HMRCs and Alizarin Red salt as a sensor for the released boronic acid is demonstrated.

  5. Ag-loaded mesoporous bioactive glasses against Enterococcus faecalis biofilm in root canal of human teeth.

    PubMed

    Fan, Wei; Wu, Daming; Ma, Tengjiao; Fan, Bing

    2015-01-01

    Ag-loaded mesoporous bioactive glass (Ag-MBG) powders were synthesized and characterized. The ions release of Ag-MBGs in Tris-HCl and the pH stability of simulated body fluids after immersing Ag-MBGs were tested. Root canals were inoculated with Enterococcus faecalis for 4 weeks, and the antibacterial activity of MBGs, Ag-MBGs and calcium hydroxide against E. faecalis biofilm were evaluated. Results showed that Ag-MBGs possessed highly ordered mesoporous structure with silver nanoparticles deposited in the mesopores, which enabled a sustained Ag ions released. The biofilms treated with Ag-MBGs showed a significant structural disruption compared with MBGs. These results indicated that Ag-MBGs possess a potent antibacterial effect against E.faecalis biofilm in root canal, and the antibacterial activity was induced by the release of Ag ions from Ag-MBGs.

  6. Imprint-coating synthesis of selective functionalized ordered mesoporous sorbents for separation and sensors

    DOEpatents

    Dai, Sheng; Burleigh, Mark C.; Shin, Yongsoon

    2001-01-01

    The present invention relates generally to mesoporous sorbent materials having high capacity, high selectivity, fast kinetics, and molecular recognition capability. The invention also relates to a process for preparing these mesoporous substrates through molecular imprinting techniques which differ from convention techniques in that a template molecule is bound to one end of bifunctional ligands to form a complex prior to binding of the bifunctional ligands to the substrate. The present invention also relates to methods of using the mesoporous sorbent materials, for example, in the separation of toxic metals from process effluents, paints, and other samples; detection of target molecules, such as amino acids, drugs, herbicides, fertilizers, and TNT, in samples; separation and/or detection of substances using chromatography; imaging agents; sensors; coatings; and composites.

  7. Bio-templated synthesis of highly ordered macro-mesoporous silica material for sustained drug delivery

    NASA Astrophysics Data System (ADS)

    Qu, Fengyu; Lin, Huiming; Wu, Xiang; Li, Xiaofeng; Qiu, Shilun; Zhu, Guangshan

    2010-05-01

    The bimodal porous structured silica materials consisting of macropores with the diameter of 5-20 μm and framework-like mesopores with the diameter of 4.7-6.0 nm were prepared using natural Manchurian ash and mango linin as macropored hard templates and P123 as mesopore soft templates, respectively. The macroporous structures of Manchurian ash and mango linin were replicated with the walls containing highly ordered mesoporous silica as well. As-synthesized dual porous silica was characterized by scanning electron microscope (SEM), powder X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption/desorption, fourier transform IR (FTIR) spectroscopy, and thermo-gravimetric analyzer (TGA). Ibuprofen (Ibu) was employed as a model drug and the release profiles showed that the dual porous material had a sustained drug delivery capability. And such highly ordered dual pore silica materials may have potential applications for bimolecular adsorption/separation and tissue repairing.

  8. Fabrication and testing of engineered forms of self-assembled monolayers on mesoporous silica (SAMMS) material

    SciTech Connect

    Mattigod, S.V.; Liu, J.; Fryxell, G.E.; Baskaran, S.; Gong, M.; Nie, Z.; Feng, X.; Klasson, K.T.

    1998-09-01

    A number of engineered forms such as flexible extrudates, beads, and rods were fabricated using thiol-SAMMS (Self-Assembled Monolayers on Mesoporous Silica) and tested for their mercury adsorption capacities. The flexible extrudate form had a mercury adsorption capacity of 340 mg/g but was found to be structurally unstable. A structurally sound bead form of thiol-SAMMS was fabricated with 5, 10, 25, and 40% by weight clay binder (attapulgite) and successfully functionalized. A structurally stable but non-optimized rod form of thiol-SAMMS was also fabricated. Bench-scale processes were developed to silanize and functionalize mesoporous silica beads made with attapulgite clay binder. Contact angle measurements were conducted to assess the degree of surface coverage by functional groups on mesoporous silica materials.

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

    PubMed

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

    2016-01-01

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

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

    PubMed Central

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

    2016-01-01

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

  11. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    PubMed Central

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-01-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures. PMID:25757800

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

    NASA Astrophysics Data System (ADS)

    Dayal, Saurabh; Kumar, C. Sasi

    2016-05-01

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

  13. Cellulose conjugated FITC-labelled mesoporous silica nanoparticles: intracellular accumulation and stimuli responsive doxorubicin release.

    PubMed

    Hakeem, Abdul; Zahid, Fouzia; Duan, Ruixue; Asif, Muhammad; Zhang, Tianchi; Zhang, Zhenyu; Cheng, Yong; Lou, Xiaoding; Xia, Fan

    2016-03-01

    Herein, we design novel cellulose conjugated mesoporous silica nanoparticle (CLS-MSP) based nanotherapeutics for stimuli responsive intracellular doxorubicin (DOX) delivery. DOX molecules are entrapped in pores of the fabricated mesoporous silica nanoparticles (MSPs) while cellulose is used as an encapsulating material through esterification on the outlet of the pores of the MSPs to avoid premature DOX release under physiological conditions. In in vitro studies, stimuli responsive DOX release is successfully achieved from DOX loaded cellulose conjugated mesoporous silica nanoparticles (DOX/CLS-MSPs) by pH and cellulase triggers. Intracellular accumulation of DOX/CLS-MSPs in human liver cancer cells (HepG2 cells) is investigated through confocal microscope magnification. Cell viability of HepG2 cells is determined as the percentage of the cells incubated with DOX/CLS-MSPs compared with that of non-incubated cells through an MTT assay.

  14. Hollow mesoporous raspberry-like colloids with removable caps as photoresponsive nanocontainers

    NASA Astrophysics Data System (ADS)

    Hu, Chi; West, Kevin R.; Scherman, Oren A.

    2016-04-01

    The fabrication, characterisation and controlled cargo release of hollow mesoporous raspberry-like colloids (HMRCs), which are assembled by utilising host-guest complexation of cucurbit[8]uril (CB[8]) are described. CB[8] is employed as a supramolecular linker to `stick' the viologen functionalised paramagnetic iron oxide nanoparticles onto an azobenzene functionalised hollow mesoporous silica core. The formed HMRCs are photoresponsive and can be reversibly disassembled upon light irradiation, endowing them with an ability to release loaded cargo under photocontrol. While the assembled HMRCs retain cargo inside their cavity, disassembled particles with their iron oxide nanoparticle `caps' removed will release the loaded cargo through the mesoporous shell of the hollow silica colloids. A model system using a boronic acid derivative as the cargo in the HMRCs and Alizarin Red salt as a sensor for the released boronic acid is demonstrated.The fabrication, characterisation and controlled cargo release of hollow mesoporous raspberry-like colloids (HMRCs), which are assembled by utilising host-guest complexation of cucurbit[8]uril (CB[8]) are described. CB[8] is employed as a supramolecular linker to `stick' the viologen functionalised paramagnetic iron oxide nanoparticles onto an azobenzene functionalised hollow mesoporous silica core. The formed HMRCs are photoresponsive and can be reversibly disassembled upon light irradiation, endowing them with an ability to release loaded cargo under photocontrol. While the assembled HMRCs retain cargo inside their cavity, disassembled particles with their iron oxide nanoparticle `caps' removed will release the loaded cargo through the mesoporous shell of the hollow silica colloids. A model system using a boronic acid derivative as the cargo in the HMRCs and Alizarin Red salt as a sensor for the released boronic acid is demonstrated. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR01016D

  15. Cellulose conjugated FITC-labelled mesoporous silica nanoparticles: intracellular accumulation and stimuli responsive doxorubicin release

    NASA Astrophysics Data System (ADS)

    Hakeem, Abdul; Zahid, Fouzia; Duan, Ruixue; Asif, Muhammad; Zhang, Tianchi; Zhang, Zhenyu; Cheng, Yong; Lou, Xiaoding; Xia, Fan

    2016-02-01

    Herein, we design novel cellulose conjugated mesoporous silica nanoparticle (CLS-MSP) based nanotherapeutics for stimuli responsive intracellular doxorubicin (DOX) delivery. DOX molecules are entrapped in pores of the fabricated mesoporous silica nanoparticles (MSPs) while cellulose is used as an encapsulating material through esterification on the outlet of the pores of the MSPs to avoid premature DOX release under physiological conditions. In in vitro studies, stimuli responsive DOX release is successfully achieved from DOX loaded cellulose conjugated mesoporous silica nanoparticles (DOX/CLS-MSPs) by pH and cellulase triggers. Intracellular accumulation of DOX/CLS-MSPs in human liver cancer cells (HepG2 cells) is investigated through confocal microscope magnification. Cell viability of HepG2 cells is determined as the percentage of the cells incubated with DOX/CLS-MSPs compared with that of non-incubated cells through an MTT assay.Herein, we design novel cellulose conjugated mesoporous silica nanoparticle (CLS-MSP) based nanotherapeutics for stimuli responsive intracellular doxorubicin (DOX) delivery. DOX molecules are entrapped in pores of the fabricated mesoporous silica nanoparticles (MSPs) while cellulose is used as an encapsulating material through esterification on the outlet of the pores of the MSPs to avoid premature DOX release under physiological conditions. In in vitro studies, stimuli responsive DOX release is successfully achieved from DOX loaded cellulose conjugated mesoporous silica nanoparticles (DOX/CLS-MSPs) by pH and cellulase triggers. Intracellular accumulation of DOX/CLS-MSPs in human liver cancer cells (HepG2 cells) is investigated through confocal microscope magnification. Cell viability of HepG2 cells is determined as the percentage of the cells incubated with DOX/CLS-MSPs compared with that of non-incubated cells through an MTT assay. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08753h

  16. Highly oriented surface-growth and covalent dye labeling of mesoporous metal-organic frameworks.

    PubMed

    Hinterholzinger, Florian M; Wuttke, Stefan; Roy, Pascal; Preusse, Thomas; Schaate, Andreas; Behrens, Peter; Godt, Adelheid; Bein, Thomas

    2012-04-14

    Mesoporous amino-functionalized metal-organic framework thin films with the UiO-68 topology were grown in a highly oriented fashion on two different self-assembled monolayers on gold. The oriented MOF films were covalently modified with the fluorescent dye Rhodamine B inside the pore system, as demonstrated with size-selective fluorescence quenching studies. Our study suggests that mesoporous metal-organic frameworks are promising hosts for the covalent attachment of numerous functional moieties in a molecularly designed crystalline environment.

  17. Synthesis and characterization of hollow mesoporous BaFe12O19 spheres

    SciTech Connect

    Xu, X; Park, J; Hong, YK; Lane, AM

    2015-02-01

    A facile method is reported to synthesize hollow mesoporous BaFe12O19 spheres using a template-free chemical etching process. Hollow BaFe12O19 spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 degrees C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. (C) 2014 Elsevier Inc. All rights reserved.

  18. Cooperative Template-Directed Assembly of Mesoporous Metal–Organic Frameworks

    SciTech Connect

    Sun, Lin-Bing; Li, Jian-Rong; Park, Jinhee; Zhou, Hong-Cai

    2012-01-11

    Despite great efforts, the development of a reliable way to assemble mesoporous metal–organic frameworks (mesoMOFs) remains a challenge. In this work, we have designed a cooperative template system, comprising a surfactant (cetyltrimethylammonium bromide) and a chelating agent (citric acid), for the generation of a mesoMOF containing a hierarchical system of mesopores interconnected with microspores. The surfactant molecules form micelles and the chelating agent bridges the MOF and the micelles, making self-assembly and crystal growth proceed under the direction of the cooperative template. However, when the surfactant or the chelating agent was applied individually, no mesoMOF was obtained.

  19. Silica mesoporous thin films as containers for benzotriazole for corrosion protection of 2024 aluminium alloys

    NASA Astrophysics Data System (ADS)

    Recloux, Isaline; Mouanga, Maixent; Druart, Marie-Eve; Paint, Yoann; Olivier, Marie-Georges

    2015-08-01

    This work contributes to the development of a new environmentally friendly alternative pretreatment for 2024 aluminium alloys to replace hexavalent chromium based conversion layers in the aeronautical field. A silica mesoporous thin film, synthesized through the evaporation induced self-assembly process, was doped with benzotriazole to obtain active corrosion protection. Inhibitor loading contents were correlated with pore characteristics. The release kinetics was studied as function of pH. The application of the doped mesoporous film on 2024 aluminium alloy revealed a slowing down of corrosion processes, demonstrating its potential as an active inhibitor storage layer.

  20. Removal of mercury from aqueous solution using mesoporous silica nanoparticles modified with polyamide receptor.

    PubMed

    He, Chunsheng; Ren, Long; Zhu, Weiping; Xu, Yufang; Qian, Xuhong

    2015-11-15

    Based on the principle of supramolecular recognition and fluorescent chemical sensors, a novel kind of material for the separation of toxic heavy metal ions was designed and synthesized. Mesoporous silica nanoparticles MCM-41 with high surface areas and large ordered pores were used as the supporting matrix. Poly-amide derivative, was grafted to the mesoporous silica nanoparticles for extracting and separating trace Hg(2+) from aqueous solution, with a short adsorption time (t=3min) and a wide range of pH application (pH 3-11). The separation material could also extract trace mercury from Traditional Chinese Medicine, and has no influence on their effective components. PMID:26232282