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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. PMID:25424473

  2. 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.

  3. 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

  4. 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.

  5. 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. PMID:23428822

  6. 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. PMID:26745008

  7. 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

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

    PubMed

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

    2015-07-15

    Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration. PMID:25795275

  9. 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 ...

  10. 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...

  11. 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

  12. Catalysis at the toulene/water interface: Octadecyl immobilized H-ZSM-5 catalyst promoted hydrolysis of water-insoluble esters

    SciTech Connect

    Ogawa, Haruo; Koh, Tensai ); Taya, Kazuo ); Chihara, Teiji , Wako )

    1994-08-01

    Octadecyltrichorosilane-treated H-ZSM-5, abbreviated as H-ZSM-5-C[sub 18] resulted in an effective catalyst for the hydrolysis of water-insoluble esters in toluene-water solvent system. These floated at the interface of the two liquids. The H-ZSM-5-C[sub 18] catalyst showed ca. 60 times the activity of H-ZSM-5 for the hydrolysis of dodecyl acetate. Acid strength of H-ZSM-5 in water (-5.6 < Ho [<=] -3.0) was maintained even after the treatment with octadecyltrichlorosilane. The treatment renders H-ZSM-5 lipophylicity and provides a quasi-lipid phase on the surface. The shape-selective properties of H-ZSM-5-C[sub 18] catalyst were observed for the hydrolysis of aliphatic esters with straight chains. 17 refs., 9 figs., 6 tabs.

  13. 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.

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

    PubMed

    Liu, Zhen; Zhang, Zhongdong; Xing, Wei; Komarneni, Sridhar; Yan, Zifeng; Gao, Xionghou; Zhou, Xiaoping

    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

  15. 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.

  16. 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.

  17. 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

  18. Ozone-assisted photocatalytic oxidation of gaseous acetaldehyde on TiO2/H-ZSM-5 catalysts.

    PubMed

    Huang, Xin; Yuan, Jian; Shi, Jianwei; Shangguan, Wenfeng

    2009-11-15

    TiO(2)/H-ZSM-5 catalysts were prepared by impregnation with different amount of TiO(2) loading and calcination at various temperatures. The catalysts were characterized by X-ray diffraction (XRD), ultraviolet and visible spectroscopy (UV-vis) and BET specific surface area. It was demonstrated that the anatase TiO(2) retained stable on H-ZSM-5 after heat treatment even at 700 degrees C. The activities of samples were investigated under the various conditions of UV, ozone and UV-ozone, respectively by the comparison of acetaldehyde degradation. It was found that the photocatalysis combined with ozonation promoted the acetaldehyde degradation. TiO(2)/H-ZSM-5 catalysts were superior to simple TiO(2) and H-ZSM-5 with respect to the ozone-assisted photocatalytic oxidation of gaseous acetaldehyde, and the activity of the catalyst TiO(2)/H-ZSM-5 (TiO(2):H-ZSM-5=2:10) is the highest one among all those prepared samples. The improvement was attributed to the synergetic effect among adsorption, ozonation and catalytic reaction. PMID:19604630

  19. 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.

  20. 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.

  1. 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.

  2. 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. PMID:25009974

  3. Influence of Alumina Binder Content on Catalytic Performance of Ni/HZSM-5 for Hydrodeoxygenation of Cyclohexanone

    PubMed Central

    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. PMID:25009974

  4. 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.

  5. Solid-state NMR investigation of acid sites in dealuminated HZSM-5 zeolite.

    PubMed

    Deng, F; Du, Y; Ye, C H

    1996-01-01

    The acid sites and the hydration behaviors of dealuminated HZSM-5 zeolites (calcined at 550, 600, 650, and 700 degrees C) were characterized by high-resolution 1H MAS, 1H{27A1} spin-echo double resonance in combination with 27A1 MAS NMR. Apart from the usually observed peaks for dealuminated zeolite HZSM-5, a narrow plus a broad peak simultaneously appears at ca. 6.9 ppm in the 1H spectra and they exhibit different decay behavior in the 1H [27A1] double-resonance experiments. The existence of the former signal indicates that Lewis acid sites may'be formed in the zeolites after calcination. By means of the spin echo double resonance technique, we observed for the first time a previously unexpected narrow signal at 5.2 ppm, which resonates on the downfield side of Bronsted acid signal (4.3 ppm) and cannot be resolved in the 1H MAS spectra. This new signal is probably due to another kind of Bronsted acid site, locating in the small cages bounded by four- and five-membered rings. Three narrow peaks at 50 ppm, 30 ppm, and 0 ppm are superimposed on a very broad signal in the 27A1 MAS NMR spectra of dried HZSM-5. The intensity of the line at 50 ppm is significantly reduced compared with that of the rehydrated sample. 27A1 MAS NMR suggests that most part of the four-coordinated framework A1 turns into a intermediate case between four- and three-coordinated A1 after the dehydration and this process is reversible upon dehydration/rehydration. While some framework A1 atoms are transformed into three-coordinated A1 species and Lewis acid sites are, thus, generated in the dealuminated zeolites. For the signal at 30 ppm, the hydration leads to a dispersion in the chemical shift or the quadrupole interaction, which broadens its linewidth in hydrated samples. PMID:8970117

  6. Structural and electronic features of a Broensted acid site in H-ZSM-5

    SciTech Connect

    Cook, S.J.; Chakraborty, A.K.; Bell, A.T.; Theodorou, D.N. Univ. of California, Berkeley )

    1993-06-24

    The authors report the results of local density functional theory calculations on a Broensted acid site of the zeolite H-ZSM-5. They have investigated the structural and electronic properties of the site. Comparison is made between their results and existing experimental data. It is shown that structural relaxation around an acid site must be performed to obtain accurate energetics for substitution of aluminum into the zeolite framework. The effects of cluster termination are studied by comparing results obtained for both isolated clusters and clusters embedded in a Madelung field generated by the zeolite framework. The properties of the electron density distribution in the region around an acidic proton indicate that the acidic moiety may be characterized as a rather soft acid. 47 refs., 5 figs., 4 tabs.

  7. Thermodynamics and kinetics of adsorption of selected monoalkylbenzenes in H-ZSM-5

    SciTech Connect

    Schumacher, R.; Karge, H.G.

    1999-03-04

    In this study, the authors present the first systematic investigation of the adsorption of n-propylbenzene, isopropylbenzene, and n-butylbenzene in H-ZSM-5. Both the sorption isotherms and the rate of sorption uptake were investigated at temperatures between 315 and 425 K. The adsorption isotherms are of type 1 and are reasonably well described by the Langmuir-Freundlich model. It is shown that the heat of adsorption of the longer sorbate molecules depends significantly on the concentration, thus indicating an increased influence of sorbate-sorbate interaction. The uptake rates are determined by Fickian diffusion. The activation energies for the diffusion process are identical for all systems (32--36 kJ/mol). The diffusivities are also in the same order of magnitude decreasing noticeably for sorbates with longer or more complex substituents. A tentative explanation based on a simple jump-rate model for intracrystalline diffusion is given.

  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. Selective dehydration of bio-ethanol to ethylene catalyzed by lanthanum-phosphorous-modified HZSM-5: influence of the fusel.

    PubMed

    Hu, Yaochi; Zhan, Nina; Dou, Chang; Huang, He; Han, Yuwang; Yu, Dinghua; Hu, Yi

    2010-11-01

    Bio-ethanol dehydration to ethylene is an attractive alternative to oil-based ethylene. The influence of fusel, main byproducts in the fermentation process of bio-ethanol production, on the bio-ethanol dehydration should not be ignored. We studied the catalytic dehydration of bio-ethanol to ethylene over parent and modified HZSM-5 at 250°C, with weight hourly space velocity (WHSV) equal to 2.0/h. The influences of a series of fusel, such as isopropanol, isobutanol and isopentanol, on the ethanol dehydration over the catalysts were investigated. The 0.5%La-2%PHZSM-5 catalyst exhibited higher ethanol conversion (100%), ethylene selectivity (99%), and especially enhanced stability (more than 70 h) than the parent and other modified HZSM-5. We demonstrated that the introduction of lanthanum and phosphorous to HZSM-5 could weaken the negative influence of fusel on the formation of ethylene. The physicochemical properties of the catalysts were characterized by ammonia temperature-programmed desorption (NH(3)-TPD), nitrogen adsorption and thermogravimetry (TG)/differential thermogravimetry (DTG)/differential thermal analysis (DTA) (TG/DTG/DTA) techniques. The results indicated that the introduction of lanthanum and phosphorous to HZSM-5 could inhibit the formation of coking during the ethanol dehydration to ethylene in the presence of fusel. The development of an efficient catalyst is one of the key technologies for the industrialization of bio-ethylene. PMID:21058319

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

    PubMed

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

    2015-04-16

    Dehydration over acidic zeolites is an important reaction class for the upgrading of biomass pyrolysis vapors to hydrocarbon fuels or to precursors for myriad chemical products. Here, we examine the dehydration of ethanol at a Brønsted acid site, T12, found in HZSM-5 using density functional theory (DFT). The geometries of both cluster and mixed quantum mechanics/molecular mechanics (QM:MM) models are prepared from the ZSM-5 crystal structure. Comparisons between these models and different DFT methods are conducted to show similar results among the models and methods used. Inclusion of the full catalyst cavity through a QM:MM approach is found to be important, since activation barriers are computed on average as 7 kcal mol(-1) lower than those obtained with a smaller cluster model. Two different pathways, concerted and stepwise, have been considered when examining dehydration and deprotonation steps. The current study shows that a concerted dehydration process is possible with a lower (4-5 kcal mol(-1)) activation barrier while previous literature studies have focused on a stepwise mechanism. Overall, this work demonstrates that fairly high activation energies (∼50 kcal mol(-1)) are required for ethanol dehydration. A concerted mechanism is favored over a stepwise mechanism because charge separation in the transition state is minimized. QM:MM approaches appear to provide superior results to cluster calculations due to a more accurate representation of charges on framework oxygen atoms. PMID:25802969

  11. 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

  12. 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. PMID:25370739

  13. Microstructured fiber@HZSM-5 core-shell catalysts with dramatic selectivity and stability improvement for the methanol-to-propylene process.

    PubMed

    Wang, Xiangyu; Wen, Ming; Wang, Chunzheng; Ding, Jia; Sun, Ying; Liu, Ye; Lu, Yong

    2014-06-18

    We report a macroscopic stainless-steel-fiber@HZSM-5 core-shell catalyst by direct growth of 27 wt% HZSM-5 on a 3D microfibrous structure using 20 μm SS fibers, demonstrating dramatic selectivity and stability improvement in the MTP process. The unprecedented performance is due to the promotion of the olefin methylation/cracking cycle in methanol-to-hydrocarbon catalysis. PMID:24798420

  14. 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.

  15. 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.

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

    PubMed

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

    2012-07-15

    TiO(2) hybridized with HZSM-5 zeolites photocatalysts were prepared by a simple solid state dispersion method. The physicochemical properties of the catalysts were characterized by X-ray diffraction, UV-vis diffuse reflectance and FT-IR spectroscopy. The photocatalytic oxidation of NO(x) over TiO(2)/HZSM-5 having different Si/Al ratios was carried out under various levels of humidity and different pre-adsorption times in dark. The TiO(2)/HZSM-5 composite catalysts exhibited higher NO conversion and lower NO(2) formation than pure TiO(2). Pre-adsorption with water vapor and the high humidity during the photoreaction were harmful to the reactivity of TiO(2) hybridized with hydrophilic HZSM-5 zeolite. However, the photocatalytic reactivity of TiO(2) hybridized with hydrophobic zeolite varied little with increase in humidity. The results indicated that the high photocatalytic reactivity of TiO(2)/HZSM-5 catalysts is largely depended on the hydrophobicity of the zeolites. PMID:22579762

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. Alkane Activation Initiated by Hydride Transfer: Co-conversion of Propane and Methanol over H-ZSM-5 Zeolite.

    PubMed

    Yu, Si-Min; Wu, Jian-Feng; Liu, Chong; Liu, Wei; Bai, Shi; Huang, Jun; Wang, Wei

    2015-06-15

    Co-conversion of alkane with another reactant over zeolite catalysts has emerged as a new approach to the long-standing challenge of alkane transformation. With the aid of solid-state NMR spectroscopy and GC-MS analysis, it was found that the co-conversion of propane and methanol can be readily initiated by hydride transfer at temperatures of ≥449 K over the acidic zeolite H-ZSM-5. The formation of (13)C-labeled methane and singly (13)C-labeled n-butanes in selective labeling experiments provided the first evidence for the initial hydride transfer from propane to surface methoxy intermediates. The results not only provide new insight into carbocation chemistry of solid acids, but also shed light on the low-temperature transformation of alkanes for industrial applications. PMID:25959356

  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. Combustion of chlorinated volatile organic compounds (VOCs) using bimetallic chromium-copper supported on modified H-ZSM-5 catalyst.

    PubMed

    Abdullah, Ahmad Zuhairi; Bakar, Mohamad Zailani Abu; Bhatia, Subhash

    2006-02-28

    The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity. PMID:16310938

  6. Fe-containing phases in hydrated cements

    SciTech Connect

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

    2014-04-01

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

  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. Gasoline-range hydrocarbons produced from three types of synthesis gas using a Mo/HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Street, Jason Tyler

    Biomass-derived hydrocarbons that include gasoline, diesel, and jet fuel will help replace finite fossil fuel hydrocarbons of the same range. This study showed that temperature could be controlled in a scaled-up reactor system using three types of syngas. The CO conversion, selectivity and amount of product created from each type of syngas were examined. Clean syngas composed of 40% H2, 20% CO, 12% CO2, 2% CH4, and 26% N2 was used to test ideal stoichiometric molar values. Clean syngas composed of 19% H2, 20% CO, 12% CO2, 2% CH4, and 47% N2 was used to test an ideal contaminate-free synthesis gas situation to mimic our particular downdraft gasifier. Gasifier wood syngas composed of 19% H2, 20% CO, 12% CO2, 2% CH4, 46% N2, and 1% O2 was used in this study to determine the feasibility of using gasified biomass syngas to produce gasolinerange hydrocarbons. Key words: Mo/HZSM-5, syngas, synthesis gas, wood syngas, catalyst, gasoline hydrocarbons, gasification, zeolite, oligomerization.

  9. 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.

  10. The role of propanal in the reaction of 2-propen-1-ol in H-ZSM-5

    SciTech Connect

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

    1995-07-01

    The adsorption of 2-propen-1-ol and propanal has been studied in H-ZSM-5 using simultaneous temperature programmed desorption (TPD) and thermogravimetric analysis (TGA) measurements and {sup 13}C NMR. For both adsorbates, the TPD-TGA results for both molecules form a large number of complex products. However, for low exposures, less than one molecule/Broensted site, the initial products can be observed. For 2-propene-1-ol, the initial reaction product, formed between 400 and 425 K, is propanal, formed through either a secondary cation or an epoxide intermediate. The intact desorption of propanal at low coverages was also observed in this temperature range. {sup 13}C NMR spectra of 2-propen-1-ol confirm the formation of propanal and condensation products of propanal. Finally, a potential energy model based on gas-phase proton affinities of the various conjugate bases along possible reaction coordinates for the reaction of 2-propen-1-ol explain the observed chemistry well. 21 refs., 7 figs., 1 tab.

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

    PubMed

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

    2015-05-27

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

  12. 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

  13. 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

  14. Conversion of polyethylene into gasoline-range fuels by two-stage catalytic degradation using silica-alumina and HZSM-5 zeolite

    SciTech Connect

    Uemichi, Yoshio; Nakamura, Junko; Itoh, Toshihiro; Sugioka, Masatoshi; Garforth, A.A.; Dwyer, J.

    1999-02-01

    A two-stage catalytic degradation of polyethylene using amorphous silica-alumina and HZSM-5 zeolite catalysts in series has been developed for converting the polymer into high-quality gasoline-range fuels. Compared with the one-stage degradation over each catalyst, the two-stage method provides some advantages. They are an improved gasoline yield and a high octane number despite low aromatics content. Significant results were obtained when silica-alumina and HZSM-5 were used in a weight ratio of 9:1 as upper and lower catalysts, respectively, in a flow reactor. The reverse sequence of catalysts showed no advantage. It was suggested that large pores and moderate acidity of the silica-alumina loaded in the upper layer operated favorably to catalyze the degradation of polyethylene into liquid hydrocarbons. The resulting oils showed low quality, and they were transformed into high-quality gasoline on the strongly acidic sites of the HZSM-5 loaded in the lower layer at the expense of oil yield. Increases in concentration of isoparaffins and aromatics contributed to the upgrading.

  15. 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

  16. 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

  17. 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.

  18. Large zeolite H-ZSM-5 crystals as models for the methanol-to-hydrocarbons process: bridging the gap between single-particle examination and bulk catalyst analysis.

    PubMed

    Hofmann, Jan P; Mores, Davide; Aramburo, Luis R; Teketel, Shewangizaw; Rohnke, Marcus; Janek, Jürgen; Olsbye, Unni; Weckhuysen, Bert M

    2013-06-24

    The catalytic, deactivation, and regeneration characteristics of large coffin-shaped H-ZSM-5 crystals were investigated during the methanol-to-hydrocarbons (MTH) reaction at 350 and 500 °C. Online gas-phase effluent analysis and examination of retained material thereof were used to explore the bulk properties of large coffin-shaped zeolite H-ZSM-5 crystals in a fixed-bed reactor to introduce them as model catalysts for the MTH reaction. These findings were related to observations made at the individual particle level by using polarization-dependent UV-visible microspectroscopy and mass spectrometric techniques after reaction in an in situ microspectroscopy reaction cell. Excellent agreement between the spectroscopic measurements and the analysis of hydrocarbon deposits by means of retained hydrocarbon analysis and time-of-flight secondary-ion mass spectrometry of spent catalyst materials was observed. The obtained data reveal a shift towards more condensed coke deposits on the outer zeolite surface at higher reaction temperatures. Zeolites in the fixed-bed reactor setup underwent more coke deposition than those reacted in the in situ microspectroscopy reaction cell. Regeneration studies of the large zeolite crystals were performed by oxidation in O2 /inert gas mixtures at 550 °C. UV-visible microspectroscopic measurements using the oligomerization of styrene derivatives as probe reaction indicated that the fraction of strong acid sites decreased during regeneration. This change was accompanied by a slight decrease in the initial conversion obtained after regeneration. H-ZSM-5 deactivated more rapidly at higher reaction temperature. PMID:23649944

  19. 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. PMID:20677757

  20. 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

  1. Theoretical study of the aluminum distribution effects on the double proton transfer mechanisms upon adsorption of 4,4'-bipyridine on H-ZSM-5.

    PubMed

    Akacem, Yamina; Castellà-Ventura, Martine; Kassab, Emile

    2012-02-01

    The aluminum distribution effects on the adsorption of 4,4'-bipyridine (44BPY) in the straight channel of H-ZSM-5 simulated by two ten-membered ring clusters (2-10T) have been investigated by DFT methods. The energetic and structural properties of the complexes formed upon interaction of 44BPY with the zeolite Brønsted acid sites for six different aluminum distributions were determined by B3LYP/6-31+G* calculations. Dispersion energies were estimated by performing single point calculations at the MP2 and M06-2X levels. Interaction energies were corrected for basis set superposition error (BSSE). The minimum energy pathways of the double proton transfer from H-ZSM-5 to 44BPY were characterized. Two mechanisms are proposed: a concerted mechanism in which both protons are simultaneously transferred giving the bidentate ion pair complex (44BPYH₂²⁺/2-10T²⁻) and a consecutive mechanism in which one proton is transferred directly leading to the monodentate ion pair complex (44BPYH⁺/2-10T⁻), whereas the second proton can be transferred according to Al distribution. The formation of monodentate or bidentate complexes strongly depends on the Al distribution. PMID:22220497

  2. 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

  3. Propane conversion on Ga-HZSM-5: Effect of aging on the dehydrogenating and acid functions using pyridine as an IR probe

    SciTech Connect

    Meriaudeau, P.; Naccache, C. ); Abdul Hamid, S.B. )

    1993-02-01

    Gallium-loaded zeolite (Ga-HZSM-5) catalysts have been extensively studied in the recent past, not only in respect of their interesting catalytic activity in the aromatization of C[sub 3]-C[sub 5] alkanes (Cyclar Process) but also in respect of theoretical considerations. There is clear evidence that in the reaction of alkanes these catalysts behave as bifunctional catalysts, the acid function being provided by the protons and the dehydrogenation function deriving from Ga[sub 2]O[sub 3] or Ga[sup n+] ions in ionic-exchange positions. Ga-HZSM-5 catalysts deactivate with time on-stream. The deactivation can result from poisoning of the acid centers and/or the dehydrogenating sites by coke deposition or from sintering or phase transformation of the dehydrogenating gallium species. The aim of the present study was to investigate the possible modifications of Ga centers and H[sup +] sites which may result from the propane reaction. The active centers were studied by infrared spectroscopy of adsorbed pyridine, pyridine adsorption being used to probe both H[sup +] and Al, Ga Lewis-acid centers. 11 refs., 2 figs., 1 tab.

  4. 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.

  5. 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

  6. 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

  7. 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. PMID:27101871

  8. 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

  9. 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

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

    SciTech Connect

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

    1993-08-01

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

  11. 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.

  12. 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. PMID:24409466

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

    SciTech Connect

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

    1995-02-01

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

  14. Direct Detection of Supramolecular Reaction Centers in the Methanol-to-Olefins Conversion over Zeolite H-ZSM-5 by (13)C-(27)Al Solid-State NMR Spectroscopy.

    PubMed

    Wang, Chao; Wang, Qiang; Xu, Jun; Qi, Guodong; Gao, Pan; Wang, Weiyu; Zou, Yunyun; Feng, Ningdong; Liu, Xiaolong; Deng, Feng

    2016-02-12

    Hydrocarbon-pool chemistry is important in methanol to olefins (MTO) conversion on acidic zeolite catalysts. The hydrocarbon-pool (HP) species, such as methylbenzenes and cyclic carbocations, confined in zeolite channels during the reaction are essential in determining the reaction pathway. Herein, we experimentally demonstrate the formation of supramolecular reaction centers composed of organic hydrocarbon species and the inorganic zeolite framework in H-ZSM-5 zeolite by advanced (13)C-(27)Al double-resonance solid-state NMR spectroscopy. Methylbenzenes and cyclic carbocations located near Brønsted acid/base sites form the supramolecular reaction centers in the zeolite channel. The internuclear spatial interaction/proximity between the (13)C nuclei (associated with HP species) and the (27) Al nuclei (associated with Brønsted acid/base sites) determines the reactivity of the HP species. The closer the HP species are to the zeolite framework Al, the higher their reactivity in the MTO reaction. PMID:26732748

  15. 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. PMID:11457329

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

    SciTech Connect

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

    1996-12-01

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

  17. 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.

  18. Multifunctional mesoporous silica catalyst

    DOEpatents

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

    2015-03-31

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

  19. 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

  20. 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

  1. Effects of Melt Thermal-Rate Treatment on Fe-Containing Phases in Hypereutectic Al-Si Alloy

    NASA Astrophysics Data System (ADS)

    Wang, Qinglei; Geng, Haoran; Zhang, Shuo; Jiang, Huawei; Zuo, Min

    2013-11-01

    In this paper, effects of melt thermal-rate treatment (MTRT) on Fe-containing phases in hypereutectic Al-Si alloy were investigated. Results show that MTRT can refine microstructures and improve castability, mechanical properties, wear characteristics, and corrosion resistance of Fe-containing Al-Si alloy. When Al-15Si-2.7Fe alloy is treated with MTRT by 1203 K (930 °C) melt: coarse primary Si and plate-like Fe-containing phase both can be refined to small blocky morphology, and the long needle-like Fe-containing phase disappears almost entirely; ultimate tensile strength and elongation are 195 MPa and 1.8 pct, and increase by 12.7 and 50 pct, respectively; and the wear loss and coefficient of friction decrease 7 to 17 and 24 to 30 pct, respectively, compared with that obtained with conventional casting technique. Corrosion resistance of the alloy treated with MTRT by 1203 K (930 °C) melt is the best, that is it has the lowest i corr value and the highest E corr value. Besides, effects of MTRT on Al-15Si-xFe (x = 0.2, 0.7, 1.7, 3.7, 4.7) alloys were also studied, MTRT can only refine microstructure and improve mechanical properties of Al-15Si alloy with 0.7 to 3.7 pct Fe content greatly in the present work.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    Stephanovich, V. A.; Laguta, V. V.

    We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-contained double perovskite multiferroics like PbFe$_{1/2}$Nb$_{1/2}$O$_3$. The theoretical part is based on our model of coexistence of long-range magnetic order and spin glass in the above substances. 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 corresponding lattice cites are occupied by spinless Nb$^{5+}$ ions) such frustrating interaction results in the fact that antiferromagnetic order is formed by $z$ projection of the spins, while their $xy$ components contribute to spin glass behaviour. Our theoretical findings are supported by the experimental evidence of coexistence of antiferromagnetic and spin glass phases in chemically disordered Fe-contained double perovskite multiferroics.

  4. 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.

  5. 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.

  6. Mesoporous carbon materials

    DOEpatents

    Dai, Sheng; Wang, Xiqing

    2013-08-20

    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.

  7. 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

  8. 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.

  9. 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

  10. Pentane conversion on dealuminated H-Y and HZSM-5

    SciTech Connect

    Hong, Y.; Gruver, V.; Fripiat, J.J.

    1996-07-01

    Kinetics of n-pentane conversion was studied in relation to the acidity of Y zeolites. Selectivity to isomerization vs. cracking depends mainly on the zeolite structure and the partial clogging of the pores. 34 refs., 5 figs., 7 tabs.

  11. Periodic Mesoporous Organosilica Nanorice

    NASA Astrophysics Data System (ADS)

    Mohanty, Paritosh; Landskron, Kai

    2009-02-01

    A periodic mesoporous organosilica (PMO) with nanorice morphology was successfully synthesized by a template assisted sol-gel method using a chain-type precursor. The PMO is composed of D and T sites in the ratio 1:2. The obtained mesoporous nanorice has a surface area of 753 m2 g-1, one-dimensional channels, and a narrow pore size distribution centered at 4.3 nm. The nanorice particles have a length of ca. 600 nm and width of ca. 200 nm.

  12. 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.

  13. 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.

  14. 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. PMID:23250616

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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).

  3. THE BIOCOMPATIBILITY OF MESOPOROUS SILICATES

    PubMed Central

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

    2008-01-01

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

  4. Synthesis and characterization of mesoporous materials

    NASA Astrophysics Data System (ADS)

    Cheng, Wei

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

  5. 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.

  6. 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

  7. Synthesis of non-siliceous mesoporous oxides.

    PubMed

    Gu, Dong; Schüth, Ferdi

    2014-01-01

    Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed. PMID:23942521

  8. 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

  9. 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

  10. 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.

  11. Synthesis of hollow and mesoporous polycaprolactone nanocapsules,

    NASA Astrophysics Data System (ADS)

    Paik, Pradip; Zhang, Yong

    2011-05-01

    New polycaprolactone (PCL) nanocapsules with a hollow core and mesoporous shell have been synthesized. The PCL nanocapsules have an average size of about 100nm and a mesopores shell of about 20nm. The size of the mesopores on the shell is about 4nm. Fluorescent dye Rhodamin 6G was loaded into the nanocapsules to demonstrate the mesoporous structure of the capsules and their ability to load small molecules. The nanocapsules with such a structure can be used in many areas for various applications such as drug and gene delivery.New polycaprolactone (PCL) nanocapsules with a hollow core and mesoporous shell have been synthesized. The PCL nanocapsules have an average size of about 100nm and a mesopores shell of about 20nm. The size of the mesopores on the shell is about 4nm. Fluorescent dye Rhodamin 6G was loaded into the nanocapsules to demonstrate the mesoporous structure of the capsules and their ability to load small molecules. The nanocapsules with such a structure can be used in many areas for various applications such as drug and gene delivery. Dr. Pradip Paik is currently an assistant professor at the University of Hyderabad (Central University), India.

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

    SciTech Connect

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

    2013-07-15

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Zhao, Elizabeth Sun

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

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. Location of laccase in ordered mesoporous materials

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  20. Mesoporous hybrid organosilica containing urethane moieties

    SciTech Connect

    Seo, You-Kyong; Park, Sung-Bae; Ho Park, Dong . E-mail: chempdh@inje.ac.kr

    2006-04-15

    Mesoporous hybrid material containing urethane moieties in functionalized long chain organic group have been synthesized by using bis[3-(triethoxysilyl) propyl urethane]ethane (BTESPUE) and tetraethoxysilane as structural ingredients. The incorporation of BTESPUE within the framework of mesoporous material was confirmed by Fourier transform-infrared, X-ray photoelectron spectroscopy, solid-state NMR spectroscopy and thermogravimetric analysis. This material had a thick wall and uniform pore, which may be attributed to the hydrogen bonding inside framework due to urethane moieties.

  1. Synthesis of mesoporous silica nanoparticles.

    PubMed

    Wu, Si-Han; Mou, Chung-Yuan; Lin, Hong-Ping

    2013-05-01

    Good control of the morphology, particle size, uniformity and dispersity of mesoporous silica nanoparticles (MSNs) is of increasing importance to their use in catalyst, adsorption, polymer filler, optical devices, bio-imaging, drug delivery, and biomedical applications. This review discusses different synthesis methodologies to prepare well-dispersed MSNs and hollow silica nanoparticles (HSNs) with tunable dimensions ranging from a few to hundreds of nanometers of different mesostructures. The methods include fast self-assembly, soft and hard templating, a modified Stöber method, dissolving-reconstruction and modified aerogel approaches. In practical applications, the MSNs prepared by these methods demonstrate good potential for use in high-performance catalysis, antireflection coating, transparent polymer-MSNs nanocomposites, drug-release and theranostic systems. PMID:23403864

  2. 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.

  3. 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

  4. 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. PMID:26544169

  5. A highly ordered cubic mesoporous silica/graphene nanocomposite.

    PubMed

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

    2013-10-21

    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. PMID:24057016

  6. 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.

  7. 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.

  8. 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.

  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. The Catalytic Cracking of Hydrocarbons: Paraffins in the HZSM-5 Zeolite

    SciTech Connect

    Martinez-Magadan, Jose M.; Mercado, Sergio M.; Santamaria, Ruben

    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. The central goal of petroleum refineries consists in the transformation of crude oil into a variety of useful products, among which fuels play a crucial role.[1] Presently, important companies are using state-of-the-art technology to investigate new and more efficient refining processes, that may additionally lead to a cleaner environment. Unfortunately, this type of investigation demands costly investment and is highly empirical[2, 3] due to the number of variables, properties, and pathways that characterize the refining processes. On the other hand, the intense competition among catalyst manufacturers has challenged basic research.

  11. 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),...

  12. 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

  13. Nonenzymatic glucose detection using mesoporous platinum.

    PubMed

    Park, Sejin; Chung, Taek Dong; Kim, Hee Chan

    2003-07-01

    Roughness of nanoscopic dimensions can be used to selectively enhance the faradaic current of a sluggish reaction. Using this principle, we constructed mesoporous structures on the surfaces of pure platinum electrodes responding even more sensitively to glucose than to common interfering species, such as L-ascorbic acid and 4-acetamidophenol. Good sensitivities, as high as 9.6 microA cm(-2) mM(-1), were reproducibly observed in the presence of high concentration of chloride ion. The selectivities, sensitivities, and stabilities determined experimentally have demonstrated the potential of mesoporous platinum as a novel candidate for nonenzymatic glucose sensors. PMID:12964749

  14. 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.

  15. 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.

  16. 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. PMID:27060365

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

    NASA Astrophysics Data System (ADS)

    Gao, Lin; Sun, Jihong; Li, Yuzhen

    2011-08-01

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

  18. Electrical Relaxation in ULTEM® and ULTEM® Containing Mesoporous Silica

    NASA Astrophysics Data System (ADS)

    Turo, Andrew; Edmondson, Charles E.; Lomax, Joseph F.; Bendler, John T.; Fontanella, John J.; Wintersgill, Mary C.

    2008-08-01

    Mesoporous silica has been added to Ultem® 1000 polyetherimide using solution casting. The mesoporous silica that was added was either uncoated or coated with polystyrene. Audio frequency dielectric relaxation studies were then carried out over the temperature range 5.5 to 550 K. Several interesting results were obtained. First, the uncoated mesoporous silica caused essentially no change in the relaxation spectrum of pure Ultem®. The polystyrene coated mesoporous silica caused rather large changes. The most striking example is the introduction of a new relaxation. This relaxation occurs at about 150 K and 1000 Hz as showing in fig. 1 via the open circles.

  19. 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).

  20. 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

  1. Synthesis of periodic mesoporous silica thin films

    SciTech Connect

    Anderson, M.T.; Martin, J.E.; Odinek, J.G.; Newcomer, P.

    1996-06-01

    We have synthesized periodic mesoporous silica thin films from homogeneous solutions. To synthesize the films, a thin layer of a pH 7 micellar coating solution that contains TMOS (tetramethoxysilane) is dip or spin-coated onto Si wafers, borosilicate glass, or quartz substrates. NH3 gas is diffused into the solution and causes rapid hydrolysis and condensation of the TMOS and the formation of periodic mesoporous thin films within 10 seconds. Combination of homogenous solutions and rapid product formation maximizes the concentration of the desired product and provides a controlled, predictable microstructure. The films have been made continuous and crack-free by optimizing initial silica concentration and film thickness. The films are being evaluated as high surface area, size-selective coatings for surface acoustic wave (SAW) sensors.

  2. 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.

  3. Mesoporous silica nanoparticles for active corrosion protection.

    PubMed

    Borisova, Dimitriya; Möhwald, Helmuth; Shchukin, Dmitry G

    2011-03-22

    This work presents the synthesis of monodisperse, mesoporous silica nanoparticles and their application as nanocontainers loaded with corrosion inhibitor (1H-benzotriazole (BTA)) and embedded in hybrid SiOx/ZrOx sol-gel coating for the corrosion protection of aluminum alloy. The developed porous system of mechanically stable silica nanoparticles exhibits high surface area (∼1000 m2·g(-1)), narrow pore size distribution (d∼3 nm), and large pore volume (∼1 mL·g(-1)). As a result, a sufficiently high uptake and storage of the corrosion inhibitor in the mesoporous nanocontainers was achieved. The successful embedding and homogeneous distribution of the BTA-loaded monodisperse silica nanocontainers in the passive anticorrosive SiOx/ZrOx film improve the wet corrosion resistance of the aluminum alloy AA2024 in 0.1 M sodium chloride solution. The enhanced corrosion protection of this newly developed active system in comparison to the passive sol-gel coating was observed during a simulated corrosion process by the scanning vibrating electrode technique (SVET). These results, as well as the controlled pH-dependent release of BTA from the mesoporous silica nanocontainers without additional polyelectrolyte shell, suggest an inhibitor release triggered by the corrosion process leading to a self-healing effect. PMID:21344888

  4. Mesoporous carbon nanomaterials as environmental adsorbents.

    PubMed

    Tripathi, Pranav K; Gan, Lihua; Liu, Mingxian; Rao, Nageswara N

    2014-02-01

    The transportation and diffusion of the guest objects or molecules in the porous carbon nanomaterials can be facilitated by reducing the pathway and resistance. The reduced pathway depends on the porous nature of carbon nanomaterials. Classification of porous carbon materials by the International Union of Pure and Applied Chemistry (IUPAC) has given a new opportunity to design the pores as per their applicability and to understand the mobility of ions, atoms, and molecules in the porous network of carbon materials and also advanced their countless applicability. However, synthesis of carbon nanomaterials with a desired porous network is still a great challenge. Although, remarkable developments have taken place in the recent years, control over the pores size and/or hierarchical porous architectures, especially in the synthesis of carbon nanospheres (CNSs) and ordered mesoporous carbon (OMCs) is still intriguing. The micro and mesoporous CNSs and OMCs have been prepared by a variety of procedures and over a wide range of compositions using various different surfactant templates and carbon precursors etc. The mechanisms of formation of micromesopore in the CNSs and OMCs are still evolving. On the other hand, the urge for adsorbents with very high adsorption capacities for removing contaminants from water is growing steadily. In this review, we address the state-of-the-art synthesis of micro and mesoporous CNSs and OMCs, giving examples of their applications for adsorptive removals of contaminants including our own research studies. PMID:24749459

  5. 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.

  6. 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.

  7. Protection of Organic Matter from Enzyme Degradation by Mineral Mesopores

    NASA Astrophysics Data System (ADS)

    Zimmerman, A. R.; Chorover, J. D.; Brantley, S. L.

    2003-12-01

    Mineral mesopores (2-50 nm diameter) may sequester organic matter (natural and pollutant) and protect it from microbial and fungal enzymatic degradation in soils and sediments. Synthetic mesoporous alumina and silica minerals with uniform pore sizes and shapes were used to test the role of mesopores in protecting organic matter from enzymatic degradation. A model humic compound, L-3-4-dihydroxyphenylalanine (L-DOPA), was sorbed to the internal surfaces of mesoporous alumina (8.2 nm diameter pores) and mesoporous silica (3.4 nm diameter pores) as well as to the external surfaces of nonporous alumina and silica analogues. A fungal derived enzyme, laccase, was added to these sorbate-sorbent pairs in aqueous solution and activity was monitored by oxygen consumption. Though enzyme activity was suppressed in both cases by mineral-enzyme interaction (enzyme inhibition likely due to adsorption of the enzyme), both the rate and total extent of enzyme-mediated degradation of mesopore-sorbed L-DOPA was 3-40 times lower than that of the externally-sorbed analogue. These results provide, for the first time, direct evidence for the viability of the proposed mesopore protection mechanism for the sequestration and preservation of sedimentary organic matter and organic contaminants. Mesopore adsorption/desorption phenomena may also help explain the slow degradation of organic contaminants in soil and sediment and may prove useful as delivery vehicles for organic compounds to agricultural, medical or environmental systems.

  8. Transport properties of fast proton conducting mesoporous silica xerogels

    NASA Astrophysics Data System (ADS)

    Colomer, M. T.; Rubio, F.; Jurado, J. R.

    Mesoporous acid-free silica xerogels exhibiting a proton conductivity of 2.0 × 10 -2 S cm -1 at 80 °C and 81% RH is reported for the first time. The proton conductivity values, lower cost and higher hydrophilicity of mesoporous silica xerogels make them potential substitutes for Nafion membranes in proton exchange membranes fuel cells (PEMFCs).

  9. The Synthesis of Cadmium Doped Mesoporous TiO2

    SciTech Connect

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

    2007-06-01

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

  10. 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

  11. [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

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

    PubMed

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

    2015-05-01

    Mesoporous silica in the forms of micro- or nanoparticles showed great potentials in the field of controlled drug delivery. However, for precision control of drug release from mesoporous silica-based delivery systems, it is critical to control the rate of biodegradation. Thus, in this study, we demonstrate a simple and robust method to fabricate "biodegradation-tunable" mesoporous silica nanorods based on capillary wetting of anodic aluminum oxide (AAO) template with an aqueous alkoxide precursor solution. The porosity and nanostructure of silica nanorods were conveniently controlled by adjusting the water/alkoxide molar ratio of precursor solutions, heat-treatment temperature, and Na addition. The porosity and biodegradation kinetics of the fabricated mesoporous nanorods were analyzed using N2 adsorption/desorption isotherm, TGA, DTA, and XRD. Finally, the performance of the mesoporous silica nanorods as drug delivery carrier was demonstrated with initial burst and subsequent "zero-order" release of anti-cancer drug, doxorubicin. PMID:25746247

  13. 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

  14. 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

  15. Contribution of mesopores in MgO-templated mesoporous carbons to capacitance in non-aqueous electrolytes

    NASA Astrophysics Data System (ADS)

    Kado, Yuya; Soneda, Yasushi; Yoshizawa, Noriko

    2015-02-01

    MgO-templated mesoporous carbons were fabricated by annealing trimagnesium dicitrate nonahydrate at various temperatures from 700 to 1000 °C with subsequent acid leaching of MgO. The obtained carbons contained a large amount of mesopores. Performances of electric double-layer capacitors using these carbons were examined for propylene carbonate electrolyte containing 1 M tetraethylammonium tetrafluoroborate. The mesoporous carbons synthesized at higher temperatures showed better rate capabilities. AC impedance measurements indicated that high-temperature annealing of the carbon precursors and the presence of mesopores were important for high rate performance. In addition, the contribution of mesopores to capacitance was more significant at higher current densities of 30 A g-1.

  16. The development of chiral nematic mesoporous materials.

    PubMed

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

    2014-04-15

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

  17. Modified Mesoporous Silica for Efficient Siloxane Capture.

    PubMed

    Jafari, Tahereh; Jiang, Ting; Zhong, Wei; Khakpash, Nasser; Deljoo, Bahareh; Aindow, Mark; Singh, Prabhakar; Suib, Steven L

    2016-03-15

    In this study, octamethylcyclotetrasiloxane (D4) was removed by using a novel modified solid adsorbent of mesoporous silica. The adsorbent was synthesized using inverse micelles with some modifications in the synthesis process (temperature of gelation) and in the post treatment conditions (calcination temperature and heating rate) with a concomitant improvement of D4 uptake. This is the first report on regulating the textural properties of the mesoporous silica material UCT-14 to develop an active silica adsorbent. These adjustments resulted in an increase of the silica surface area from 391 to 798 m(2)·g(-1), which leads to a high capacity (686 mg·g(-1)) of D4-capture for the silica synthesized at 80 °C, calcined at 450 °C with the heating rate of 100 °C·min(-1) (Si-Syn80). This adsorbent showed comparable adsorption performance with the widely used commercial silica gel under dry and humid condition. Recyclability tests on the commercial silica gel and mesoporous silica synthesized at 120 °C and calcined at 450 °C with a heating rate of 100 °C·min(-1) (called Si-Syn120 or Si-450 or Si-100 °C·min(-1)) indicated that the Si-Syn120 (capacity drop 10%) is more efficient than silica gel (capacity drop 15%) after three cycles. Although, the presence of moisture (25%) in the nitrogen gas stream led to capacity reduction in both Si-Syn120 and commercial silica gel, the modified UCT-14 shows slightly better resistance to humid condition. PMID:26890152

  18. Fluorescence properties of dye doped mesoporous silica

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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 referenc 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.

  19. Mesoporous silica-titania composed materials.

    PubMed

    Messina, Paula V; Morini, Marcela A; Sierra, María B; Schulz, Pablo C

    2006-08-01

    Titania mesosized particles were obtained by TiCl4 hydrolysis in Aerosol OT/water/n-hexane microemulsion. These particles were incorporated in surfactant templated silica mesoporous materials of MCM-41 and MCM-50 structures. Results depended on the surfactant: hexadecyltrimethylammonium bromide templated materials retained the honeycomb structure with small modifications in their characteristics. The dodecyltrimethylammonium bromide templated material changed from honeycomb to lamellar structure when the titania particles were included, with dramatic changes in the structure characteristics. The didodecyldimethylammonium bromide templated lamellar structure was retained after TIO2 inclusion, with a slight increase in the specific area, pore diameter and pore walls thickness. PMID:16600274

  20. 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.

  1. Branched artificial nanofinger arrays by mesoporous interfacial atomic rearrangement.

    PubMed

    Kong, Biao; Tang, Jing; Zhang, Yueyu; Selomulya, Cordelia; Gong, Xingao; Liu, Yang; Zhang, Wei; Yang, Jianping; Wang, Wenshuo; Sun, Xiaotian; Wang, Yufei; Zheng, Gengfeng; Zhao, Dongyuan

    2015-04-01

    The direct production of branched semiconductor arrays with highly ordered orientation has proven to be a considerable challenge over the last two decades. Here we report a mesoporous interfacial atomic rearrangement (MIAR) method to directly produce highly crystalline, finger-like branched iron oxide nanoarrays from the mesoporous nanopyramids. This method has excellent versatility and flexibility for heteroatom doping of metallic elements, including Sn, Bi, Mn, Fe, Co, Ni, Cu, Zn, and W, in which the mesoporous nanopyramids first absorb guest-doping molecules into the mesoporous channels and then convert the mesoporous pyramids into branching artificial nanofingers. The crystalline structure can provide more optoelectronic active sites of the nanofingers by interfacial atomic rearrangements of doping molecules and mesopore channels at the porous solid-solid interface. As a proof-of-concept, the Sn-doped Fe2O3 artificial nanofingers (ANFs) exhibit a high photocurrent density of ∼1.26 mA/cm(2), ∼5.25-fold of the pristine mesoporous Fe2O3 nanopyramid arrays. Furthermore, with surface chemical functionalization, the Sn-doped ANF biointerfaces allow nanomolar level recognition of metabolism-related biomolecules (∼5 nm for glutathione). This MIAR method suggests a new growth means of branched mesostructures, with enhanced optoelectronic applications. PMID:25764364

  2. 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.

  3. Mesoporous silica material TUD-1 as a drug delivery system.

    PubMed

    Heikkilä, T; Salonen, J; Tuura, J; Hamdy, M S; Mul, G; Kumar, N; Salmi, T; Murzin, D Yu; Laitinen, L; Kaukonen, A M; Hirvonen, J; Lehto, V-P

    2007-02-22

    For the first time the feasibility of siliceous mesoporous material TUD-1 (Technische Universiteit Delft) for drug delivery was studied. Model drug, ibuprofen, was adsorbed into TUD-1 mesopores via a soaking procedure. Characterizations with nitrogen adsorption, XRD, TG, HPLC and DSC demonstrated the successful inclusion of ibuprofen into TUD-1 host. The amount of ibuprofen adsorbed into the nanoreservoir of TUD-1 material was higher than reported for other mesoporous silica drug carriers (drug/carrier 49.5 wt.%). Drug release studies in vitro (HBSS buffer pH 5.5) demonstrated a fast and unrestricted liberation of ibuprofen, with 96% released at 210 min of the dissolution assay. The drug dissolution profile of TUD-1 material with the random, foam-like three-dimensional mesopore network and high accessibility to the dissolution medium was found to be much faster (kinetic constant k = 10.7) and more diffusion based (release constant n = 0.64) compared to a mesoporous MCM-41 material with smaller, unidirectional mesopore channels (k = 4.7, n = 0.71). Also, the mesoporous carriers were found to significantly increase the dissolution rate of ibuprofen, when compared to the pure crystalline form of the drug (k = 0.6, n = 0.96). TUD-1 was constituted as a potential drug delivery device with fast release property, with prospective applications in the formulation of poorly soluble drug compounds. PMID:17046183

  4. Silica-based mesoporous nanoparticles for controlled drug delivery.

    PubMed

    Kwon, Sooyeon; Singh, Rajendra K; Perez, Roman A; Abou Neel, Ensanya A; Kim, Hae-Won; Chrzanowski, Wojciech

    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

  5. Incorporation of antimicrobial compounds in mesoporous silica film monolith.

    PubMed

    Izquierdo-Barba, Isabel; Vallet-Regí, María; Kupferschmidt, Natalia; Terasaki, Osamu; Schmidtchen, Artur; Malmsten, Martin

    2009-10-01

    Incorporation of the antimicrobial peptide LL-37 (LLGDFFRKSKEKIGKEFKRIVQRIKDFLRNLVPRTES), as well as low molecular weight antimicrobial chlorhexidine, into mesoporous silica was obtained using an EISA one-pot synthesis method. FTIR confirmed efficient encapsulation of both LL-37 and chlorhexidine into mesoporous silica, while XRD and TEM showed that antimicrobial agent incorporation can be achieved without greatly affecting the structure of the mesoporous silica. The modified mesoporous silica released LL-37 and chlorhexidine slowly, reaching maximum release after about 200 h. The release rate could also be controlled through incorporation of SH groups in the pore walls, adding to pore hydrophobicity and reducing the release rate by about 50% compared to the unmodified mesoporous silica. Mesoporous silica containing either LL-37 or chlorhexidine displayed potent bactericidal properties against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. While chlorhexidine-loaded mesoporous silica displayed an accompanying high toxicity, as judged from hemolysis, LDH release, and MTT assay, the corresponding material containing LL-37 showed very low toxicity by all these assays, comparable to that observed for mesoporous silica in the absence of antibacterial drug, as well as to the negative controls in the respective assays. Mesoporous silica containing LL-37 therefore holds potential as an implantable material or a surface coating for such materials, as it combines potent bactericidal action with low toxicity, important features for controlling implant-related infections, e.g., for multi-resistant pathogens or for cases where access to the infection site of systemically administered antibiotics is limited due to collagen capsule formation or other factors. PMID:19628277

  6. 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

  7. Distributions of noble metal Pd and Pt in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Arbiol, J.; Cabot, A.; Morante, J. R.; Chen, Fanglin; Liu, Meilin

    2002-10-01

    Mesoporous silica nanostructures have been synthesized and loaded with Pd and Pt catalytic noble metals. It is found that Pd forms small nanoclusters (3-5 nm) on the surface of the mesoporous structure whereas Pt impregnation results in the inclusion of Pt nanostructures within the silica hexagonal pores (from nanoclusters to nanowires). It is observed that these materials have high catalytic properties for CO-CH4 combustion, even in a thick film form. In particular, results indicate that the Pt and Pd dispersed in mesoporous silica are catalytically active as a selective filter for gas sensors.

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. Optically tunable chiral nematic mesoporous cellulose films.

    PubMed

    Schlesinger, Maik; Hamad, Wadood Y; MacLachlan, Mark J

    2015-06-21

    Demand for sustainable functional materials has never been larger. The introduction of functionality into pure cellulose might be one step forward in this field as it is one of the most abundant natural biopolymers. In this paper, we demonstrate a straightforward and scalable way to produce iridescent, mesoporous cellulose membranes with tunable colors and porosity. Concomitant assembly of cellulose nanocrystals (CNCs) and condensation of silica precursors results in CNC-silica composites with chiral nematic structures and tunable optical properties. Removal of the stabilizing silica matrix by alkaline or acid treatment gives access to novel chiral nematic mesoporous cellulose (CNMC) films. Importantly, the optical properties and the mesoporosity can be controlled by either varying the silica-to-CNC ratio, or by varying the substrate used during the evaporation-induced self-assembly process. In order to introduce additional functionality, CNMC has been used to stabilize gold nanoparticles with three different concentrations by wet impregnation. These materials are stable in water and can potentially function in sensors, tissue engineering or functional membranes. PMID:25972020

  14. Mesoporous carbon incorporated metal oxide nanomaterials as supercapacitor electrodes.

    PubMed

    Jiang, Hao; Ma, Jan; Li, Chunzhong

    2012-08-01

    Supercapacitors have attracted huge attention in recent years as they have the potential to satisfy the demand of both huge energy and power density in many advanced technologies. However, poor conductivity and cycling stability remains to be the major challenge for its widespread application. Various strategies have been developed for meeting the ever-increasing energy and power demands in supercapacitors. This Research News article aims to review recent progress in the development of mesoporous carbon incorporated metal oxide nanomaterials, especially metal oxide nanoparticles confined in ordered mesoporous carbon and 1D metal oxides coated with a layer of mesoporous carbon for high-performance supercapacitor applications. In addition, a recent trend in supercapacitor development - hierarchical porous graphitic carbons (HPGC) combining macroporous cores, mesoporous walls, and micropores as an excellent support for metal oxides - is also discussed. PMID:23030034

  15. 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

  16. 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...

  17. 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.

  18. 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

  19. Mesoporous silica magnetite nanocomposite synthesized by using a neutral surfactant

    NASA Astrophysics Data System (ADS)

    Souza, K. C.; Salazar-Alvarez, G.; Ardisson, J. D.; Macedo, W. A. A.; Sousa, E. M. B.

    2008-05-01

    Magnetite nanoparticles coated by mesoporous silica were synthesized by an alternative chemical route using a neutral surfactant and without the application of any functionalization method. The magnetite (Fe3O4) nanoparticles were prepared by precipitation from aqueous media, and then coated with mesoporous silica by using nonionic block copolymer surfactants as the structure-directing agents. The mesoporous SiO2-coated Fe3O4 samples were characterized by x-ray diffraction, Fourier-transform infrared spectroscopy, N2 adsorption-desorption isotherms, transmission electron microscopy, 57Fe Mössbauer spectroscopy, and vibrating sample magnetometry. Our results revealed that the magnetite nanoparticles are completely coated by well-ordered mesoporous silica with free pores and stable (~8 nm thick) pore walls, and that the structural and magnetic properties of the Fe3O4 nanoparticles are preserved in the applied synthesis route.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. In-situ immobilization of enzymes in mesoporous silicas

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

  5. 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.

  6. 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.

  7. 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

  8. Grafting Sulfated Zirconia on Mesoporous Silica

    SciTech Connect

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

    2007-06-01

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

  9. 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

  10. Mesoporous titanium dioxide coating for metallic implants.

    PubMed

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

    2012-01-01

    A bioactive mesoporous titanium dioxide (MT) coating for surface drug delivery has been investigated to develop a multifunctional implant coating, offering quick bone bonding and biological stability. An evaporation induced self-assembly (EISA) method was used to prepare a mesoporous titanium dioxide coating of the anatase phase with BET surface area of 172 m(2)/g and average pore diameter of 4.3 nm. Adhesion tests using the scratch method and an in situ screw-in/screw-out technique confirm that the MT coating bonds tightly with the metallic substrate, even after removal from bone. Because of its high surface area, the bioactivity of the MT coating is much better than that of a dense TiO(2) coating of the same composition. Quick formation of hydroxyapatite (HA) in vitro can be related to enhance bonding with bone. The uptake of antibiotics by the MT coating reached 13.4 mg/cm(3) within a 24 h loading process. A sustained release behavior has been obtained with a weak initial burst. By using Cephalothin as a model drug, drug loaded MT coating exhibits a sufficient antibacterial effect on the material surface, and within millimeters from material surface, against E.coli. Additionally, the coated and drug loaded surfaces showed no cytotoxic effect on cell cultures of the osteoblastic cell line MG-63. In conclusion, this study describes a novel, biocompatiblemesoporous implant coating, which has the ability to induce HA formation and could be used as a surface drug-delivery system. PMID:21954047

  11. 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. PMID:12240191

  12. 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

  13. Gyroidal mesoporous multifunctional nanocomposites via atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Werner, Jörg G.; Scherer, Maik R. J.; Steiner, Ullrich; Wiesner, Ulrich

    2014-07-01

    We demonstrate the preparation of rationally designed, multifunctional, monolithic and periodically ordered mesoporous core-shell nanocomposites with tunable structural characteristics. Three-dimensionally (3D) co-continuous gyroidal mesoporous polymer monoliths are fabricated from a solution-based triblock terpolymer-resol co-assembly and used as the functional templates for the fabrication of free-standing core-shell carbon-titania composites using atomic layer deposition (ALD). The deposition depth into the torturous gyroidal nanonetwork is investigated as a function of ALD conditions and the resulting composites are submitted to different thermal treatments. Results suggest that ALD can homogenously coat mesoporous templates with well defined pore sizes below 50 nm and thicknesses above 10 μm. Structural tunability like titania shell thickness and pore size control is demonstrated. The ordered nanocomposites exhibit triple functionality; a 3D continuous conductive carbon core that is coated with a crystalline titania shell that in turn is in contact with a 3D continuous mesopore network in a compact monolithic architecture. This materials design is of interest for applications including energy conversion and storage. Gyroidal mesoporous titania monoliths can be obtained through simultaneous titania crystallization and template removal in air.We demonstrate the preparation of rationally designed, multifunctional, monolithic and periodically ordered mesoporous core-shell nanocomposites with tunable structural characteristics. Three-dimensionally (3D) co-continuous gyroidal mesoporous polymer monoliths are fabricated from a solution-based triblock terpolymer-resol co-assembly and used as the functional templates for the fabrication of free-standing core-shell carbon-titania composites using atomic layer deposition (ALD). The deposition depth into the torturous gyroidal nanonetwork is investigated as a function of ALD conditions and the resulting composites are

  14. Synthesis and characterization of mesoporous semiconductors and their energy applications

    NASA Astrophysics Data System (ADS)

    Kang, Chris Byung-hwa

    In this dissertation, we examine the structure and physical properties of mesoporous group IV materials. Two different synthetic routes were developed to synthesize mesoporous germanium powder and thin film mesoporous silicon. The structural of these materials was confirmed by various analytical techniques. The electrochemical behavior of mesoporous silicon was further explored for applications as anodes in lithium ion batteries. The thermal conductivity was also measured and the electrical conductivity was tuned for potential applications as thermoelectrics. Ordered nanostructured germanium composite materials were produced using solution-phase surfactant templating methods. Anionic germanium/surfactand frameworks with a 2-D hexagonal structure were prepared and then condensed to form zero-valent porous germanium using oxidative coupling. The majority of the cationic surfactant inside the pores can be removed, resulting in mesoporous germanium with surface areas up to 500 m2/g. Thin film of mesoporous silicon was produced from polymer template porous silica films at relatively low temperature (<700 C) using magnesium vapor as reducing agent. The final porous silicon retains its ordered cubic mesoporosity. The lithium ion cycling performance of mesoporous silicon anodes was then examined. Mesoporous silicon films formed directly on a metal current collector showed stable cycling with excellent coulomb efficiency over 3000 cycles with capacities up to 3000 mAh/g at cycling rates between 1C to 20C. The results indicate porous silicon material in this size scale can accommodate the volume expansion associated with Li alloying without cracking or loosing contact with the current collector. The thermal conductivity of mesoporous silicon was also measured using the 3 omega method. Periodic pores and grain boundaries enhance phonon scattering to dissipate thermal energy throughout the material, resulting in a decrease in the thermal conductivity by 3-5 orders of magnitude

  15. 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.

  16. Application of ordered mesoporous carbon in solid phase microextraction for fast mass transfer and high sensitivity.

    PubMed

    Zheng, Juan; Wang, Kun; Liang, Yeru; Zhu, Fang; Wu, Dingcai; Ouyang, Gangfeng

    2016-05-21

    Due to unique high-surface-area ordered mesoporous channels interconnected with 3D network-like mesopores and π-π interactions between carbon frameworks and analytes, the as-prepared ordered mesoporous carbon-coated fiber exhibited a large adsorption amount, fast mass transport and high sensitivity. PMID:27137527

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

    PubMed

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

    2016-03-14

    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. PMID:26585611

  18. 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

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

    PubMed

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

    2014-06-01

    In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described. PMID:24828540

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

    PubMed

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

    2014-03-15

    In this work, a protocol to synthesize monodisperse mesoporous silica microparticles via a unique microfluidic jet spray-drying route is reported for the first time. The microparticles demonstrated highly ordered hexagonal mesostructures with surface areas ranging from ~900 up to 1500 m(2)/g and pore volumes from ~0.6 to 0.8 cm(3)/g. The particle size could be easily controlled from ~50 to 100 μm from the same diameter nozzle via changing the initial solute content, or changing the drying temperature. The ratio of the surfactant (CTAB) and silica (TEOS), and the amount of water in the precursor were found to affect the degree of ordering of mesopores by promoting either the self-assembly of the surfactant-silica micelles or the condensation of the silica as two competing processes in evaporation induced self-assembly. The drying rate and the curvature of particles also affected the self-assembly of the mesostructure. The particle mesostructure is not influenced by the inlet drying temperature in the range of 92-160 °C, with even a relatively low temperature of 92 °C producing highly ordered mesoporous microparticles. The spray-drying derived mesoporous silica microparticles, while of larger sizes and more rapidly synthesized, showed a comparable performance with the conventional mesoporous silica MCM-41 in controlled release of a dye, Rhodamine B, indicating that these spray dried microparticles could be used for the immobilisation and controlled release of small molecules. PMID:24461839

  1. 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

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

    PubMed Central

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

    2014-01-01

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

  3. 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.

  4. 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}.

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

    PubMed

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

    2014-01-01

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

  6. Photocatalytic activity of a hierarchically macro/mesoporous titania.

    PubMed

    Wang, Xinchen; Yu, Jimmy C; Ho, Chunman; Hou, Yidong; Fu, Xianzhi

    2005-03-15

    Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules. PMID:15752052

  7. 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...

  8. Synthesis of continuous mesoporous alumina films with large-sized cage-type mesopores by using diblock copolymers.

    PubMed

    Jiang, Xiangfen; Suzuki, Norihiro; Bastakoti, Bishnu Prasad; Wu, Kevin C-W; Yamauchi, Yusuke

    2012-06-01

    Mesoporous alumina films with large-sized cage-type mesopores were prepared by using commercially available diblock copolymer (PS-b-PEO) and economic inorganic salt (AlCl(3)) as aluminum source. The obtained mesopore sizes drastically expand from 35 nm to 80 nm when the amount of ethanol in the precursor solutions were controlled. More interestingly, under an optimized amount of ethanol as co-solvent, there was no significant change of micelle morphology on the substrate, even though the relative amount of PS-b-PEO to alumina source was dramatically varied. When the amount of alumina precursor was decreased, the pore walls gradually became thinner, thereby improving pore connectivity. The ordered mesoporous alumina films obtained in this study exhibit high thermal stability up to 1000 °C, and their frameworks are successfully crystallized to γ-alumina phase. This technique could also be applicable for creating other metal oxide thin films with large mesopores. PMID:22556035

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  10. 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

  11. 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.

  12. 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

  13. Selective SERS Sensing Modulated by Functionalized Mesoporous Films.

    PubMed

    López-Puente, Vanesa; Angelomé, Paula C; Soler-Illia, Galo J A A; Liz-Marzán, Luis M

    2015-11-25

    A hybrid material comprising metal nanoparticles embedded in functionalized mesoporous thin films was constructed, and its use as a selective SERS-based sensor was demonstrated. The presence of specific functional groups in the pore network allows control over the surface chemistry of the pores, tuning the selectivity for specific molecules. Amino-functionalized hybrid mesoporous thin films were used in a proof of concept experiment, to discern the presence of methylene blue (MB) in mixtures with acid blue (AB), with no need for any sample pretreatment step. Selective detection of MB was possible through entrapment of AB in the mesoporous matrix, based on its high affinity for amino groups. The sensor selectivity can be tuned by varying the solution pH, rendering a pH responsive surface and thus, selective SERS-based sensing. The developed sensors allow specific detection of molecules in complex matrixes. PMID:26536368

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Zirconia-silica based mesoporous desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  20. 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

  1. 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.

  2. Lower Permittivity Characteristic of Mesoporous-Alumina/Epoxy Composite due to Particle Porosity

    NASA Astrophysics Data System (ADS)

    Kurimoto, Muneaki; Murakami, Yoshinobu; Nagao, Masayuki

    Introduction of metal oxide nanoparticles to polymer composite material is known to have unique dielectric behavior and significant advantage in the electrical insulation performance of electrical power apparatus. This paper presents an attempt to derive the dielectric characteristics of polymer composite filled with the metal oxide particle which has mesoporous structure. Experiments were carried out in the epoxy composites filled with alumina microparticles which have the mesoporous structure (mesoporous-alumina/epoxy composites) with different particle content. Based on the measurement of the specific gravity of mesoporous-alumina/epoxy composites, the porosity of mesoporous-alumina particle in the epoxy matrix was found to be higher than that of nonporous-alumina particle. Furthermore, we evaluated relative permittivity of mesoporous-alumina/epoxy composites by measuring the capacitance of its specimens. As the results, we verified that the permittivity of mesoporous-alumina/epoxy composites was lower than that of nonporous-alumina/epoxy composites due to the particle porosity.

  3. 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.

  4. 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.

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

    PubMed

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

    2011-09-21

    We report a general reaction container effect in the nanocasting synthesis of mesoporous metal oxides. The size and shape of the container body in conjunction with simply modifying the container opening accessibility can be used to control the escape rate of water and other gas-phase byproducts in the calcination process, and subsequently affect the nanocrystal growth of the materials inside the mesopore space of the template. In this way, the particle size, mesostructure ordering, and crystallinity of the final product can be systemically controlled. The container effect also explain some of the problems with reproducibility in previously reported results. PMID:21861449

  6. Hypercrosslinked Phenolic Polymers with Well Developed Mesoporous Frameworks

    SciTech Connect

    Mahurin, Shannon Mark; Dai, Sheng

    2015-01-01

    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 aromatic-based polymers with robust frameworks.

  7. 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

  8. 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.

  9. Phase State and Dynamics of Fluids in Mesoporous Solids

    NASA Astrophysics Data System (ADS)

    Valiullin, Rustem

    2011-03-01

    Fundamental understanding of the correlations between the phase state and dynamics of fluids confined to mesoporous solids is an important prerequisite for their optimal use in practical applications. The present contribution describes some recent progress in the exploration of such interrelations using nuclear magnetic resonance. In particular, transport properties of fluids during gas-liquid, solid-liquid and liquid-liquid transitions occurring in pore spaces of mesoporous solids are discussed and are shown to bear strong correlations. From the results presented it will, in particular, become evident that molecular diffusivity is a sensitive microscopic parameter not only to the thermodynamic state of the system, but also the history of its preparation.

  10. Diffusion NMR of Fluids Confined to Mesopores under High Pressures

    NASA Astrophysics Data System (ADS)

    Zeigermann, Philipp; Dvoyashkin, Muslim; Gläser, Roger; Valiullin, Rustem

    2011-03-01

    Supercritical fluids are extensively used in various chemical applications including processes involving porous solids. The knowledge of their transport in bulk as well as under spatial confinements is critical for modeling and optimizing chemical reactions. In this contribution, we describe a high-pressure cell designed for pulsed field gradient NMR studies of diffusion of supercritical solvents in mesoporous materials. Some preliminary results on diffusion properties of ethane in bulk phase and confined to pores of mesoporous silicon obtained in a broad range of pressures below and above the critical temperature are reported.

  11. Container Effect in Nanocasting Synthesis of Mesoporous Metal Oxides

    SciTech Connect

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

    2011-08-23

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

  12. 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...

  13. 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

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

    PubMed

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

    2016-09-23

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol-gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol-gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug. PMID:27533108

  15. CO₂ adsorption on amine-functionalized periodic mesoporous benzenesilicas.

    PubMed

    Sim, Kyohyun; Lee, Nakwon; Kim, Joonseok; Cho, Eun-Bum; Gunathilake, Chamila; Jaroniec, Mietek

    2015-04-01

    CO2 adsorption was investigated on amine-functionalized mesoporous silica (SBA-15) and periodic mesoporous organosilica (PMO) samples. Hexagonally (p6mm) ordered mesoporous SBA-15 and benzene-PMO (BPMO) samples were prepared in the presence of Pluronic P123 block copolymer template under acidic conditions. Three kinds of amine-containing organosilanes and polyethylenimine were used to functionalize SBA-15 and BPMO. Small-angle X-ray scattering and nitrogen adsorption isotherms showed that these samples featured ordered mesostructure, high surface area, and narrow pore size distributions. Solid-state (13)C- and (29)Si cross-polarization magic-angle spinning NMR spectra showed chemical linkage between amine-containing modifiers and the surface of mesoporous materials. The chemically linked amine-containing modifiers were found to be on both the inner and outer surfaces. N-[3-(trimethoxysilyl)propyl]ethylenediamine-modified BPMO (A2-BPMO) sample exhibited the highest CO2 uptake (i.e., ∼3.03 mmol/g measured on a volumetric adsorption analyzer) and the fastest adsorption rate (i.e., ∼13 min to attain 90% of the maximum amount) among all the samples studied. Selectivity and reproducibility measurements for the A2-BPMO sample showed quite good performance in flowing N2 gas at 40 mL/min and CO2 gas of 60 mL/min at 25 °C. PMID:25742049

  16. 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

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

    PubMed

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

    2014-06-01

    In this paper, we study synthesis and characteristics of mesoporous silica nanotubes modified by titanium dioxide, as well as their antimicrobial properties and influence on mitochondrial activity of mouse fibroblast L929. Nanocrystalized titania is confined in mesopores of silica nanotubes and its light activated antibacterial response is revealed. The analysis of the antibacterial effect on Escherichia coli. (ATCC 25922) shows strong enhancement during irradiation with the artificial visible and ultraviolet light in respect to the commercial catalyst and control sample free from the nanomaterials. In darkness, the mesoporous silica/titania nanostructures exhibited antibacterial activity dependent on the stirring speed of the suspension containing nanomaterials. Obtained micrograph proved internalization of the sample into the microorganism trough the cell membrane. The analysis of the mitochondrial activity and amount of lactate dehydrogenase released from mouse fibroblast cells L929 in the presence of the sample were determined with LDH and WST1 assays, respectively. The synthesized silica/titania antibacterial agent also exhibits pronounced photoinduced inactivation of the bacterial growth under the artificial visible and UV light irritation in respect to the commercial catalyst. Additionally, mesoporous silica/titania nanotubes were characterized in details by means of high resolution transmission electron microscopy (HR-TEM), XRD and BET Isotherm. PMID:24676537

  18. Solution Plasma Process for Template Removal in Mesoporous Silica Synthesis

    NASA Astrophysics Data System (ADS)

    Pootawang, Panuphong; Saito, Nagahiro; Takai, Osamu

    2010-12-01

    The plasma discharge in aqueous solution was scientifically studied and applied to template removal in mesoporous silica synthesis. Highly dispersed spherical mesoporous silica particles were synthesized by the ternary surfactant system containing the Pluronic P123 copolymer (EO20PO69EO20), sodium dodecylbenzene sulfonate, and 1,1,2,2,3,3,4,4,4-nonafluoro-1-butane sulfonate, via the sol-gel method in acid solutions. The solution plasma process (SPP), instead of conventional thermal calcinations, was used to remove the template. The mechanism of the removal of the organic template occurred via oxidation by the hydroxyl radicals generated during discharge. The transformation of a mesopore structure from a disordered wormlike structure to a hexagonally arranged structure was observed by X-ray diffraction analysis and was confirmed by transmission electron microscopy. The results of the thermal analysis and functional group identification of mesoporous silica after SPP showed evidence of organic template removal. The surface area calculated using the Brunauer-Emmett-Teller (BET) theory and the mean pore diameter results could be used to evaluate the plasma efficiency, demonstrating that this method does not affect the pore size in the case of discharge in a solution of pH 3 compared with the results of thermal calcination. Hence, SPP was proved to be highly efficient for organic template removal, exhibiting short consumption time and less contamination.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  20. Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene.

    PubMed

    Liu, Lei; Deng, Qing-Fang; Agula, Bao; Zhao, Xu; Ren, Tie-Zhen; Yuan, Zhong-Yong

    2011-08-01

    Metal-free ordered mesoporous carbons were demonstrated to be robust catalysts for direct dehydrogenation of propane to propylene, in the absence of any auxiliary steam, exhibiting high activity and selectivity, as well as long catalytic stability, in comparison with nanostructured carbons. PMID:21687889

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

  3. 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.

  4. 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).

  5. 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).

  6. 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.

  7. 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.

  8. Multifunctional mesoporous silica nanocomposite nanoparticles for theranostic applications.

    PubMed

    Lee, Ji Eun; Lee, Nohyun; Kim, Taeho; Kim, Jaeyun; Hyeon, Taeghwan

    2011-10-18

    Clever combinations of different types of functional nanostructured materials will enable the development of multifunctional nanomedical platforms for multimodal imaging or simultaneous diagnosis and therapy. Mesoporous silica nanoparticles (MSNs) possess unique structural features such as their large surface areas, tunable nanometer-scale pore sizes, and well-defined surface properties. Therefore, they are ideal platforms for constructing multifunctional materials that incorporate a variety of functional nanostructured materials. In this Account, we discuss recent progress by our group and other researchers in the design and fabrication of multifunctional nanocomposite nanoparticles based on mesoporous silica nanostructures for applications to simultaneous diagnosis and therapy. Versatile mesoporous silica-based nanocomposite nanoparticles were fabricated using various methods. Here, we highlight two synthetic approaches: the encapsulation of functional nanoparticles within a mesoporous silica shell and the assembly of nanoparticles on the surface of silica nanostructures. Various nanoparticles were encapsulated in MSNs using surfactants as both phase transfer agents and pore-generating templates. Using MSNs as a scaffold, functional components such as magnetic nanoparticles and fluorescent dyes have been integrated within these systems to generate multifunctional nanocomposite systems that maintain their individual functional characteristics. For example, uniform mesoporous dye-doped silica nanoparticles immobilized with multiple magnetite nanocrystals on their surfaces have been fabricated for their use as a vehicle capable of simultaneous magnetic resonance (MR) and fluorescence imaging and drug delivery. The resulting nanoparticle-incorporated MSNs were then tested in mice with tumors. These in vivo experiments revealed that these multifunctional nanocomposite nanoparticles were delivered to the tumor sites via passive targeting. These nanocomposite

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Jin, Zhao

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

  11. 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

  12. 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

  13. 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

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

    SciTech Connect

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

    2013-05-15

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

  15. 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.

  16. Highly ordered mesoporous silica nanoparticles and their application to DNA separation

    NASA Astrophysics Data System (ADS)

    Lee, Hye Sun; Chang, Jeong Ho

    2008-12-01

    This work describes the innovative development of high throughput human DNA purification process using the molecular self-assembled mesoporous silica nanoparticles. The mesoporous silica nanoparticles were prepared by sol-gel method and the formation of molecular self-assembled monolayers with functional groups was chemically demonstrated. The surface modification of functional groups was performed with aminofunctionallized organic silanes on mesoporous silica nanoparticles and the results of DNA separation was represented with electrophoresis images.

  17. 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. PMID:21988174

  18. 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

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

    SciTech Connect

    Seong Huh

    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 Cu{sup 2+} adsorption capacity tests, The ratio of two different organic groups inside of mesopores of these MSNs could be fine-tuned. These MSNs serve as a useful model system to study substrate selectivity in catalytic reactions and sorption phenomena. For example, the Cu{sup 2+} adsorption capacity of these materials was dictated by the chemical nature of the mesopores generated by the different organic functional groups. An investigation of the substrate selectivity of the bifunctionalized MSNs in a competitive nitroaldol reaction using an equimolar amount of two competing 4-nitrobenzaldehyde derivatives was performed. Shape-controlled bifunctional MSNs were employed as the catalysts. The properties of the MSNs were investigated using various spectroscopic methods and electron microscopy. The more hydrophobic the surface organic groups are, the higher the ratio of hydrophobic final product. This is the first example to demonstrate the selection of substrate using physicochemical nature of the mesopore surface other than the conventional shape selection in zeolite systems. I also created a cooperative dual catalyst system that is

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

    NASA Astrophysics Data System (ADS)

    Huh, Seong

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

  1. 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

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

    SciTech Connect

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

    2014-11-01

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

  3. 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

  4. In Situ Loading of Drugs into Mesoporous Silica SBA-15.

    PubMed

    Wan, Mi Mi; Li, Yan Yan; Yang, Tian; Zhang, Tao; Sun, Xiao Dan; Zhu, Jian Hua

    2016-04-25

    In a new strategy for loading drugs into mesoporous silica, a hydrophilic (heparin) or hydrophobic drug (ibuprofen) is encapsulated directly in a one-pot synthesis by evaporation-induced self-assembly. In situ drug loading significantly cuts down the preparation time and dramatically increases the loaded amount and released fraction of the drug, and appropriate drug additives favor a mesoporous structure of the vessels. Drug loading was verified by FTIR spectroscopy and release tests, which revealed much longer release with a larger amount of heparin or ibuprofen compared to postloaded SBA-15. Besides, the in vitro anticoagulation properties of the released heparin and the biocompatibility of the vessels were carefully assessed, including activated partial thromboplastin time, thrombin time, hemolysis, platelet adhesion experiments, and the morphologies of red blood cells. A concept of new drug-release agents with soft core and hard shell is proposed and offers guidance for the design of novel drug-delivery systems. PMID:26999658

  5. 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.

  6. Oriented mesoporous nanopyramids as versatile plasmon-enhanced interfaces.

    PubMed

    Kong, Biao; Tang, Jing; Selomulya, Cordelia; Li, Wei; Wei, Jing; Fang, Yin; Wang, Yongcheng; Zheng, Gengfeng; Zhao, Dongyuan

    2014-05-14

    We developed a facile interfacial oriented growth and self-assembly process to fabricate three-dimensional (3D) aligned mesoporous iron oxide nanopyramid arrays (NPAs). The unique NPAs possess a 3D mesostructure with multiple features, including high surface area (~175 m(2)/g), large pore size (~20 nm), excellent flexibility (bent over 150 times), and scalability at the foot scale for practical applications. More importantly, these NPAs structures enable versatile enhancement of localized surface plasmon resonance and photoelectrochemical conversion. The integration of plasmonic gold with 3D NPAs remarkably improves the performance of photoelectrochemical conversion, leading to ~6- and 83-fold increases of the photocurrent under simulated solar and visible-light illumination, respectively. The fabrication and investigation of NPAs provide a new paradigm for preparing unconventional mesoporous oriented thin films and further suggest a new strategy for designing plasmonic metal/semiconductor systems for effective solar energy harvesting. PMID:24786963

  7. 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. PMID:19441565

  8. 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

  9. 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

  10. 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

  11. 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

  12. A series of highly stable mesoporous metalloporphyrin Fe-MOFs.

    PubMed

    Wang, Kecheng; Feng, Dawei; Liu, Tian-Fu; Su, Jie; Yuan, Shuai; Chen, Ying-Pin; Bosch, Mathieu; Zou, Xiaodong; Zhou, Hong-Cai

    2014-10-01

    A series of mesoporous metalloporphyrin Fe-MOFs, namely PCN-600(M) (M = Mn, Fe, Co, Ni, Cu), have been synthesized using the preassembled [Fe3O(OOCCH3)6] building block. PCN-600 exhibits a one-dimensional channel as large as 3.1 nm and the highest experimental pore volume of 1.80 cm(3)g(-1) among all the reported porphyrinic MOFs. It also shows very high stability in aqueous solutions with pH values ranging from 2-11 and is to our knowledge the only mesoporous porphyrinic MOF stable under basic aqueous conditions. PCN-600(Fe) has been demonstrated as an effective peroxidase mimic to catalyze the co-oxidation reaction. PMID:25208035

  13. Flash freezing route to mesoporous polymer nanofibre networks.

    PubMed

    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 m(2) 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

  15. 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.

  16. 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.

  17. Catalytic mesoporous Janus nanomotors for active cargo delivery.

    PubMed

    Ma, Xing; Hahn, Kersten; Sanchez, Samuel

    2015-04-22

    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

  18. 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.

  19. 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.

  20. 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.

  1. Electronic Parameters of Mesoporous Silicon Upon Adsorption of Plant Viruses

    NASA Astrophysics Data System (ADS)

    Vashpanov, Yuriy; Son, Jung-Young; Kwack, Kae-Dal; Shin, Seung-Jung

    2008-06-01

    Changes in the electronic parameters of mesoporous silicon upon adsorption of nematodetransmitted polyhedral (NEPO) viruses of plant [tomato ringspot virus (TORSV), grapevine virus A (GVA), and grapevine fan leaf virus (GFLV)] measured at room temperature are investigated. The adsorption of these viruses affected essentially on the electronic characteristic of the porous material. The measurement of the electronic characteristics of porous silicon can be applied to the creation of detectors for the presence of viruses in a given environment.

  2. 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

  3. Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

    SciTech Connect

    Yu Changlin; Yu, Jimmy C.; Chan Mui

    2009-05-15

    A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO{sub 2} microspheres was developed. Formation of mesoporous TiO{sub 2} and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO{sub 2} microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO{sub 2} microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide. - Graphical abstract: A novel method for preparing fluorinated mesoporous TiO{sub 2} microspheres was developed by a combined ultrasonic and hydrothermal treatment. The fluorinated TiO{sub 2} microspheres show high crystallinity, stability and enhanced photocatalytic activity.

  4. 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

  5. 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.

  6. 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

  7. 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

  8. 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. PMID:23586307

  9. Catalytic upgrading of xylan over mesoporous Y catalyst.

    PubMed

    Kim, Seong-Soo; Jun, Bo Ram; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Kim, Tae-Wan; Park, Young-Kwon

    2014-04-01

    In-situ catalytic cracking of xylan, a model compound of hemicellulose, was carried out using pyrolysis-gas chromatography/mass spectrometry over mesoporous Y for the first time. Experiments were conducted at three different temperatures, 400 degrees C, 450 degrees C, and 500 degrees C, to investigate the effect of reaction temperature. Three different biomass-to-catalyst ratios, 1:1, 1:2, and 1:3, were tested at 500 degrees C to examine the effect of catalyst dose. In addition, the catalytic activity of mesoporous Y was compared with that of Al-MCM-41. The catalysts used were characterized by N2 adsorption-desorption, temperature programmed desorption of NH3, and X-ray diffraction. The main pyrolysis products of xylan were acids, hydrocarbons, phenolics, oxygenates, aromatics, and polycyclic aromatic hydrocarbons. Mesoporous Y, which has acid sites with larger quantity and stronger acidity than those of Al-MCM-41, was shown to enhance the quality of bio-oil to a larger extent, producing a larger quantity of high-value-added products, such as aromatics and furans. PMID:24734712

  10. Study of carbon monoxide oxidation on mesoporous platinum.

    PubMed

    Esterle, Thomas F; Russell, Andrea E; Bartlett, Philip N

    2010-09-10

    H(1) mesoporous platinum surfaces formed by electrodeposition from lyotropic liquid crystalline templates have high electroactive surface areas (up to 60 m(2) g(-1)) provided by the concave surface within their narrow (≈2 nm diameter) pores. In this respect, they are fundamentally different from the flat surfaces of ordinary Pt electrodes or the convex surfaces of high-surface-area Pt nanoparticles. Cyclic voltammetry of H(1) mesoporous Pt films in acid solution is identical to that for polycrystalline Pt, suggesting that the surfaces of the pores are made up of low-index Pt faces. In contrast, CO stripping voltammetry on H(1) mesoporous Pt is significantly different from the corresponding voltammetry on polycrystalline Pt and shows a clear prewave for CO oxidation and the oxidation CO at lower overpotential. These differences in CO stripping are related to the presence of trough sites where the low-index Pt faces that make up the concave surface of the pore walls meet. PMID:20578119

  11. Evaluation of thermoporometry for characterization of mesoporous materials.

    PubMed

    Yamamoto, Takuji; Endo, Akira; Inagi, Yuki; Ohmori, Takao; Nakaiwa, Masaru

    2005-04-15

    The accuracy of thermoporometry (TPM) in terms of the characterization of SBA-15 is examined based on a model that classifies the water in the mesopores into two different types: freezable pore water, which can form cylindrical ice crystals, and nonfreezable pore water, which cannot undergo a phase transition during a differential scanning calorimetry (DSC) measurement. Applying the empirical relationship between the sizes of the ice crystals formed in the mesopores and the solidification temperature of the freezable pore water to a thermogram (a recording of the heat flux during the solidification of the freezable pore water) yielded a size distribution of the ice crystals. The size of the ice crystals increased slightly with repetitive freezing, indicating that the mesopores were enlarged by formation of the ice crystals. Adding the thickness, t(nf), of the nonfreezable pore water layer to the ice crystal-size distribution calculated from the thermogram allowed for the determination of the porous properties of SBA-15. The porous properties attained from TPM experiments were compared with the results attained through the combination of Ar gas adsorption experiments and nonlocal density functional theory (NLDFT) analysis. The porous properties determined by TPM were confirmed to be quite sensitive to the t(nf) value. PMID:15780301

  12. 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

  13. 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.

  14. 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.

  15. Nucleation Pathways of CO2 Condensation under Mesoporous Templated Glass

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Byran, Matthew S.; Warren, Garfield T.; Sokol, Paul E.; Indiana University Team; NIST Collaboration

    2015-03-01

    Carbon capture and storage (CCS) are important elements in reducing greenhouse gas emission and combating global warming. The adsorption behavior of CO2 under mesoporous confinement at room temperature is particularly relevant. , Small Angle Scattering of X-ray (SAXS) and Neutron (SANS) were used to probe the adsorption process of CO2 under such mesoporous confinement MCM-41 and details of nucleation pathways were mapped out by fitting the scattering intensities with adsorption models. From both experiments, the nucleation of CO2 on the inner pore surface of MCM-41 is found to be a two-step process; high density liquid phase CO2 first forms uniform layers following the long range translational symmetry of the porous matrix, above one CO2 filling, determined by the pore size and temperature, capillary condensation initiates. The nucleation sites formed during capillary condensation start to separate the long range symmetry from the one at uniform layers. Finally, SAXS and SANS techniques are compared and they both showed their unique properties of probing the filling-dependent structures of adsorbed CO2 under such mesoporous system.

  16. Hollow periodic mesoporous organosilica nanospheres by a facile emulsion approach.

    PubMed

    Ma, Xiaobo; Zhang, Junjie; Dang, Meng; Wang, Jin; Tu, Zenzen; Yuwen, Lihui; Chen, Guotao; Su, Xiaodan; Teng, Zhaogang

    2016-08-01

    Periodic mesoporous organosilicas (PMOs) with homogeneously incorporated organic groups, highly ordered mesopores, and controllable morphology have attracted increasing attention. In this work, one-step emulsion approach for preparation of hollow periodic mesoporous organosilica (HPMO) nanospheres has been established. The method is intrinsically simple and does not require any sacrificial templates, corrosive and toxic etching agents. The obtained HPMO nanospheres have high surface area (∼950m(2)g(-1)), accessible ordered mesochannels (∼3.4nm), large pore volume (∼3.96cm(3)g(-1)), high condensation degree (77%), and diameter (∼560nm), hollow chamber size (∼400nm), and shell thickness (∼80nm). Furthermore, cytotoxicity show the cell viability is higher than 86% after incubating with the HPMO nanospheres at a concentration of up to 1200μgmL(-1) for 24h. The hemolysis of HPMO nanospheres is lower than 1.1% at concentrations ranging from 10 to 2000μgmL(-1). The lower hemolysis and cytotoxicity make the HPMO nanospheres great promise for future biomedical applications. PMID:27156086

  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. Biomolecule-assisted route to prepare titania mesoporous hollow structures.

    PubMed

    Ding, Shangjun; Wang, Yaoming; Hong, Zhanglian; Lü, Xujie; Wan, Dongyun; Huang, Fuqiang

    2011-10-01

    Amino acids, as a particularly important type of biomolecules, have been used as multifunctional templates to intelligently construct mesoporous TiO(2) hollow structures through a simple solvothermal reaction. The structure-directing behaviors of various amino acids were systematically investigated, and it was found that these biomolecules possess the general capability to assist mesoporous TiO(2) hollow-sphere formation. At the same time, the nanostructures of the obtained TiO(2) are highly dependent on the isoelectric points (pI) of amino acids. Their molecular-structure variations can lead to pI differences and significantly influence the final TiO(2) morphologies. Higher-pI amino acids (e.g., L-lysine and L-arginine) have better structure-directing abilities to generate nanosheet-assembled hollow spheres and yolk/shell structures. The specific morphologies and mesopore size of these novel hollow structures can also be tuned by adjusting the titanium precursor concentration. Heat treatment in air and vacuum was further conducted to transform the as-prepared structures to porous nanoparticle-assembled hollow TiO(2) and TiO(2)/carbon nanocomposites, which may be potentially applied in the fields of photocatalysts, dye-sensitized solar cells, and Li batteries. This study provides some enlightenment on the design of novel templates by taking advantage of biomolecules. PMID:21882272

  19. Silica-based mesoporous nanobiomaterials as promoter of bone regeneration process.

    PubMed

    Shadjou, Nasrin; Hasanzadeh, Mohammad

    2015-11-01

    Silica-based mesostructured nanomaterials have emerged as a full family of biomaterials with tremendous potential to address the requirements for the bone regeneration process. This review focuses on more recent advances in bone regeneration process based on silica-based mesoporous biomaterials during 2012 to January 2015. In this review, we describe application of silica-based mesoporous mesostructured nanomaterials (possessing pore sizes in the range 2-50 nm) for the bone regeneration process. 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. The effect of structural and textural properties of mesoporous materials on the development of new biomaterials for treatment of different bone pathologies such as infection, osteoporosis, cancer, and so forth is discussed. In addition, silica-based mesoporous bioactive glass, as a potential drug/growth factor carrier, is reviewed, which includes the composition-structure-drug delivery relationship and the functional effect on the antibacteria and tissue-stimulation properties. Also, application of different mesoporous materials on construction of 3D macroporous scaffolds for bone tissue engineering was disused. Finally, this review discusses the possibility of covalently grafting different osteoinductive agents to the silica-based mesoporous scaffold surface that act as attracting signals for bone cells to promote the bone regeneration process. PMID:26011776

  20. A reconstruction strategy to synthesize mesoporous SAPO molecular sieve single crystals with high MTO catalytic activity.

    PubMed

    Wang, Chan; Yang, Miao; Li, Mingrun; Xu, Shutao; Yang, Yue; Tian, Peng; Liu, Zhongmin

    2016-05-11

    Mesoporous SAPO-34 single crystals with tunable porosity and Si content have been fast synthesized within 4 hours by a reconstruction strategy, which show excellent hydrothermal stability and MTO catalytic activity. This new strategy is further proven to be applicable to prepare other mesoporous SAPO molecular sieve single crystals. PMID:27101359

  1. Synthesis of organic-inorganic hybrid mesoporous tin oxophosphate in the presence of anionic surfactant.

    PubMed

    Mal, Nawal Kishor; Fujiwara, Masahiro; Matsukata, Masahiko

    2005-11-01

    Synthesis of novel mesoporous hybrid tin oxophosphate is reported from phenylphosphonic acid as the only precursor of phosphorus in the presence of anionic surfactant (SDS), which possesses a wormhole mesoporous structure and is stable even after calcination at 550 degrees C. PMID:16228034

  2. 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. PMID:20024287

  3. 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.

  4. A bio-catalytically driven Janus mesoporous silica cluster motor with magnetic guidance.

    PubMed

    Ma, Xing; Sanchez, Samuel

    2015-03-28

    A bio-catalytic Janus motor based on the mesoporous silica cluster (JMSC) is fabricated. Chemically conjugated catalase triggers the decomposition of H2O2 to produce driving force by bubble propulsion, while a metallic (Ni) coating layer allows for magnetic guidance of the motor. The JMSC motor can act as a delivery vehicle with cargo loading inside its mesopores. PMID:25407318

  5. Ionic liquid decorated mesoporous silica nanoparticles: a new high-performance hybrid electrolyte for lithium batteries.

    PubMed

    Li, Yang; Wong, Ka-Wai; Ng, Ka-Ming

    2016-03-10

    We report a novel hybrid electrolyte based on mesoporous silica nanoparticles decorated with an ionic liquid, which exhibits a superior lithium ion transference number of >0.8, and an excellent electrochemical window of >5 V with attractive ionic conductivity. The insights obtained pave a new way for the preparation of high-performance electrolytes with mesoporous structures. PMID:26926805

  6. 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.

  7. A facile route to synthesize endurable mesopore containing ZSM-5 catalyst for methanol to propylene reaction.

    PubMed

    Sun, Chao; Du, Junming; Liu, Jian; Yang, Yisu; Ren, Nan; Shen, Wei; Xu, Hualong; Tang, Yi

    2010-04-21

    A novel route is proposed for the preparation of mesopore containing zeolite ZSM-5 via in situ hydrothermal treatment of a solution containing alkali-dissolved SBA-15 containing carbonized surfactant P123 in the mesopores; it exhibited prominent stability enhancement for methanol to propylene reaction. PMID:20461876

  8. Ultrasound assisted morphological control of mesoporous silica with improved lysozyme adsorption.

    PubMed

    Sun, Shumin; Wang, Shen; Wang, Peiyuan; Wu, Qiong; Fang, Shaoming

    2015-03-01

    The morphological control of mesoporous silica without any additives has attracted much attention. Discrete rod-like and string-of-beads like mesoporous SBA-15 can be achieved under ultrasound irradiation without changing the composition of synthesis system. The smaller particles of SBA-15 showed improved lysozyme immobilization capacity and higher adsorption rate over conventional rope-like SBA-15. PMID:25150609

  9. 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

  10. 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

  11. Effect of Nickel Contents on the Microstructure of Mesoporous Nickel Gadolinium-Doped Ceria

    NASA Astrophysics Data System (ADS)

    Ahn, Seunghyun; Koo, Hyun; Bae, Sung-Hwan; Park, Chan; Cho, Guyoung; Chang, Ikwhang; Cha, Suk-Won; Yoo, Young-Sung

    2013-12-01

    The effect of NiO contents on the microstructure of mesoporous NiO-Gd0.25Ce0.75O2-x (NiO-GDC) composite for intermediate temperature solid oxide fuel cells (IT-SOFC) was investigated. Mesoporous NiO-GDC powders with different NiO contents were synthesized by self-assembly hydrothermal method using tri-block copolymer, Pluronic F127, as a structure directing agent. Grain growth/agglomeration behaviors of NiO particles and changes of mesoporous structure of GDC particles were characterized by microstructural analyses. NiO-GDC powders were composed of GDC nano particles with ordered mesopore inside the particles and octahedral NiO grains with truncated-edges. As the amount of NiO increases, specific area value of mesoporous NiO-GDC was decreased, and the agglomeration/growth behavior of NiO grains was accelerated.

  12. Mesoporous hybrids containing Eu 3+ complexes covalently bonded to SBA-15 functionalized: Assembly, characterization and photoluminescence

    NASA Astrophysics Data System (ADS)

    Li Kong, Li; Yan, Bing; Li, Ying

    2009-07-01

    A novel series of luminescent mesoporous organic-inorganic hybrid materials has been prepared by linking Eu 3+ complexes to the functionalized ordered mesoporous SBA-15 which was synthesis by a co-condensation process of 1,3-diphenyl-1,3-propanepione (DBM) modified by the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC), tetraethoxysilane (TEOS), Pluronic P123 surfactant as a template. It was demonstrated that the efficient intramolecular energy transfer in the mesoporous material Eu(DBMSi-SBA-15) 3phen mainly occurred between the modified DBM (named as DBM-Si) and the central Eu 3+ ion. So the Eu(DBMSi-SBA-15) 3phen showed characteristic emission of Eu 3+ ion under UV irradiation with higher luminescence quantum efficiency. Moreover, the mesoporous hybrid materials exhibited excellent thermal stability as the lanthanide complex was covalently bonded to the mesoporous matrix.

  13. 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.

  14. 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

  15. Synthesis of highly-ordered mesoporous carbon/silica nanocomposites and derivative hierarchically mesoporous carbon from a phenyl-bridged organosiloxane

    NASA Astrophysics Data System (ADS)

    Wu, Zhiwang; Pang, Jiebin; Lu, Yunfeng

    2009-11-01

    Mesoporous carbon/silica nanocomposites and derivative hierarchically mesoporous carbon have been prepared using 1,4-bis(triethoxysilyl)benzene (BTEB) as a precursor for a carbon/silica network and Pluronic P123 (HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H) as a template for highly-ordered hexagonal pores. Co-assembly of BTEB and P123 and subsequent carbonization results in a mesoporous carbon/silica nanocomposite with hexagonally oriented pores. Removal of the silica component in the carbon/silica network creates a second porosity in the network and results in hierarchically mesoporous carbon. The mesostructure of these materials was characterized by transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), and N2 sorption.

  16. 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.

  17. Nano-hard template synthesis of pure mesoporous NiO and its application for streptavidin protein immobilization.

    PubMed

    Wahab, Mohammad A; Darain, Farzana

    2014-04-25

    A simple and efficient immobilization of streptavidin protein (with hexa-histidine tag) onto the surface of mesoporous NiO is described. Before immobilization of streptavidin protein (with hexa-histidine tag) onto the surface of mesoporous NiO, we first synthesized well-organized mesoporous NiO by a nanocasting method using mesoporous silica SBA-15 as the hard template. Then, the well-organized mesoporous NiO particles were characterized by small angle x-ray diffraction (XRD), wide angle XRD, nitrogen adsorption/desorption, and transmission electron microscopy (TEM). TEM and small angle XRD suggested the formation of mesoporous NiO materials, whereas the wide angle XRD pattern of mesoporous NiO indicated that the nickel precursor had been transformed into crystalline NiO. The N2 sorption experiments demonstrated that the mesoporous NiO particles had a high surface area of 281 m2 g(-1), a pore volume of 0.51 cm3 g(-1) and a pore size of 4.8 nm. Next, the immobilization of streptavidin protein (with hexa-histidine tag) onto the surface of mesoporous NiO was studied. Detailed analysis using gel electrophoresis confirmed that this approach can efficiently bind his-tagged streptavidin onto the surface of mesoporous NiO material since the mesoporous NiO provides sufficient surface sites for the binding of streptavidin via non-covalent ligand binding with the histidine tag. PMID:24670980

  18. Samarium-doped mesoporous TiO2 nanoparticles with improved photocatalytic performance for elimination of gaseous organic pollutants

    NASA Astrophysics Data System (ADS)

    Tang, Jianting; Chen, Xiaomiao; Liu, Yu; Gong, Wei; Peng, Zhenshan; Cai, Tiejun; Luo, Lianjing; Deng, Qian

    2013-01-01

    Mesoporous TiO2 doped with different amounts of Sm were prepared via a sol-gel route with Pluronic P123 as template. The materials were characterized by X-ray diffraction, transmission electron microscopy, and N2 sorption experiments, etc. The photocatalytic activity of the mesoporous TiO2 was tested in elimination of gaseous methanol and acetone. The Sm doped mesoporous TiO2 have higher activity than those of the commercial photocatalyst (Degussa, P25) and Sm doped TiO2 counterparts without mesopore structure under ultraviolet light irradiation. A possible mechanism was proposed to account for the high photocatalytic activity of the Sm doped mesoporous TiO2. The superior activity of the Sm doped mesoporous TiO2 may be attributed to the synergic effect of the high surface area, mesopore structure and doped Sm species.

  19. Cobalt oxide and nitride particles supported on mesoporous carbons as composite electrocatalysts for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Chen, Ming; Shao, Leng-Leng; Gao, Ze-Min; Ren, Tie-Zhen; Yuan, Zhong-Yong

    2015-07-01

    The composite electrocatalysts of cobalt oxide/mesoporous carbon and cobalt nitride/mesoporous carbon are synthesized via a convenient oxidation and subsequent ammonia nitridation of cobalt particles-incorporated mesoporous carbon, respectively. The cobalt oxide and nitride particles are uniformly imbedded in mesoporous carbon matrix, forming the unique composites with high surface area and mesopore architecture, and the resultant composites are evaluated as counter electrode materials, exhibiting good catalytic activity for the reduction of triiodide. The composites of cobalt nitride and mesoporous carbon are superior to the counterparts of cobalt oxide and mesoporous carbon in catalyzing the triiodide reduction, and the dye-sensitized solar cell with the composites achieves an optimum power conversion efficiency of 5.26%, which is comparable to the one based on the conventional Pt counter electrode (4.88%).

  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. 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

  3. Selective catalysis utilizing bifunctionalized MCM-41 mesoporous materials

    SciTech Connect

    Strosahl, Kasey Jean

    2005-05-01

    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){sub 3}Si{approx}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 {approx}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. Mesoporous Few-Layer Graphene Platform for Affinity Biosensing Application.

    PubMed

    Ali, Md Azahar; Singh, Chandan; Mondal, Kunal; Srivastava, Saurabh; Sharma, Ashutosh; Malhotra, Bansi D

    2016-03-30

    A label-free, highly reproducible, sensitive, and selective biosensor is proposed using antiapolipoprotein B 100 (AAB) functionalized mesoporous few-layer reduced graphene oxide and nickel oxide (rGO-NiO) nanocomposite for detection of low density lipoprotein (LDL) molecules. The formation of mesoporous rGO-NiO composite on indium tin oxide conductive electrode has been accomplished via electrophoretic technique using colloidal suspension of rGO sheets and NiO nanoparticles. This biosensor shows good stability obtained by surface conjugation of antibody AAB molecules with rGO-NiO matrix by EDC-NHS coupling chemistry. The defect-less few layer rGO sheets, NiO nanoparticles (nNiO) and formation of nanocomposite has been confirmed by Raman mapping, electron microscopic studies, X-ray diffraction, and electrochemical techniques. The synthesized rGO-NiO composite is mesoporous dominated with a small percentage of micro and macroporous structure as is evident by the results of Brunauer-Emmett-Teller experiment. Further, the bioconjugation of AAB with rGO-NiO has been investigated by Fourier transform-infrared spectroscopy studies. The kinetic studies for binding of antigen-antibody (LDL-AAB) and analytical performance of this biosensor have been evaluated by the impedance spectroscopic method. This biosensor exhibits an excellent sensitivity of 510 Ω (mg/dL)(-1) cm(-2) for detection of LDL molecules and is sensitive to 5 mg/dL concentration of LDL in a wide range of 0-130 mg/dL. Thus, this fabricated biosensor is an efficient and highly sensitive platform for the analysis of other antigen-antibody interactions and biomolecules detection. PMID:26950488

  5. Sol Gel-Derived SBA-16 Mesoporous Material

    PubMed Central

    Rivera-Muñoz, Eric M.; Huirache-Acuña, Rafael

    2010-01-01

    The aim of this article is to review current knowledge related to the synthesis and characterization of sol gel-derived SBA-16 mesoporous silicas, as well as a review of the state of the art in this issue, to take stock of knowledge about current and future applications. The ease of the method of preparation, the orderly structure, size and shape of their pores and control, all these achievable through simple changes in the method of synthesis, makes SBA-16 a very versatile material, potentially applicable in many areas of science and molecular engineering of materials. PMID:20957080

  6. 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.

  7. 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.

  8. 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.

  9. Corrosion protection of mesoporous bioactive glass coating on biodegradable magnesium

    NASA Astrophysics Data System (ADS)

    Wang, Xiaojian; Wen, Cuie

    2014-06-01

    A mesoporous bioactive glass (MBG) coating was synthesized and coated on pure Mg substrate using a sol-gel dip-coating method. The MBG coating uniformly covered the Mg substrate with a thickness of ˜1.5 μm. Electrochemical and immersion tests were performed in order to investigate the biodegradation performance of Mg with and without different surface coatings in simulated body fluids (SBF) at 37 °C. Results revealed that the MBG coated Mg displayed a significantly lower biodegradation rate, in comparison with normal bioactive glass (BG) coated and uncoated Mg samples.

  10. 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

  11. Synthesis of white light emitting mesoporous carbon-silica nanocomposite

    NASA Astrophysics Data System (ADS)

    Sato, Koji; Ishikawa, Yukari; Matsumura, Akihiro; Ishii, Yosuke; Kawasaki, Shinji

    2011-05-01

    White light emitting mesoporous carbon-silica (MPCS) was synthesized by serially adding triblock copolymer (Pluronic, F127), ethanol (EtOH), tetraethoxysilane (TEOS), hydrochloric acid aqueous (HCl) and phenol-formaldehyde resin (resol) followed by the heat treatments of carbonization and oxidation. The PL intensity of MPCS showed a tendency to be strong with increasing of HCl concentration in >= 0.2 M. The pore size of MPCS that emits white light was 8 ~ 9 nm and the specific surface area was 320 ~ 418 m2 / g.

  12. "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.

  13. Structure and Luminescence Properties of Eu3+-Doped Cubic Mesoporous Silica Thin Films

    PubMed Central

    2010-01-01

    Eu3+ ions-doped cubic mesoporous silica thin films with a thickness of about 205 nm were prepared on silicon and glass substrates using triblock copolymer as a structure-directing agent using sol–gel spin-coating and calcination processes. X-ray diffraction and transmission electron microscopy analysis show that the mesoporous silica thin films have a highly ordered body-centered cubic mesoporous structure. High Eu3+ ion loading and high temperature calcination do not destroy the ordered cubic mesoporous structure of the mesoporous silica thin films. Photoluminescence spectra show two characteristic emission peaks corresponding to the transitions of5D0-7F1 and 5D0-7F2 of Eu3+ ions located in low symmetry sites in mesoporous silica thin films. With the Eu/Si molar ratio increasing to 3.41%, the luminescence intensity of the Eu3+ ions-doped mesoporous silica thin films increases linearly with increasing Eu3+ concentration. PMID:20672132

  14. 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. PMID:21305093

  15. 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.

  16. 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

  17. Bovine Serum Albumin Adsorption in Mesoporous Titanium Dioxide: Pore Size and Pore Chemistry Effect.

    PubMed

    Liu, Chang; Guo, Yanhua; Hong, Qiliang; Rao, Chao; Zhang, Haijuan; Dong, Yihui; Huang, Liangliang; Lu, Xiaohua; Bao, Ningzhong

    2016-04-26

    Understanding the mechanism of protein adsorption and designing materials with high sensitivity, high specificity and fast response are critical to develop the next-generation biosensing and diagnostic platforms. Mesoporous materials with high surface area, tunable pores, and good thermal/hydrostatic stabilities are promising candidates in this field. Because of the excellent biocompatibility, titanium dioxide has received an increasing interest in the past decade for biomedical applications. In this work, we synthesized mesoporous titanium dioxide with controlled pore sizes (7.2-28.0 nm) and explored their application for bovine serum albumin (BSA) adsorption. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption/desorption experiments were performed to characterize the mesoporous TiO2 samples before and after BSA adsorption. Isothermal microcalorimetry was applied to measure both the adsorption heat and conformation rearrangement heat of BSA in those mesopores. We also carried out thermogravimetry measurements to qualitatively estimate the concentration of hydroxyl groups, which plays an important role in stabilizing BSA in-pore adsorption. The adsorption stability was also examined by leaching experiments. The results showed that TiO2 mesopores can host BSA adsorption when their diameters are larger than the hydrodynamic size of BSA (∼9.5 nm). In larger mesopores studied, two BSA molecules were adsorbed in the same pores. In contrast to the general understanding that large mesopores demonstrate poor stabilities for protein adsorptions, the synthesized mesoporous TiO2 samples demonstrated good leaching stabilities for BSA adsorption. This is probably due to the combination of the mesoporous confinement and the in-pore hydroxyl groups. PMID:27048991

  18. One-step synthesis of degradable T1-FeOOH functionalized hollow mesoporous silica nanocomposites from mesoporous silica spheres

    NASA Astrophysics Data System (ADS)

    Peng, Yung-Kang; Tseng, Yu-Jui; Liu, Chien-Liang; Chou, Shang-Wei; Chen, Yu-Wei; Tsang, S. C. Edman; Chou, Pi-Tai

    2015-01-01

    The combination of a hollow mesoporous structure and a magnetic resonance (MR) contrast agent has shown its potential in simultaneous drug delivery and cell tracking applications. However, the preparation of this kind of nanocomposite is complicated and usually takes several days, which is unsuitable for scaled-up production. To overcome these hurdles, we report herein a facile method to synthesize iron oxide hydroxide functionalized hollow mesoporous silica spheres (FeOOH/HMSS) in a one-step manner. By carefully controlling the reaction kinetics of K2FeO4 in water, the gram-scale production of FeOOH/HMSS can be readily achieved at 60 °C for as short as 30 min. Most importantly, this synthetic process is also cost-effective and eco-friendly in both the precursor (K2FeO4 and H2O) and the product (FeOOH). The mechanism for the formation of a hollow structure was carefully investigated, which involves the synergetic effect of the surfactant CTAB and the side product KOH. Having outstanding biocompatibility, these degradable nanocolloids also demonstrate their feasibility in in vitro/vivo MR imaging and in vitro drug delivery.The combination of a hollow mesoporous structure and a magnetic resonance (MR) contrast agent has shown its potential in simultaneous drug delivery and cell tracking applications. However, the preparation of this kind of nanocomposite is complicated and usually takes several days, which is unsuitable for scaled-up production. To overcome these hurdles, we report herein a facile method to synthesize iron oxide hydroxide functionalized hollow mesoporous silica spheres (FeOOH/HMSS) in a one-step manner. By carefully controlling the reaction kinetics of K2FeO4 in water, the gram-scale production of FeOOH/HMSS can be readily achieved at 60 °C for as short as 30 min. Most importantly, this synthetic process is also cost-effective and eco-friendly in both the precursor (K2FeO4 and H2O) and the product (FeOOH). The mechanism for the formation of a

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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. PMID:22836788

  4. 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

  5. Mesoporous Phosphate Heterostructures: Synthesis and Application on Adsorption and Catalysis

    NASA Astrophysics Data System (ADS)

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

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

  6. 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.

  7. 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.

  8. Synthesis and characterization of nanocrystalline mesoporous zirconia using supercritical drying.

    PubMed

    Tyagi, Beena; Sidhpuria, Kalpesh; Shaik, Basha; Jasra, Raksh Vir

    2006-06-01

    Synthesis of nano-crystalline zirconia aerogel was done by sol-gel technique and supercritical drying using n-propanol solvent at and above supercritical temperature (235-280 degrees C) and pressure (48-52 bar) of n-propanol. Zirconia xerogel samples have also been prepared by conventional thermal drying method to compare with the super critically dried samples. Crystalline phase, crystallite size, surface area, pore volume, and pore size distribution were determined for all the samples in detail to understand the effect of gel drying methods on these properties. Supercritical drying of zirconia gel was observed to give thermally stable, nano-crystalline, tetragonal zirconia aerogels having high specific surface area and porosity with narrow and uniform pore size distribution as compared to thermally dried zirconia. With supercritical drying, zirconia samples show the formation of only mesopores whereas in thermally dried samples, substantial amount of micropores are observed along with mesopores. The samples prepared using supercritical drying yield nano-crystalline zirconia with smaller crystallite size (4-6 nm) as compared to higher crystallite size (13-20 nm) observed with thermally dried zirconia. PMID:17025056

  9. Nanostructured mesoporous materials for lithium-ion battery applications

    NASA Astrophysics Data System (ADS)

    Balaya, P.; Saravanan, K.; Hariharan, S.; Ramar, V.; Lee, H. S.; Kuezma, M.; Devaraj, S.; Nagaraju, D. H.; Ananthanarayanan, K.; Mason, C. W.

    2011-06-01

    The Energy crisis happens to be one of the greatest challenges we are facing today. In this view, much effort has been made in developing new, cost effective, environmentally friendly energy conversion and storage devices. The performance of such devices is fundamentally related to material properties. Hence, innovative materials engineering is important in solving the energy crisis problem. One such innovation in materials engineering is porous materials for energy storage. Porous electrode materials for lithium-ion batteries (LIBs) offer a high degree of electrolyte-electrode wettability, thus enhancing the electrochemical activity within the material. Among the porous materials, mesoporous materials draw special attention, owing to shorter diffusion lengths for Li+ and electronic movement. Nanostructured mesoporous materials also offer better packing density compared to their nanostructured counterparts such as nanopowders, nanowires, nanotubes etc., thus opening a window for developing electrode materials with high volumetric energy densities. This would directly translate into a scenario of building batteries which are much lighter than today's commercial LIBs. In this article, the authors present a simple, soft template approach for preparing both cathode and anode materials with high packing density for LIBs. The impact of porosity on the electrochemical storage performance is highlighted.

  10. Preparation and characterization of bioactive mesoporous wollastonite - Polycaprolactone composite scaffold.

    PubMed

    Wei, Jie; Chen, Fangping; Shin, Jung-Woog; Hong, Hua; Dai, Chenglong; Su, Jiancan; Liu, Changsheng

    2009-02-01

    A well-defined mesoporous structure of wollastonite with high specific surface area was synthesized using surfactant P123 (triblock copolymer) as template, and its composite scaffolds with poly(epsilon-caprolactone) (PCL) were fabricated by a simple method of solvent casting-particulate leaching. The measurements of the water contact angles suggest that the incorporation of either mesoporous wollastonite (m-WS) or conventional wollastonite (c-WS) into PCL could improve the hydrophilicity of the composites, and the former was more effective than the later. The bioactivity of the composite scaffold was evaluated by soaking the scaffolds in a simulated body fluid (SBF) and the results show that the m-WS/PCL composite (m-WPC) scaffolds can induce a dense and continuous layer of apatite after soaking for 1 week, as compared with the scattered and discrete apatite particles on the c-WS/PCL composite (c-WPC) scaffolds. The m-WPC had a significantly enhanced apatite-forming bioactivity compared with the c-WPC owing to the high specific surface area and pore volume of m-WS. In addition, attachment and proliferation of MG(63) cells on m-WPC scaffolds were significantly higher than that of c-WPC, revealing that m-WPC scaffolds had excellent biocompatibility. Such improved properties of m-WPC should be helpful for developing new biomaterials and may have potential use in hard tissue repair. PMID:19019424

  11. 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.

  12. Hollow mesoporous silica nanoparticles for intracellular delivery of fluorescent dye

    PubMed Central

    2011-01-01

    In this study, hollow mesoporous silica nanoparticles (HMSNs) were synthesized using the sol-gel/emulsion approach and its potential application in drug delivery was assessed. The HMSNs were characterized, by transmission electron microscopy (TEM), Scanning Electron Microscopy (SEM), nitrogen adsorption/desorption and Brunauer-Emmett-Teller (BET), to have a mesoporous layer on its surface, with an average pore diameter of about 2 nm and a surface area of 880 m2/g. Fluorescein isothiocyanate (FITC) loaded into these HMSNs was used as a model platform to assess its efficacy as a drug delivery tool. Its release kinetic study revealed a sequential release of FITC from the HMSNs for over a period of one week when soaked in inorganic solution, while a burst release kinetic of the dye was observed just within a few hours of soaking in organic solution. These FITC-loaded HMSNs was also found capable to be internalized by live human cervical cancer cells (HeLa), wherein it was quickly released into the cytoplasm within a short period of time after intracellular uptake. We envision that these HMSNs, with large pores and high efficacy to adsorb chemicals such as the fluorescent dye FITC, could serve as a delivery vehicle for controlled release of chemicals administered into live cells, opening potential to a diverse range of applications including drug storage and release as well as metabolic manipulation of cells. PMID:21208421

  13. 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

  14. Colloidal mesoporous silica nanoparticles enhance the biological activity of resveratrol.

    PubMed

    Summerlin, Natalie; Qu, Zhi; Pujara, Naisarg; Sheng, Yong; Jambhrunkar, Siddharth; McGuckin, Michael; Popat, Amirali

    2016-08-01

    The naturally occurring polyphenol resveratrol (RES) has attracted increasing attention in recent years due to its antioxidant, anti-inflammatory, and anticancer activity. However, resveratrol's promising potential as a nutraceutical is hindered by its poor aqueous solubility, which limits its biological activity. Here we show that encapsulating resveratrol in colloidal mesoporous silica nanoparticles (MCM-48-RES) enhances its saturated solubility by ∼95% and increases its in vitro release kinetics compared to pure resveratrol. MCM-48-RES showed high loading capacity (20% w/w) and excellent encapsulation efficiency (100%). When tested against HT-29 and LS147T colon cancer cell lines, MCM-48-RES-mediated in vitro cell death was higher than that of pure resveratrol, mediated via the PARP and cIAP1 pathways. Finally, MCM-48-RES treatment also inhibited lipopolysaccharide-induced NF-κB activation in RAW264.7 cells, demonstrating improved anti-inflammatory activity. More broadly, our observations demonstrate the potential of colloidal mesoporous silica nanoparticles as next generation delivery carriers for hydrophobic nutraceuticals. PMID:27060664

  15. Tablet preformulations of indomethacin-loaded mesoporous silicon microparticles.

    PubMed

    Tahvanainen, Maria; Rotko, Tanja; Mäkilä, Ermei; Santos, Hélder A; Neves, Diogo; Laaksonen, Timo; Kallonen, Aki; Hämäläinen, Keijo; Peura, Marko; Serimaa, Ritva; Salonen, Jarno; Hirvonen, Jouni; Peltonen, Leena

    2012-01-17

    In this study, indomethacin-loaded thermally oxidized mesoporous silicon microparticles (TOPSi-IMC) were formulated into tablets with excipients in order to improve the dissolution and permeability properties of the poorly soluble drug. Formulations of TOPSi-IMC particles and excipients were prepared at different TOPSi-IMC particle ratios (25, 30 and 35%). The formulations were compressed by direct compression technique with a single punch tablet machine. For comparison, a formulation containing the bulk IMC (indomethacin) and the same excipients without thermally oxidized mesoporous silicon microparticles particles (TOPSi) was prepared and compressed into tablets. The TOPSi-IMC tablets were characterised according to weight, thickness, crushing strength, disintegration time and dissolution rate. The results of this study show that TOPSi-IMC particles can be compressed to a conventional tablet. The release rate of the drug and its permeation across intestinal cells model (Caco-2) from TOPSi-IMC tablets was improved compared to the bulk IMC tablets. The dissolution rate and permeability of IMC from the tablets decreased with increasing ratio of the TOPSi-IMC particles in the formulation. The phenomenon is, presumably, a result of the loss of unique pore structure of the particles due to deformation of the particles under the compression load. PMID:22063301

  16. 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

  17. Influence of spatial configurations on electromagnetic interference shielding of ordered mesoporous carbon/ordered mesoporous silica/silica composites.

    PubMed

    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

  18. Influence of spatial configurations on electromagnetic interference shielding of ordered mesoporous carbon/ordered mesoporous silica/silica composites

    NASA Astrophysics Data System (ADS)

    Wang, Jiacheng; Zhou, Hu; Zhuang, Jiandong; Liu, Qian

    2013-11-01

    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.

  19. Anion Binding in Self-Assembled Monolayers in Mesoporous Supports (SAMMS)

    SciTech Connect

    Mattigod, Shas V.; Fryxell, Glen E.; Parker, Kent E.

    2007-02-19

    The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity. By lining the pore surfaces of mesoporous silica with self-assembled monolayer of organosilanes terminated with chemically selective ligands, a powerful new class of heavy metal sorbents has been realized, called self-assembled monolayers on mesoporous supports (SAMMS) [1-18]. When this interfacial functionality is composed of cationic transition metal complexes, a valuable new class of anion exchange material came into being [19]. Yoshitake and co-workers, have extended this concept to include other transition metal cations in similar cationic complexes inside mesoporous silica [20-23]. Other amine-based ligands (including polymer-based systems) were also explored, and the highest binding capacity was found with the diethylenetriamine ligand [20]. This synthetic strategy allows the chemist to easily modify both the metal center and ligand field, thereby tailoring chemical selectivity at multiple levels.

  20. Magnetic properties of mesoporous cobalt-silica-alumina ternary mixed oxides

    SciTech Connect

    Pal, Nabanita; Seikh, Md. Motin; Bhaumik, Asim

    2013-02-15

    Mesoporous cobalt-silica-alumina mixed oxides with variable cobalt content have been synthesized through slow evaporation method by using Pluronic F127 non-ionic surfactant as template. N{sub 2} sorption analysis of the template-free mixed oxide samples revealed that these mesoporous materials have high BET surface areas together with large mesopores. Powder XRD, TEM, EDS, FT IR and EPR spectroscopic analysis have been employed to understand the nature of the mesophases, bonding and composition of the materials. Low temperature magnetic measurements of these mixed oxide materials show the presence of ferromagnetic correlation at elevated temperature though at low temperature paramagnetic to ferrimagnetic transition is observed. Highlights: Black-Right-Pointing-Pointer Mesoporous cobalt-silica-alumina ternary mixed oxides. Black-Right-Pointing-Pointer High surface area and mesoporosity in magnetic materials. Black-Right-Pointing-Pointer Ferromagnetic correlation at elevated temperature. Black-Right-Pointing-Pointer Low temperature paramagnetic to ferrimagnetic transition.

  1. Highly efficient VOx/SBA-15 mesoporous catalysts for oxidative dehydrogenation of propane.

    PubMed

    Liu, Yong-Mie; Cao, Yong; Zhu, Ka-Ke; Yan, Shi-Run; Dai, Wei-Lin; He, He-Yong; Fan, Kang-Nian

    2002-12-01

    Highly dispersed vanadia species on SBA-15 mesoporous silica have been found to exhibit a highly efficient catalytic performance for the oxidative dehydrogenation (ODH) of propane to light olefins (propene + ethylene). PMID:12478769

  2. Synthesis of Mesoporous Aluminophosphates as Potential Catalysts in the Upgrading Petroleum Feedstocks

    SciTech Connect

    Ingram, Conrad, PH.D.

    2002-03-20

    This project focuses on the synthesis of mesoporous aluminophosphate (AlPO) catalysts for application in the acid catalyzed conversion of large petroleum feedstock compounds to Useful middle distillates and naphtha transportation fuels.

  3. 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.

  4. Synthesis of mesoporous maghemite with high surface area and its adsorptive properties

    NASA Astrophysics Data System (ADS)

    Asuha, S.; Zhao, Y. M.; Zhao, S.; Deligeer, W.

    2012-07-01

    Mesoporous maghemite (γ-Fe2O3) with high surface area was prepared by the thermal decomposition of Fe-urea complex ([Fe(CON2H4)6](NO3)3) with the aid of cetyltrimethyl ammonium bromide (CTAB), and its adsorption ability for the removal of fluoride was investigated. X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, transmission electron micrograph (TEM) observations, and magnetic measurements show that the γ-Fe2O3 has a mesoporous structure and its crystallite size, specific surface area, and magnetic properties can be controlled by varying the content of CTAB in [Fe(CON2H4)6](NO3)3. The maximum adsorption capacity of the mesoporous γ-Fe2O3 for fluoride is estimated to be 7.9 mg/g, which suggests that the mesoporous γ-Fe2O3 is an excellent adsorbent for fluoride.

  5. Synthesis of bifunctionalized mesoporous organosilica spheres for high-performance liquid chromatography.

    PubMed

    Zhu, Guiru; Yang, Qihua; Jiang, Dongmei; Yang, Jie; Zhang, Lei; Li, Ying; Li, Can

    2006-01-27

    Phenyl-functionalized mesoporous ethane-silicas with spherical morphology were synthesized by one-step co-condensation of phenyltrimethoxysilane (PTMS) and 1,2-bis(trimethoxysily)ethane (BTME) using a triblock copolymer EO(20)PO(70)EO(20) (P123) as template with the aid of a co-surfactant (cetyltrimethylammonium bromide, CTAB) and a co-solvent (ethanol) in acidic medium. Powder X-ray diffraction (XRD), nitrogen sorption measurement and scanning electron microscopy (SEM) show that phenyl-functionalized ethane-silica has wormhole-like mesostructure and perfect spherical morphology. The chemical stability of phenyl-functionalized mesoporous ethane-silica in basic medium is greatly improved owing to the ethane groups bridged in the mesoporous framework. This work also demonstrates that the phenyl-functionalized mesoporous ethane-silica spheres are excellent packing materials for potential application in the reversed-phase high-performance liquid chromatography (HPLC). PMID:16325828

  6. FINAL REPORT. ACTINIDE-SPECIFIC INTERFACIAL CHEMISTRY OF MONOLAYER COATED MESOPOROUS CERAMICS

    EPA Science Inventory

    The objective of this program was the design, synthesis and evaluation of high-efficiency, high-capacity sorbent materials capable of selectively sequestering actinides and other radionuclides from complex aqueous mixtures. Self-assembled monolayers on mesoporous supports (SAMMS)...

  7. 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. PMID:26934043

  8. Multicompartment mesoporous silica nanoparticles with branched shapes: an epitaxial growth mechanism.

    PubMed

    Suteewong, Teeraporn; Sai, Hiroaki; Hovden, Robert; Muller, David; Bradbury, Michelle S; Gruner, Sol M; Wiesner, Ulrich

    2013-04-19

    Mesoporous nanomaterials have attracted widespread interest because of their structural versatility for applications including catalysis, separation, and nanomedicine. We report a one-pot synthesis method for a class of mesoporous silica nanoparticles (MSNs) containing both cubic and hexagonally structured compartments within one particle. These multicompartment MSNs (mc-MSNs) consist of a core with cage-like cubic mesoporous morphology and up to four branches with hexagonally packed cylindrical mesopores epitaxially growing out of the cubic core vertices. The extent of cylindrical mesostructure growth can be controlled via a single additive in the synthesis. Results suggest a path toward high levels of architectural complexity in locally amorphous, mesostructured nanoparticles, which could enable tuning of different pore environments of the same particle for specific chemistries in catalysis or drug delivery. PMID:23599490

  9. Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

    NASA Astrophysics Data System (ADS)

    Barry, Louse; Copley, Mark; Holmes, Justin D.; Otway, David J.; Kazakova, Olga; Morris, Michael A.

    2007-12-01

    Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO 2:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.

  10. Development and characterization of spin coated oxide films with mesoporous structure

    NASA Astrophysics Data System (ADS)

    Paik, Jong-Ah

    2003-10-01

    Mesoporous materials offer unique opportunities for applications requiring low density and low thermal conductivity due to high porosity with uniform pore size. The diversity of the sol-gel process to modify the inorganic framework around the pore structure extends the application of mesoporous materials to the fields of sensors and catalysis. This dissertation provides the first report in which mesoporous films were adapted for MEMS applications. Mesoporous SiO2 and Al2O3 films were prepared by spin coating using block copolymers as the structure-directing agents. The resulting films were over 50% porous with uniform pore size of 8 nm average diameter (+/-3 nm) and an extremely smooth surface. The unique mesoporous morphology leads to novel behavior including extremely high etching rates and the ability to etch underlying layers. Surface micromachining methods were used to fabricate such MEMS structures as micro bridges, cantilevers and membranes, from the mesoporous oxides. Research studies on spin-coated silica and hybrid organic-inorganic silica films addressed the question of how mesostructures generated from a block copolymer surfactant were affected by processing conditions. The hybrid system was synthesized using a one-step process in which MTES (methyltriethoxysilane) was combined with TEOS (tetraethylorthosilicate). Two separate ternary phase diagrams, one for the silica system and one for the hybrid system, were established. Both a hexagonal and a cubic pore structure were observed depending on the composition of the coating solutions, and high porosity was measured with films located at the transition region between two pore structures. Another topic investigated in this dissertation is the development of mesoporous materials with a crystallized oxide framework. An approach for synthesizing mesoporous alpha-Al2O3 powder was successfully developed. Mesoporous TiO2 films (anatase phase) were also successfully synthesized and these films show resistance to

  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. Morphology and photocatalysis of mesoporous titania thin films annealed in different atmosphere for degradation of methyl orange

    NASA Astrophysics Data System (ADS)

    Ma, Qing; Qin, Tian Pang; Liu, Shao Jun; Weng, Lv Qian; Dong, Wen Yi

    2011-07-01

    The effect of different annealing atmosphere on the morphology and photocatalytic activity of mesoporous TiO2 thin films by dip-coating technique is investigated. The annealing temperature and atmosphere causes significant change of the morphology, thermal stability, photoluminescence, and photocatalytic properties of mesoporous TiO2 films. As-prepared mesoporous thin films have an amorphous structure that is transformed to crystalline TiO2 with well-maintained mesoporous structure at 450°C in various annealing atmosphere except that the mesoporous structure is fully destroyed for films annealed in air. Films annealed in N2 show the enhanced UV photodegradation of methyl orange (MO) resulting from the enhanced crystallinity in these films evidenced by XRD and Raman spectra. These findings can be used to tailor the structure and morphology of mesoporous TiO2 films and thus improve their photocatalytic activity for efficient removal of dye effluents in wastewater.

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

    PubMed

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

    2015-08-19

    Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed. PMID:26168190

  14. Synthesis and microwave absorbing properties of FeNi alloy incorporated ordered mesoporous carbon-silica nanocomposite

    NASA Astrophysics Data System (ADS)

    Li, Guoxian; Guo, Yunxia; Sun, Xin; Wang, Tao; Zhou, Jianhua; He, Jianping

    2012-11-01

    Ordered mesoporous carbon-silica/FeNi nanocomposite were prepared by a sol-gel method and following sintering process. The electromagnetic parameters were measured in the 0.5-18 GHz range. Compared with ordered mesoporous carbon-silica composite, the permittivity of ordered mesoporous carbon-silica/FeNi nanocomposite decreases, while the permeability almost remains unchanged. The optimal reflection loss of ordered mesoporous carbon-silica/FeNi nanocomposite can reach -45.6 dB at 11.1 GHz for a layer thickness of 3.0 mm. The enhanced microwave absorption of the mesoporous carbon-silica/FeNi nanocomposite is due to better balance between the complex permittivity and permeability, geometrical effect, as well as multiple reflections by the ordered mesoporous structure.

  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. Ordered mesoporous CoMOx (M = Al or Zr) mixed oxides for Fischer-Tropsch synthesis.

    PubMed

    Ahn, Chang-Il; Lee, Yun Jo; Um, Soong Ho; Bae, Jong Wook

    2016-04-01

    A superior structural stability of the ordered mesoporous CoMOx synthesized by using the KIT-6 template was observed under Fischer-Tropsch reaction conditions. The enhanced stability was attributed to a strong interaction of the irreducible metal oxides with the mesoporous Co3O4 by forming Co3O4-ZrO2 (or Co3O4-Al2O3), which resulted in showing a stable activity. PMID:26963504

  17. Synthesis, characterization, and CO(2) adsorptive behavior of mesoporous AlOOH-supported layered hydroxides.

    PubMed

    Chang, Yen-Po; Chen, Yu-Chun; Chang, Po-Hsueh; Chen, San-Yuan

    2012-07-01

    A novel CO(2) solid sorbent was prepared by synthesizing and modifying AlOOH-supported CaAl layered double hydroxides (CaAl LDHs), which were prepared by using mesoporous alumina (γ-Al(2)O(3)) and calcium chloride (CaCl(2)) in a hydrothermal urea reaction. The nanostructured CaAl LDHs with nanosized platelets (3-30 nm) formed and dispersed inside the crystalline framework of mesoporous AlOOH (boehmite). By calcination of AlOOH-supported LDHs at 700 °C, the mesoporous CaAl metal oxides exhibited ordered hexagonal mesoporous arrays or uniform nanotubes with a large surface area of 273 m(2) g(-1) , a narrow pore size distribution of 6.2 nm, and highly crystalline frameworks. The crystal structure of the calcined mesoporous CaAl metal oxides was multiphasic, consisting of CaO/Ca(OH)(2), Al(2)O(3), and CaAlO mixed oxides. The mesoporous metal oxides were used as a solid sorbent for CO(2) adsorption at high temperatures and displayed a maximum CO(2) capture capacity (≈45 wt %) of the sorbent at 650 °C. Furthermore, it was demonstrated that the mesoporous CaAl oxides showed a more rapid adsorption rate (for 1-2 min) and longer cycle life (weight change retention: 80 % for 30 cycles) of the sorbent because of the greater surface area and increased number of activated sites in the mesostructures. A simple model for the formation mechanism of mesoporous metal oxides is tentatively proposed to account for the synergetic effect of CaAl LDHs on the adsorption of CO(2) at high temperature. PMID:22488944

  18. 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.

  19. 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

  20. 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

  1. Controlling stability of gold nanoparticles in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Bore, Mangesh Tukaram

    Metal particles deposited on oxide supports are used extensively as heterogeneous catalysts. By using a suitable combination of active metal phases and supports, the catalysts are designed for high activity, selectivity and mechanical strength. However, catalysts undergo deactivation, with poisoning, fouling, sintering and volatilization being some of the common reasons for loss of catalyst activity. For supported metal catalysts, sintering of metal particles is a major cause of catalyst deactivation. The rate and extent of sintering of supported metals depends upon temperature, atmosphere, support, promoter and metal. It is known that gold nanoparticles show high reactivity for CO oxidation at low temperature, but only when the Au particles are very small (<5 nm). Gold nanoparticles supported on silica show rapid sintering at 200°C--400°C. Porosity of support could play an important role in controlling the sintering of metal particles. But the role of pore size, pore curvature and structure is difficult to study with conventional supported metal catalysts. Surfactant templated mesoporous silica is a promising support material since it provides well defined pores of uniform size and structure. Hence, these silica supports provide ideal model systems for control of nanoparticle sintering. Limitations of mesoporous silica are its low hydrothermal stability at elevated temperatures and its inert nature. The pores of mesoporous silica reportedly collapse at temperatures above 500°C and gold nanoparticles supported on reducible oxides such as TiO2, CO3O4 and Fe2O 3 are more active compared to pure silica for CO oxidation. In this work highly dispersed gold nanoparticles (<2 nm) were prepared within the pores of silica with pore sizes ranging from 2.2 nm to 6.5 nm and differing pore architecture (2D-hexagonal, 3D-hexagonal, cubic and pores coiled-up in spherical geometry). In the 2D-hexagonal pore structure, the pores are one dimensional and terminate on the particle

  2. Application of hierarchical MFI zeolite for the catalytic pyrolysis of Japanese larch.

    PubMed

    Park, Kyu-Hong; Park, Hyun Ju; Kim, Jeongnam; Ryoo, Ryong; Jeon, Jong-Ki; Park, Junhong; Park, Young-Kwon

    2010-01-01

    The catalytic pyrolysis of Japanese larch was carried out over a hierarchical MFI zeolite (Meso MFI C16). The zeolite was synthesized using an amphiphilic organosilane as a mesopore-directing agent, and its catalytic activity was compared with that of the conventional HZSM-5 and the mesoporous material from HZSM-5 (MMZ(ZSM-5)). The effect of the hierarchical MFI zeolite on the product distribution and chemical composition of the bio-oil was also examined. The hierarchical MFI zeolite exhibited the highest activity in deoxygenation and aromatization during the catalytic pyrolysis of Japanese larch. In particular, it showed high selectivity for valuable aromatics, such as benzene, toluene, and xylenes (BTX), even though it decreased the organic fraction of bio-oil. Its higher mesoporosity resulted, however, in an increase in the coke amount and in undesirable products, such as polycyclic aromatic hydrocarbons (PAHs). PMID:20352861

  3. 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

  4. 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.

  5. General and controllable synthesis of novel mesoporous magnetic iron oxide@carbon encapsulates for efficient arsenic removal.

    PubMed

    Wu, Zhangxiong; Li, Wei; Webley, Paul A; Zhao, Dongyuan

    2012-01-24

    A facile ammonia-atmosphere pre-hydrolysis post-synthetic route that can uniformly and selectively deposit Fe(2) O(3) nanoparticles in the predefined mesopores (5.6 nm) of a bimodal (2.3, 5.6 nm) mesoporous carbon matrix is demonstrated. The mesoporous magnetic Fe(2) O(3) @C encapsulates show excellent performance for arsenic capture with remarkable adsorption capacity, fast uptake rate, easy magnetic separation, and good cyclic stability. PMID:22213225

  6. Synthesis, characterization, and application of surface-functionalized ordered mesoporous nanoparticles

    SciTech Connect

    Chung, Po-Wen

    2009-12-15

    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.

  7. Monodisperse spherical mesoporous silica particles: fast synthesis procedure and fabrication of photonic-crystal films

    NASA Astrophysics Data System (ADS)

    Trofimova, E. Yu; Kurdyukov, D. A.; Yakovlev, S. A.; Kirilenko, D. A.; Kukushkina, Yu A.; Nashchekin, A. V.; Sitnikova, A. A.; Yagovkina, M. A.; Golubev, V. G.

    2013-04-01

    A procedure for the synthesis of monodisperse spherical mesoporous silica particles (MSMSPs) via the controlled coagulation of silica/surfactant clusters into spherical aggregates with mean diameters of 250-1500 nm has been developed. The synthesis is fast (taking less than 1 h) because identical clusters are simultaneously formed in the reaction mixture. The results of microscopic, x-ray diffraction, adsorption and optical measurements allowed us to conclude that the clusters are ˜15 nm in size and have hexagonally packed cylindrical pore channels. The channel diameters in MSMSPs obtained with cethyltrimethylammonium bromide and decyltrimethylammonium bromide as structure-directing agents were 3.1 ± 0.15 and 2.3 ± 0.12 nm, respectively. The specific surface area and the pore volume of MSMSP were, depending on synthesis conditions, 480-1095 m2 g-1 and 0.50-0.65 cm3 g-1. The MSMSP were used to grow opal-like photonic-crystal films possessing a hierarchical macro-mesoporous structure, with pores within and between the particles. A selective filling of mesopore channels with glycerol, based on the difference between the capillary pressures in macro- and mesopores, was demonstrated. It is shown that this approach makes it possible to control the photonic bandgap position in mesoporous opal films by varying the degree of mesopore filling with glycerol.

  8. 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.

  9. 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. PMID:25935284

  10. Applications of mesoporous materials as excipients for innovative drug delivery and formulation.

    PubMed

    Shen, Shou-Cang; Ng, Wai Kiong; Chia, Leonard Sze Onn; Dong, Yuan-Cai; Tan, Reginald Beng Hee

    2013-01-01

    Due to uniquely ordered nanoporous structure and high surface area as well as large pore volume, mesoporous materials have exhibited excellent performance in both controlled drug delivery with sustained release profiles and formulation of poorly aqueoussoluble drugs with enhanced bioavailability. Compared with other bulk excipients, mesoporous materials could achieve a higher loading of active ingredients and a tunable drug release profile, as the high surface density of surface hydroxyl groups offered versatility to be functionalized. With drug molecules stored in nano sized channels, the pore openings could be modified using functional polymers or nano-valves performing as stimuli-responsive release devices and the drug release could be triggered by environmental changes or other external effects. In particular, mesoporous silica nanoparticles (MSN) have attracted much attention for application in functional target drug delivery to the cancer cell. The smart nano-vehicles for drug delivery have showed obvious improvements in the therapeutic efficacy for tumor suppression as compared with conventional sustained release systems, although further progress is still needed for eventual clinical applications. Alternatively, unmodified mesoporous silica also exhibited feasible application for direct formulation of poorly water-soluble drugs to enhance dissolution rate, solubility and thus increase the bioavailability after administration. In summary, mesoporous materials offer great versatility that can be used both for on-demand oral and local drug delivery, and scientists are making great efforts to design and fabricate innovative drug delivery systems based on mesoporous drug carriers. PMID:23470004

  11. 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. PMID:26117771

  12. 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

  13. Direct template synthesis of mesoporous carbon and its application to supercapacitor electrodes

    SciTech Connect

    Yoon, Songhun; Oh, Seung M.; Lee, Chulwee

    2009-08-05

    A direct templating method which is facile, inexpensive and suitable for the large scale production of mesoporous carbon is reported herein. A meso-structure surfactant/silicate template was made in a solution phase and resorcinol-formaldehyde as a carbon precursor was incorporated into the template solution. After aging, carbonization and hydrofluoric acid (HF) etching, mesoporous carbon was obtained. Using X-ray diffraction, scanning and transmission electron microscopy and nitrogen sorption, the synthesis mechanism of the mesoporous carbon was elucidated. According to the small angle X-ray scattering measurements, the surface became smoother after the removal of the silica, indicating that the silica was mostly located at the pore surface of the carbon. Also, the calculation of the pore volume demonstrated that the silica was transferred into the pores of the carbon without structural collapse during HF etching. When the prepared mesoporous carbon was applied to a supercapacitor electrode, the rectangular shape of the cyclic voltammogram was less collapsed, even at a high scan rate, which is indicative of its high rate capability. This was due to the low resistance of the electrolyte in the pores (3.8 {Omega} cm{sup 2}), which was smaller than that of conventional activated carbon electrodes and even comparable to that of ordered mesoporous carbon electrodes. This improved performance was probably due to the well developed mesoporosity and high pore connectivity of the prepared mesoporous carbon.

  14. 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

  15. Selenium@mesoporous carbon composite with superior lithium and sodium storage capacity.

    PubMed

    Luo, Chao; Xu, Yunhua; Zhu, Yujie; Liu, Yihang; Zheng, Shiyou; Liu, Ying; Langrock, Alex; Wang, Chunsheng

    2013-09-24

    Selenium-impregnated carbon composites were synthesized by infusing Se into mesoporous carbon at a temperature of 600 °C under vacuum. Ring-structured Se8 was produced and confined in the mesoporous carbon, which acts as an electronic conductive matrix. During the electrochemical process in low-cost LiPF6/EC/DEC electrolyte, low-order polyselenide intermediates formed and were stabilized by mesoporous carbon, which avoided the shuttle reaction of polyselenides. Exceptional electrochemical performance of Se/mesoporous carbon composites was demonstrated in both Li-ion and Na-ion batteries. In lithium-ion batteries, Se8/mesoporous carbon composite cathodes delivered a reversible capacity of 480 mAh g(-1) for 1000 charge/discharge cycles without any capacity loss, while in Na-ion batteries, it provided initial capacity of 485 mAh g(-1) and retained 340 mAh g(-1) after 380 cycles. The Se8/mesoporous carbon composites also showed excellent rate capability. As the current density increased from 0.1 to 5 C, the capacity retained about 46% in Li-ion batteries and 34% in Na-ion batteries. PMID:23944942

  16. 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.

  17. Impact of nanopore morphology on cell viability on mesoporous polymer and carbon surfaces.

    PubMed

    Chavez, Vicki L; Song, Lingyan; Barua, Sutapa; Li, Xinxin; Wu, Quanyan; Zhao, Dongyuan; Rege, Kaushal; Vogt, Bryan D

    2010-08-01

    Topography at the nanoscale can lead to dramatic changes in the adhesion of cells to surfaces and their subsequent viability. For biological applications, including tissue engineering and cell-based sensing, the large internal surface area of ordered mesoporous carbons provides an opportunity for enhanced sensitivity and performance, but the mesostructure also affects the topography of the material. In this work, we probe the viability and adhesion of osteoblasts on ordered mesoporous materials with different morphologies and matrix chemistries. FDU-15 (hexagonal) and FDU-16 (cubic) films were processed at either 350 degrees C (polymeric) or 800 degrees C (carbon) to provide these different materials. For the films processed at 350 degrees C, the cell adhesion was markedly improved on the mesoporous films in comparison to a dense film analog, consistent with many reports in the literature that nanostructuring of surfaces improves the viability and adhesion of osteoblasts. Conversely, osteoblast adhesion was reduced on the carbonized surfaces processed at 800 degrees C when ordered mesopores were introduced, particularly for the cubic mesostructure (FDU-16). We attribute the decrease in cell adhesion to the propensity of the ordered mesoporous carbon films to sorb organics from aqueous solution, which could lead to removal of adhesion-promoting compounds at the film surface. These results suggest that cell viability on mesoporous polymer and carbon films can be controlled through simple changes in the pyrolysis temperature. PMID:20144750

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. Mesoporous-Silica-Functionalized Nanoparticles for Drug Delivery.

    PubMed

    Giret, Simon; Wong Chi Man, Michel; Carcel, Carole

    2015-09-28

    The ever-growing interest for finding efficient and reliable methods for treatment of diseases has set a precedent for the design and synthesis of new functional hybrid materials, namely porous nanoparticles, for controlled drug delivery. Mesoporous silica nanoparticles (MSNPs) represent one of the most promising nanocarriers for drug delivery as they possess interesting chemical and physical properties, thermal and mechanical stabilities, and are biocompatibile. In particular, their easily functionalizable surface allows a large number of property modifications further improving their efficiency in this field. This Concept article deals with the advances on the novel methods of functionalizing MSNPs, inside or outside the pores, as well as within the walls, to produce efficient and smart drug carriers for therapy. PMID:26250991

  3. Improved gene transfer with histidine-functionalized mesoporous silica nanoparticles.

    PubMed

    Brevet, David; Hocine, Ouahiba; Delalande, Anthony; Raehm, Laurence; Charnay, Clarence; Midoux, Patrick; Durand, Jean-Olivier; Pichon, Chantal

    2014-08-25

    Mesoporous silica nanoparticles (MSN) were functionalized with aminopropyltriethoxysilane (MSN-NH2) then L-histidine (MSN-His) for pDNA delivery in cells and in vivo. The complexation of pDNA with MSN-NH2 and MSN-His was first studied with gel shift assay. pDNA complexed with MSN-His was better protected from DNase degradation than with MSN-NH2. An improvement of the transfection efficiency in cells was observed with MSN-His/pDNA compared to MSN-NH2/pDNA, which could be explained by a better internalization of MSN-His. The improvement of the transfection efficiency with MSN-His was also observed for gene transfer in Achilles tendons in vivo. PMID:24853464

  4. Silicalites and Mesoporous Silica Nanoparticles for photodynamic therapy.

    PubMed

    Hocine, Ouahiba; Gary-Bobo, Magali; Brevet, David; Maynadier, Marie; Fontanel, Simon; Raehm, Laurence; Richeter, Sébastien; Loock, Bernard; Couleaud, Pierre; Frochot, Céline; Charnay, Clarence; Derrien, Gaëlle; Smaïhi, Monique; Sahmoune, Amar; Morère, Alain; Maillard, Philippe; Garcia, Marcel; Durand, Jean-Olivier

    2010-12-15

    The synthesis of silicalites and Mesoporous Silica Nanoparticles (MSN), which covalently incorporate original water-soluble photosensitizers for PDT applications is described. PDT was performed on MDA-MB-231 breast cancer cells. All the nanoparticles showed significant cell death after irradiation, which was not correlated with (1)O(2) quantum yield of the nanoparticles. Other parameters are involved and in particular the surface and shape of the nanoparticles which influence the pathway of endocytosis. Functionalization with mannose was necessary to obtain the best results with PDT due to an active endocytosis of mannose-functionalized nanoparticles. The quantity of mannose on the surface should be carefully adjusted as a too high amount of mannose impairs the phototoxicity of the nanoparticles. Fluorescein was also encapsulated in MCM-41 type MSN in order to localize the nanoparticles in the organelles of the cells by confocal microscopy. The MSN were localized in lysosomes after active endocytosis by mannose receptors. PMID:20934496

  5. 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

  6. 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

  7. N-heptane adsorption and desorption in mesoporous materials

    NASA Astrophysics Data System (ADS)

    Zaleski, R.; Gorgol, M.; Błazewicz, A.; Kierys, A.; Goworek, J.

    2015-06-01

    Positron Annihilation Lifetime Spectroscopy (PALS) was used for an in situ monitoring of adsorption and desorption processes. The disordered and ordered porous silica as well as the porous polymer were used as adsorbents, while an adsorbate in all the cases was n-heptane. The lifetimes and particularly the intensities of the ortho-positronium(o-Ps) components depend strongly on the adsorbate pressure. The analysis of these dependencies allows us to identify several processes, which are taking place during sorption. At low pressure, an island-like growth of the first layers of the adsorbate on the silica, in a contrary to a swelling of the polymer, is observed. A size of the pores, which remain empty, is estimated at the subsequent stages of the adsorbate condensation and evaporation. The adsorbate thrusting into micropores is deduced at p/p0 > 0.6 whilst the mesopores are still not completely filled.

  8. 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.

  9. Fabrication of mesoporous cerium dioxide films by cathodic electrodeposition.

    PubMed

    Kim, Young-Soo; Lee, Jin-Kyu; Ahn, Jae-Hoon; Park, Eun-Kyung; Kim, Gil-Pyo; Baeck, Sung-Hyeon

    2007-11-01

    Mesoporous cerium dioxide (Ceria, CeO2) thin films have been successfully electrodeposited onto ITO-coated glass substrates from an aqueous solution of cerium nitrate using CTAB (Cetyltrimethylammonium Bromide) as a templating agent. The synthesized films underwent detailed characterizations. The crystallinity of synthesized CeO2 film was confirmed by XRD analysis and HR-TEM analysis, and surface morphology was investigated by SEM analysis. The presence of mesoporosity in fabricated films was confirmed by TEM and small angle X-ray analysis. As-synthesized film was observed from XRD analysis and HR-TEM image to have well-crystallized structure of cubic phase CeO2. Transmission electron microscopy and small angle X-ray analysis revealed the presence of uniform mesoporosity with a well-ordered lamellar phase in the CeO2 films electrodeposited with CTAB templating. PMID:18047150

  10. Hydrothermal Synthesis of Meso-porous Materials using Diatomaceous Earth

    NASA Astrophysics Data System (ADS)

    Jing, Z.; Kato, S.; Maeda, H.; Ishida, E. H.

    2007-03-01

    In order to sustain the inherent properties of diatomaceous earth (DE), a low-temperature synthesis of mesoporous material from DE was carried out using a hydrothermal processing technique under saturated steam pressure at 200 °C for 12 h. The experimental results showed that the most important strength-producing constituent in the solidified specimens was tobermorite formed by hydrothermal processing, and the addition of slaked lime was favorable to tobermorite formation. At Ca/Si ratio around 0.83 in the starting material, tobermorite appeared to form readily. A high autoclave curing temperature (200 °C), or a longer curing time (12 h) seemed to accelerate the tobermorite formation, thus leading to a higher strength development.

  11. Mesoporous silica nanoparticles in tissue engineering--a perspective.

    PubMed

    Rosenholm, Jessica Maria; Zhang, Jixi; Linden, Mika; Sahlgren, Cecilia

    2016-02-01

    In this review, we summarize the latest developments and give a perspective on future applications of mesoporous silica nanoparticles (MSNs) in regenerative medicine. MSNs constitute a flexible platform for controlled delivery of drugs and imaging agents in tissue engineering and stem cell therapy. We highlight the recent advances in applying MSNs for controlled drug delivery and stem cell tracking. We touch upon novel functions of MSNs in real time imaging of drug release and biological function, and as tools to control the chemical and mechanical environment of stem cells. We discuss the need for novel model systems for studying biofunctionality and biocompatibility of MSNs, and how the interdisciplinary activities within the field will advance biotechnology research. PMID:26784861

  12. 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

  13. 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.

  14. 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

  15. 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

  16. Functionalized mesoporous silica nanoparticles for oral delivery of budesonide

    NASA Astrophysics Data System (ADS)

    Yoncheva, K.; Popova, M.; Szegedi, A.; Mihaly, J.; Tzankov, B.; Lambov, N.; Konstantinov, S.; Tzankova, V.; Pessina, F.; Valoti, M.

    2014-03-01

    Non-functionalized and amino-functionalized mesoporous silica nanoparticle were loaded with anti-inflammatory drug budesonide and additionally post-coated with bioadhesive polymer (carbopol). TEM images showed spherical shape of the nanoparticles and slightly higher polydispersity after coating with carbopol. Nitrogen physisorption and thermogravimetic analysis revealed that more efficient loading and incorporation into the pores of nanoparticles was achieved with the amino-functionalized silica carrier. Infrared spectra indicated that the post-coating of these nanoparticles with carbopol led to the formation of bond between amino groups of the functionalized carrier and carboxyl groups of carbopol. The combination of amino-functionalization of the carrier with the post-coating of the nanoparticles sustained budesonide release. Further, an in vitro model of inflammatory bowel disease showed that the cytoprotective effect of budesonide loaded in the post-coated silica nanoparticles on damaged HT-29 cells was more pronounced compared to the cytoprotection obtained with pure budesonide.

  17. 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

  18. Mesoporous silica nanoparticles deliver DNA and chemicals into plants

    NASA Astrophysics Data System (ADS)

    Torney, François; Trewyn, Brian G.; Lin, Victor S.-Y.; Wang, Kan

    2007-05-01

    Surface-functionalized silica nanoparticles can deliver DNA and drugs into animal cells and tissues. However, their use in plants is limited by the cell wall present in plant cells. Here we show a honeycomb mesoporous silica nanoparticle (MSN) system with 3-nm pores that can transport DNA and chemicals into isolated plant cells and intact leaves. We loaded the MSN with the gene and its chemical inducer and capped the ends with gold nanoparticles to keep the molecules from leaching out. Uncapping the gold nanoparticles released the chemicals and triggered gene expression in the plants under controlled-release conditions. Further developments such as pore enlargement and multifunctionalization of these MSNs may offer new possibilities in target-specific delivery of proteins, nucleotides and chemicals in plant biotechnology.

  19. Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures.

    PubMed

    Bracco, Silvia; Beretta, Mario; Cattaneo, Alice; Comotti, Angiolina; Falqui, Andrea; Zhao, Ke; Rogers, Charles; Sozzani, Piero

    2015-04-13

    New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p-divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 10(8) Hz at 325 K), as detected by solid-state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I2 vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl-fluoro-phenylene rotors, affecting their motion and the dielectric properties. PMID:25689486

  20. White light emitting Mesoporous Carbon-Silica Nanocomposite

    NASA Astrophysics Data System (ADS)

    Matsumura, Akihiro; Ishii, Yosuke; Sato, Koji; Ishikawa, Yukari; Kawasaki, Shinji

    2011-05-01

    Visible photoluminescence (PL) from oxidized mesoporous carbon-silica nanocomposite (MPCS) prepared by the triconstituent co-assembly method is reported. White PL from MPCS was observed by naked eye at room temperature. Oxidation effects on carbon-silica bonding states and transmittance were investigated. PL intensity decreased with decreasing of carbon dangling bond density by oxidation at above 500 °C. The transmittance of MPCS at excitation and emission wavelengths increased with increasing of oxidation temperature. It is concluded that PL intensity is determined by the balance between PL related carbon density and transmittance. We proposed an additional wet oxidation that can increase PL intensity by the increase of transmittance under suppressing carbon desorption.

  1. 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

  2. Synthesis of mesoporous zirconia using an amphoteric surfactant

    SciTech Connect

    Kim, A.Y.; Bruinsma, P.J.; Chen, Y.L.; Liu, J.

    1996-12-31

    An amphoteric surfactant, cocamidopropyl betaine, was used for the synthesis of mesoporous zirconia. The carboxylate functionality of the surfactant permitted strong bonding with soluble zirconium species, while the quaternary ammonium group ensured large headgroup area and high solubility under acidic conditions. An amphoteric co-template [betaine, or (carboxymethyl)trimethylammonium hydroxide] improved uniformity of the hexagonal mesophase. Transmission electron microscopy (TEM) of the as-synthesized zirconium sulfate mesophase indicated hexagonal mesostructure, and low-angle X-ray diffraction (XRD) showed a 41 {angstrom} primary d-spacing and two higher order reflections of a hexagonal lattice. High surface area zirconia was produced by controlled base treatment of the hexagonal mesophase with sodium hydroxide, followed by calcination. TEM and XRD indicated that the mesostructure was stable to 350 C.

  3. 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

  4. An ordered mesoporous Ag superstructure synthesized via a template strategy for surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Tian, Cuifeng; Li, Jiang; Ma, Chunsheng; Wang, Ping; Sun, Xiaohong; Fang, Jixiang

    2015-07-01

    Surface-enhanced Raman scattering (SERS) substrates with high density and uniformity of nanogaps are proven to enhance the reproducibility and sensitivity of the Raman signal. Up to now, the syntheses of a highly ordered gold or silver superstructure with a controllable nanoparticle size and a well-defined particle gap have been quite limited. Here, we reported an ordered mesoporous silver superstructure replicated by using ordered mesoporous KIT-6 and SAB-15 as templates. By means of a nanocasting process, the ordered mesoporous Ag superstructure was successfully synthesized, which shows uniform distribution of the nanowire diameter (10 nm) and nanogap size (~2 nm), thus exhibiting a high Raman enhancement of ~109. The finite difference time-domain (FDTD) results indicate that the ordered mesoporous Ag superstructure has a uniform distribution of hot spots. Therefore, the mesoporous silica template strategy presented here could lead to a new class of high quality SERS substrates providing extraordinary potential for diverse applications.Surface-enhanced Raman scattering (SERS) substrates with high density and uniformity of nanogaps are proven to enhance the reproducibility and sensitivity of the Raman signal. Up to now, the syntheses of a highly ordered gold or silver superstructure with a controllable nanoparticle size and a well-defined particle gap have been quite limited. Here, we reported an ordered mesoporous silver superstructure replicated by using ordered mesoporous KIT-6 and SAB-15 as templates. By means of a nanocasting process, the ordered mesoporous Ag superstructure was successfully synthesized, which shows uniform distribution of the nanowire diameter (10 nm) and nanogap size (~2 nm), thus exhibiting a high Raman enhancement of ~109. The finite difference time-domain (FDTD) results indicate that the ordered mesoporous Ag superstructure has a uniform distribution of hot spots. Therefore, the mesoporous silica template strategy presented here could

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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

  10. 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(+). PMID:25019261

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

    PubMed

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

    2012-03-21

    Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors. PMID:22352760

  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. Preparation, Characterization and Photocatalytic Activity of Lanthanum Doped Mesoporous Titanium Dioxide

    NASA Astrophysics Data System (ADS)

    Shi, Zhong-liang; Lai, Hong; Yao, Shu-hua; Wang, Shao-feng

    2012-02-01

    Lanthanum doped mesoporous titanium dioxide photocatalysts with different La content were synthesized by template method using tetrabutyltitanate (Ti(OC4H9)4) as precursor and Pluronic P123 as template. The catalysts were characterized by thermogravimetric differential thermal analysis, N2 adsorption-desorption measurements, X-ray diffraction, and UV-Vis adsorption spectroscopy. The effect of La3+ doping concentration from 0.1% to 1% on the photocatalytic activity of mesoporous TiO2 was investigated. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of about 10 nm with high surface area of 165 m2/g. X-ray photoelectron spectroscopy measurements indicated the presence of C in the doped samples in addition to La. Compared with pure mesoporous TiO2, the La-doped samples extended the photoabsorption edge into the visible light region. The results of phenol photodecomposition showed that La-doped mesoporous TiO2 exhibited higher photocatalytic activities than pure mesoporous TiO2 under UV and visible light irradiation.

  15. 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

  16. 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

  17. Photon-Manipulated Drug Release from Mesoporous Nanocontainer Controlled by Azobenzene-Modified Nucleic Acid

    PubMed Central

    Yuan, Quan; Zhang, Yunfei; Chen, Tao; Lu, Danqing; Zhao, Zilong; Zhang, Xiaobing; Li, Zhenxing; Yan, Chun-Hua; Tan, Weihong

    2012-01-01

    Herein a photon manipulated mesoporous release system was constructed based on azobenzene-modified nucleic acids. In this system, the azobenzene-incorporated DNA double strands were immobilized at the pore mouth of meso-porous silica nanoparticles. The photo-isomerization of azobenzene induced dehybridization/hybridization switch of complementary DNA, causing uncapping/capping of pore gates of mesoporous silica. This nanoplatform permits holding of guest molecules within the nanopores under visible light but release them when light wavelength turns to UV range. These DNA/mesoporous silica hybrid nanostructures were exploited as carriers for cancer cell chemotherapy drug doxorubicin (DOX) due to its stimuli-responsive property as well as good biocompatibility via MTT assay. It is found that the drug release behavior is light wavelength sensitive. Switching of the light from visible to UV range uncapped the pores causes the release of DOX from the mesoporous silica nanospheres and an obvious cytotoxic effect on cancer cells. We envision that this photo-controlled drug release system could find potential applications in cancer therapy. PMID:22670595

  18. 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

  19. 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. PMID:26134074

  20. 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

  1. Magnetic Fluorescent Delivery Vehicle using Uniform Mesoporous Silica Spheres Embedded with Monodisperse Magnetic and Semiconductor Nanocrystals

    SciTech Connect

    Kim, Jaeyun; Lee, Ji Eun; Lee, Jinwoo; Yu, Jung Ho; Kim, Byoung Chan; An, Kwangjin; Hwang, Yosun; Shin, Chae-Ho; Park, Je-Geun; Kim, Jungbae; Hyeon, Taeghwan

    2006-01-25

    Uniform sized colloidal nanocrystals have attracted much attention, because of their unique magnetic and optical properties, as compared with those of their bulk counterparts. Especially magnetic nanocrystals and quantum dots have been intensively pursued for biomedical applications such as contrast enhancement agents in magnetic resonance imaging, magnetic carriers for drug delivery system, biological labeling and diagnostics. Due to their large pore sizes and high surface areas, mesoporous materials and its composites with nanocrystals have attracted considerable attention. In order to use the nanocrystals as functional delivery carriers and catalytic supports, nanocrystals coated with porous silica shells are desirable. Herein, we report a synthetic procedure for the fabrication of monodisperse nanocrystals embedded in uniform pore-sized mesoporous silica spheres. As a representative example, we synthesized monodisperse magnetite (Fe3O4) nanocrystals embedded in mesoporous silica spheres and both magnetite nanocrystals and CdSe/ZnS quantum dots embedded in mesoporous silica spheres. Furthermore, these mesoporous silica spheres were applied to the uptake and controlled release of drugs.

  2. Sustainable mesoporous carbons as storage and controlled-delivery media for functional molecules.

    PubMed

    Saha, Dipendu; Payzant, E Andrew; Kumbhar, Amar S; Naskar, Amit K

    2013-06-26

    Here, we report the synthesis of surfactant-templated mesoporous carbons from lignin, which is a biomass-derived polymeric precursor, and their potential use as a controlled-release medium for functional molecules such as pharmaceuticals. To the best of our knowledge, this is the first report on the use of lignin for chemical-activation-free synthesis of functional mesoporous carbon. The synthesized carbons possess the pore widths within the range of 2.5-12.0 nm. In this series of mesoporous carbons, our best result demonstrates a Brunauer-Emmett-Teller (BET) surface area of 418 m(2)/g and a mesopore volume of 0.34 cm(3)/g, which is twice the micropore volume in this carbon. Because of the dominant mesoporosity, this engineered carbon demonstrates adsorption and controlled release of a representative pharmaceutical drug, captopril, in simulated gastric fluid. Large-scale utilization of these sustainable mesoporous carbons in applications involving adsorption, transport, and controlled release of functional molecules is desired for industrial processes that yield lignin as a coproduct. PMID:23731336

  3. Mesoporous hybrid NiOx-MnOx nanoprisms for flexible solid-state asymmetric supercapacitors.

    PubMed

    Wei, Chengzhen; Cheng, Cheng; Ma, Lan; Liu, Mengna; Kong, Dechen; Du, Weimin; Pang, Huan

    2016-06-28

    Mesoporous hybrid NiOx-MnOx nanoprisms have been successfully prepared in this work. The synthesis process involves a facile solvothermal method for preparation of Ni-Mn precursor particles and a subsequent annealing treatment. These mesoporous hybrid NiOx-MnOx nanoprisms have a high surface area of 101.6 m(2) g(-1). When evaluated as electrode materials in supercapacitors, the as-prepared mesoporous hybrid NiOx-MnOx nanoprisms deliver a specific capacitance of 1218 F g(-1) at a current density of 2.0 A g(-1). More importantly, the mesoporous hybrid NiOx-MnOx nanoprisms were successfully used to construct flexible solid-state asymmetric supercapacitors. The device shows a specific capacitance of 149.1 mF cm(-2) at 2.0 mA cm(-2), a good cycling stability with only 2.9% loss of capacitance after 5000 charge-discharge cycles, and good mechanical flexibility under different bending angles. These results support the promising application of mesoporous hybrid NiOx-MnOx nanoprisms as advanced supercapacitor materials. PMID:27295406

  4. 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. PMID:26936391

  5. 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.

  6. A hydrothermal synthesis of Pr3+ doped mesoporous TiO2 for UV light photocatalysis.

    PubMed

    Wang, Yong; Chen, Guihua; Shen, Qianhong; Yang, Hui; Li, Liquan; Song, Yanjiang

    2014-07-01

    Pr3+ doped mesoporous TiO2 photocatalysts with a different molar ratio of Pr to Ti were prepared by a hydrothermal method using triblock copolymer as the template. The as-prepared samples were systematically characterized by X-ray diffraction, N2 adsorption-desorption, X-ray photoelectron spectra, transmission electron microscopy and UV-visible diffuse reflectance spectroscopy. The characterizations indicated all the samples had mesoporous structure and narrow pore size distribution. Pr3+ doping enlarged the surface area and decreased the crystallite size. The surface area of the samples varied from 136 to 170 m2/g, and the average crystallite size ranged between 5.04 and 7.60 nm. The effect of Pr3+ doping amount on the photocatalytic activity of mesoporous TiO2 was evaluated by the degradation of methyl orange under UV light irradiation. The results showed that the suitable amount of Pr3+ doped samples exhibited the higher photocatalytic activity than mesoporous TiO2. Among the samples, 1 at.% Pr3+ doped mesoporous TiO2 showed the highest photocatalytic activity. PMID:24757971

  7. 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

  8. Synthesis of ZSM-5 with intracrystal or intercrystal mesopores by polyvinyl butyral templating method.

    PubMed

    Zhu, Haibo; Liu, Zhicheng; Kong, Dejin; Wang, Yangdong; Yuan, Xiaohong; Xie, Zaiku

    2009-03-15

    Three facile routes were utilized to synthesize ZSM-5 materials with intracrystal or intercrystal mesopores, where the polyvinyl butyral gel served as mesopore directing template. The three routes were divided into two synthesis strategies: the hydrothermal treatment of silica/PVB composite and re-crystallization of preformed zeolite precursor with the assistance of PVB gel. The fabrication of silica/PVB composite was accomplished by two routes including sol-gel process and impregnation method. The resulting composite was undergone hydrothermal treatment. During the crystallization PVB was occluded in the ZSM-5 crystal, creating intracrystal mesopores in the zeolite. The last route for the synthesis of mesoporous ZSM-5 was realized by re-crystallization of preformed ZSM-5 zeolite in the presence of PVB. This route involved the pre-crystallization of the amorphous aluminosilicate to produce the pre-formed ZSM-5 precursor. Upon further crystallization of the mixture of PVB gel and pre-formed ZSM-5, the ZSM-5 precursor was transformed into ZSM-5 aggregate of nanocrystals, while the PVB gel was occluded in the ZSM-5 particles. Removal of the template generated the typical microporosity associated with ZSM-5 structure along with intercrystal mesoporosity produced from the PVB. The mesoporous ZSM-5 exhibited enhanced catalytic activity in the toluene disproportionation and transalkylation with C(9) and C(10) aromatics. PMID:19101681

  9. Curcumin loaded mesoporous silica: an effective drug delivery system for cancer treatment.

    PubMed

    Kotcherlakota, Rajesh; Barui, Ayan Kumar; Prashar, Sanjiv; Fajardo, Mariano; Briones, David; Rodríguez-Diéguez, Antonio; Patra, Chitta Ranjan; Gómez-Ruiz, Santiago

    2016-03-01

    In the present study, we report the delivery of anti-cancer drug curcumin to cancer cells using mesoporous silica materials. A series of mesoporous silica material based drug delivery systems (S2, S4 and S6) were first designed and developed through the amine functionalization of KIT-6, MSU-2 and MCM-41 followed by the loading of curcumin. The curcumin loaded materials were characterized with several physico-chemical techniques and thoroughly screened on cancer cells to evaluate their in vitro drug delivery efficacy. All the curcumin loaded silica materials exhibited higher cellular uptake and inhibition of cancer cell viability compared to pristine curcumin. The effective internalization of curcumin in cancer cells through the mesoporous silica materials initiated the generation of intracellular reactive oxygen species and the down regulation of poly ADP ribose polymerase (PARP) enzyme levels compared to free curcumin leading to the activation of apoptosis. This study shows that the anti-cancer activity of curcumin can be potentiated by loading onto mesoporous silica materials. Therefore, we strongly believe that mesoporous silica based curcumin loaded drug delivery systems may have future potential applications for the treatment of cancers. PMID:26674254

  10. Preparation, characterization and oxygen sensing properties of luminescent carbon dots assembled mesoporous silica microspheres.

    PubMed

    Wang, Li; Zhang, Haoran; Zhou, Xiaohua; Liu, Yingliang; Lei, Bingfu

    2016-09-15

    In this paper, our effort was focused on preparation and oxygen sensing of luminescence carbon dots (CDs) assembled hollow mesoporous silica microspheres (HMSMs) and mesoporous silica microspheres (MSMs). MSMs doped with CDs showed shorter response time and recovery time comparing with HMSMs doped with CDs. This feature can be attributed to ordered channel structure of mesoporous carrier which can promote the gas diffusion effectively. While HMSMs doped with CDs shows a higher oxygen quenching response and the degree of quenching reach 80.35%. The response time was determined to be about 7s and the emission intensities of the samples were effectively reduced as the concentration of oxygen increased. These results indicate that the system we have developed can be used for oxygen detection in wide concentration range and is especially accurate for very low oxygen concentrations. The obtained CDs grafted hollow mesoporous silica microspheres (HMSMs) and mesoporous silica microspheres (MSMs) samples appears to be a promising sensing material for environmental detection application and would also find applications in catalyst, electrode, or related fields. PMID:27309945

  11. 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

  12. Hierarchical porous silicon carbide with controlled micropores and mesopores for electric double layer capacitors

    NASA Astrophysics Data System (ADS)

    Kim, Myeongjin; Oh, Ilgeun; Kim, Jooheon

    2015-05-01

    Three-dimensional hierarchical micro and mesoporous silicon carbide spheres (MMPSiC) are prepared by the template method and carbonization reaction via the aerosol spray drying method. The mesopores are generated by the self-assembly of the structure-directing agents, whereas the micropores are derived from the partial evaporation of Si atoms during carbonization. To investigate the effect of mesopore size on electrochemical performance, three types of MMPSiC with different mesopore size were fabricated by using three different structure directing agents (cetyltriethylammonium bromide (CTAB), Polyethylene glycol hexadecyl ether (Brij56), and Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123)). The MMPSiC electrode prepared with Brij56 exhibits the highest charge storage capacity with a specific capacitance of 253.7 F g-1 at a scan rate of 5 mV s-1 and 87.9% rate performance from 5 to 500 mV s-1 in 1 M Na2SO4 aqueous electrolyte. The outstanding electrochemical performance might be because of the ideal mesopore size, which effectively reduces the resistant pathways for ion diffusion in the pores and provides a large accessible surface area for ion transport/charge storage. These encouraging results demonstrate that the MMPSiC prepared with Brij56 is a promising candidate for high performance electrode materials for supercapacitors.

  13. 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

  14. High-activity mesoporous Pt/Ru catalysts for methanol oxidation.

    PubMed

    Franceschini, Esteban A; Bruno, Mariano M; Williams, Federico J; Viva, Federico A; Corti, Horacio R

    2013-11-13

    High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores. PMID:24083938

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

    SciTech Connect

    Wang Jun; Zhou Jideng; Li Zhanshuang; He Yang; Lin Shuangshuang; Liu Qi; Zhang Milin; Jiang Zhaohua

    2010-11-15

    We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs having different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted

  16. Development of novel mesoporous silicates for bioseparations and biocatalysis

    NASA Astrophysics Data System (ADS)

    Katiyar, Amit

    The recent growth of the biopharmaceutical industry is due to the discovery of monoclonal antibodies and recombinant DNA technologies. Large-scale production of therapeutic proteins and monoclonal antibodies requires efficient technologies to separate products from complex synthesis mixtures. Chromatography is widely used for this purpose at both the analytical and process scales. Research in the last three decades has provided an improved understanding of the thermodynamic and mass transfer effects underlying the chromatographic behavior of biomolecules, leading to improvements in chromatographic equipment, separation media, and operating procedures. This dissertation reports on the development of ordered mesoporous silica-based adsorbents for chromatographic protein separations. The synthesis of mesoporous materials with different structural properties is reported here. Protein adsorption and enzymatic catalysis studies were conducted to evaluate the chromatographic performance of these materials. Initial studies focused on small pore materials (MCM-41), which had high protein adsorption capacities. These high protein loadings were attributed to high external surface area (˜600 m 2/g), meaning that MCM-41 materials are of limited use for size-selective chromatographic protein separation. Synthesis strategies were developed to produce large pore fibrous and spherical SBA-15 particles. The effects of synthesis conditions on particle properties are presented. Large pore Spherical ordered SBA-15 materials were used to demonstrate for the first time the size-selective separation of proteins. BSA and lysozyme were tagged with fluorescent molecules, allowing direct visualization of the size selective separation of these proteins. Flow microcalorimetry (FMC) results were used to interpret the size-selective behavior of these materials. The potential of siliceous SBA-15 materials to serve as hosts for enzymes in biocatalytic transformations was also explored. Materials

  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. Highly ordered periodic mesoporous organosilica nanoparticles with controllable pore structures

    NASA Astrophysics Data System (ADS)

    Guan, Buyuan; Cui, Yan; Ren, Zhongyuan; Qiao, Zhen-An; Wang, Li; Liu, Yunling; Huo, Qisheng

    2012-09-01

    A general synthetic procedure for highly ordered and well-dispersed periodic mesoporous organosilica (PMO) nanoparticles is reported based on a single cationic surfactant cetyltrimethylammonium bromide (CTAB) and simple silica sources with organic bridging groups via an ammonia-catalyzed sol-gel reaction. By changing the bridging group in the silica sources, the pore structures of the as-made particles with three-dimensional hexagonal (P63/mmc), cubic (Pm3n), two-dimensional hexagonal (P6mm), and wormlike structure were evidenced by powder X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The size range of the nanoparticles can be adjusted from 30 nm to 500 nm by variation of the ammonia concentration or the co-solvent content of the reaction medium. The PMO nanoparticles with high concentration of organic groups in the framework offered good thermal stability, good dispersion in low polarity solvent and high adsorption of small hydrophobic molecules. Finally, the dye functionalized PMO nanoparticles show low cytotoxicity and excellent cell permeability, which offers great potential for biomedical applications.A general synthetic procedure for highly ordered and well-dispersed periodic mesoporous organosilica (PMO) nanoparticles is reported based on a single cationic surfactant cetyltrimethylammonium bromide (CTAB) and simple silica sources with organic bridging groups via an ammonia-catalyzed sol-gel reaction. By changing the bridging group in the silica sources, the pore structures of the as-made particles with three-dimensional hexagonal (P63/mmc), cubic (Pm3n), two-dimensional hexagonal (P6mm), and wormlike structure were evidenced by powder X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The size range of the nanoparticles can be adjusted from 30 nm to 500 nm by variation of the ammonia concentration or the co-solvent content of the reaction medium. The PMO nanoparticles with high concentration of organic

  19. 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

  20. 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.

  1. Mesoporous silica nanoparticles with organo-bridged silsesquioxane framework as innovative platforms for bioimaging and therapeutic agent delivery.

    PubMed

    Du, Xin; Li, Xiaoyu; Xiong, Lin; Zhang, Xueji; Kleitz, Freddy; Qiao, Shi Zhang

    2016-06-01

    Mesoporous silica material with organo-bridged silsesquioxane frameworks is a kind of synergistic combination of inorganic silica, mesopores and organics, resulting in some novel or enhanced physicochemical and biocompatible properties compared with conventional mesoporous silica materials with pure Si-O composition. With the rapid development of nanotechnology, monodispersed nanoscale periodic mesoporous organosilica nanoparticles (PMO NPs) and organo-bridged mesoporous silica nanoparticles (MSNs) with various organic groups and structures have recently been synthesized from 100%, or less, bridged organosilica precursors, respectively. Since then, these materials have been employed as carrier platforms to construct bioimaging and/or therapeutic agent delivery nanosystems for nano-biomedical application, and they demonstrate some unique and/or enhanced properties and performances. This review article provides a comprehensive overview of the controlled synthesis of PMO NPs and organo-bridged MSNs, physicochemical and biocompatible properties, and their nano-biomedical application as bioimaging agent and/or therapeutic agent delivery system. PMID:27017579

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. "Host-guest" chemistry in the synthesis of ordered nonsiliceous mesoporous materials.

    PubMed

    Wan, Ying; Yang, Haifeng; Zhao, Dongyuan

    2006-07-01

    On the basis of the consideration of "host-guest" chemistry, the interactions between guest molecules are highlighted in the synthesis of nonsiliceous mesoporous materials by the "soft-template" and "hard-template" approaches. A generalized "acid-base pair" concept is utilized in selecting appropriate guest molecules to prepare highly ordered mesoporous metal oxides, phosphates, and borates with diversified structures. Mesoscopically ordered polymer and carbon frameworks with uniformly large pore sizes are derived from the self-assembly of an organic surfactant with an organic guest. Properly building the guest unit and decorating the host are important in replicating ordered nonsiliceous single-crystal nanoarrays. Outlooks on the potential possibilities for synthesizing ordered mesoporous nonsiliceous materials are presented as well. PMID:16846206

  7. 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

  8. Preparing mesoporous carbon and silica with rosin-silica composite gel.

    PubMed

    Liu, Haidi; Du, Shangfeng; Chen, Yunfa

    2009-02-01

    Mesoporous carbon and mesoporous silica were prepared respectively with a same rosin-silica nanocomposite gel which was synthesized by cogelating tetra-ethyl-oxy-silane (silica source) and rosin (carbon source). Carbonizing the gel in nitrogen and then etching away silica with alkaline solution, mesoporous carbon with specific surface area larger than 800 m2/g was obtained. If calcining the gel at high temperature in air for given time, porous silica with surface area higher than 700 m2/g was done. BET measurement was employed to investigate the pore distribution and surface area of the samples. Most of the pores in both the porous carbon and porous silica were mesoscale, which makes the materials potential in enzyme supports for bio-catalyzed reaction or adsorbents for contaminants with large molecular size. PMID:19441395

  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. 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.

  11. Mesoporous TiO2 implants for loading high dosage of antibacterial agent

    NASA Astrophysics Data System (ADS)

    Park, Se Woong; Lee, Donghyun; Choi, Yong Suk; Jeon, Hoon Bong; Lee, Chang-Hoon; Moon, Ji-Hoi; Kwon, Il Keun

    2014-06-01

    We have fabricated mesoporous thin films composed of TiO2 nanoparticles on anodized titanium implant surfaces for loading drugs at high doses. Surface anodization followed by treatment with TiO2 paste leads to the formation of mechanically stable mesoporous thin films with controllable thickness. A series of antibacterial agents (silver nanoparticles, cephalothin, minocycline, and amoxicillin) were loaded into the mesoporous thin films and their antibacterial activities were evaluated against five bacterial species including three oral pathogens. Additionally, two agents (silver nanoparticles and minocycline) were loaded together on the thin film and tested for antibacterial effectiveness. The combination of silver nanoparticles and minocycline was found to display a wide range of effectiveness against all tested bacteria.

  12. 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.

  13. 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

  14. Foamed mesoporous carbon/silicon composite nanofiber anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Yuxin; Wen, Xiufang; Chen, Juan; Wang, Shengnian

    2015-05-01

    A new porous composite nanofiber manufacturing route, combining electrospinning and foaming processes, was developed. In this process, aluminum acetylacetonate (AACA) was introduced as the foaming agent in nanofibers made of polyacrylonitrile (PAN)/silicon (Si) nanoparticles. PAN/Si composite nanofibers were first produced through an electrospinning process and mesopores were then generated by foaming nanofibers via AACA sublimation. After further carbonization, the obtained mesoporous carbon/silicon composite nanofiber mats were tested as the anode material for lithium ion batteries. Within this composite anode, mesopores provide needed buffering space to accommodate the large volume expansion and consequent stress induced inside silicon during lithiation. This effectively mitigates silicon pulverization issue and helps achieve higher reversible capacity and better capacity retention in later battery tests when compared with anodes made of nonporous composites nanofibers and carbon nanofibers alone.

  15. 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

  16. 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.

  17. Mesoporous TiO2 spheres with a nitridated conducting layer

    SciTech Connect

    Yoon, Sukeun; Bridges, Craig A; Unocic, Raymond R; Paranthaman, Mariappan Parans

    2013-01-01

    Nitridated TiO2 mesoporous spheres have been synthesized by hydrothermal processing followed by post-nitridation with NH3. Characterization data reveal a nitridated conducting layer, in addition to a mesoporous, and nanosized building-block morphology resulting in a large surface area. The samples have an average pore size and surface area of, respectively, 10 nm and 87 m2/g. The nitridated TiO2 mesoporous spheres exhibit a high capacity of > 200 mAh/g with good cyclability and high rate capability, as the nitridated conducting layer and favorable morphology of nanosized spheres provides good electrical contact, accommodates cycling induced strain smoothly, and facilitates lithium-ion diffusion.

  18. A Single-Step Synthesis of Electroactive Mesoporous ProDOT-Silica Structures.

    PubMed

    Kim, Jeonghun; Kim, Byeonggwan; Anand, Chokkalingam; Mano, Ajayan; Zaidi, Javaid S M; Ariga, Katsuhiko; You, Jungmok; Vinu, Ajayan; Kim, Eunkyoung

    2015-07-13

    The single-step preparation of highly ordered mesoporous silica hybrid nanocomposites with conjugated polymers was explored using a novel cationic 3,4-propylenedioxythiophene (ProDOT) surfactant (PrS). The method does not require high-temperature calcination or a washing procedure. The combination of self-assembly of the silica surfactant and in situ polymerization of the ProDOT tail is responsible for creation of the mesoporosity with ultralarge pores, large pore volume, and electroactivity. As this novel material exhibits excellent textural parameters together with electrical conductivity, we believe that this could find potential applications in various fields. This novel concept of creating mesoporosity without a calcination process is a significant breakthrough in the field of mesoporous materials and the method can be further generalized as a rational preparation of various mesoporous hybrid materials having different structures and pore diameters. PMID:26037244

  19. Fabrication of ordered mesoporous carbon film supporting vanadium oxides for electrochemical supercapacitor

    NASA Astrophysics Data System (ADS)

    Zhao, Chunxia; Li, Junshen; Cao, Jinqiao; Chen, Wen

    2015-11-01

    Ordered mesoporous carbon film supporting vanadium oxide nanoparticles has been synthesized via ultrasound-assistant impregnation method with ordered mesoporous carbon C-FDU15 film as the host and V2O5 sol as the guest precursor. The hybrids exhibit type IV sorption isotherms with H2 hysteresis loop, indicating the well-retained characteristics of ordered mesoporous structure. The capacitance of the materials is enhanced with V2O5 loading. Particularly, the hybrids with 32.26 wt.% V2O5 loading yield an important capacitance of 128 F/g in 1 mol/L KNO3 electrolyte under a potential range from -0.6 V to 0.6 V. The improved specific capacitance of the hybrids is proposed to be the combination of the double-layer capacitance of ordered porous structure and the pseudocapacitance derived from V2O5.

  20. 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. PMID:20638505

  1. Enhanced Quantum Confined Stark Effect in a mesoporous hybrid multifunctional system

    NASA Astrophysics Data System (ADS)

    Gogoi, M.; Deb, P.; Sen, D.; Mazumder, S.; Kostka, A.

    2014-06-01

    Quantum Confined Stark Effect in hybrid of CdTe quantum dot with superparamagnetic iron oxide nanoparticles in both nonporous and mesoporous silica matrix has been realized. The observed QCSE is due to the local electric field induced by charge dispersion at SiO2/polar solvent interface. Enhanced Stark shift of 89.5 meV is observed in case of mesoporous hybrid structure and the corresponding local electric field has been evaluated as 4.38×104 V/cm. The enhancement is assumed to be caused by greater density of charge in the mesoporous hybrid. The conjugation of superparamagnetic nanoparticles in this tailored hybrid microstructure has not imparted any alteration to the Stark shift, but has added multifunctional attribute. The present study on the local electric field induced enhanced QCSE with wavelength modulation towards red end paves the way of developing magneto-fluorescent hybrid systems for biomedical imaging application.

  2. 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.

  3. 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

  4. Label-Free Luminescent Mesoporous Silica Nanoparticles for Imaging and Drug Delivery

    PubMed Central

    Chen, Hongmin; Zhen, Zipeng; Tang, Wei; Todd, Trever; Chuang, Yen-Jun; Wang, Lianchun; Pan, Zhengwei; Xie, Jin

    2013-01-01

    We report herein a straightforward and label-free approach to prepare luminescent mesoporous silica nanoparticles. We found that calcination at 400 °C can grant mesoporous organosilica nanoparticles with strong fluorescence of great photo- and chemical stability. The luminescence is found to originate from the carbon dots generated from the calcination, rather than the defects in the silica matrix as was believed previously. The calcination does not impact the particles' abilities to load drugs and conjugate to biomolecules. In a proof-of-concept study, we demonstrated that doxorubicin (Dox) can be efficiently encapsulated into these fluorescent mesoporous silica nanoparticles. After coupled to c(RGDyK), the nanoconjugates can efficiently home to tumors through interactions with integrin αvβ3 overexpressed on the tumor vasculature. This calcination-induced luminescence is expected to find wide applications in silica-based drug delivery, nanoparticle coating, and immunofluorescence imaging. PMID:24052805

  5. 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

  6. Transcription of G-quartet supramolecular aggregates into hierarchical mesoporous silica nanotubes.

    PubMed

    Min, Liang; Li, Tao; Tan, Qi; Tan, Xiaoping; Pan, Wu; He, Li; Zhang, Jie; Ou, Encai; Xu, Weijian

    2016-05-01

    The use of 5-guanosine monophosphate (GMP) with Sr(2+) ions to form G-quadruplex bundles as supramolecular templates for the preparation of hierarchical mesoporous silica nanotube materials is reported here, and some mesopores with a diameter of 4-22 nm were obtained. Furthermore, some mesopore channels which run perpendicularly to the center axis of the tube and penetrate right through the outer wall of the nanotubes were achieved by removing the templates. Besides, porous hollow silica spheres were obtained by changing some of the reaction conditions during the process of preparation. Their structures are stable even after high temperature calcination. A formation mechanism was proposed and discussed, and their structures were characterized using a number of means including X-ray diffraction, IR spectra, N2 adsorption-desorption isotherms, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). PMID:27068442

  7. Mesoporous polyaniline film on ultra-thin graphene sheets for high performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Yan, Jun; Fan, Zhuangjun; Wei, Tong; Zhang, Milin; Jing, Xiaoyan

    2014-02-01

    A facile approach has been developed to fabricate mesoporous PANI film on ultra-thin graphene nanosheet (G-mPANI) hybrid by in situ polymerization using graphene-mesoporous silica composite as template. Due to its mesoporous structure, over-all conductive network, G-mPANI electrode displays a specific capacitance of 749 F g-1 at 0.5 A g-1 with excellent rate capability (remains 73% even at 5.0 A g-1), much higher than that of pristine PANI electrode (315 F g-1 at 0.5 A g-1, 39% retention at 5.0 A g-1) in 1 mol L-1 H2SO4 aqueous solution. More interestingly, the G-mPANI hybrid can maintain 88% of its initial capacitance compared to 45% for pristine PANI after 1000 cycles, suggesting a superior electrochemical cyclic stability.

  8. Melting and freezing of argon in a granular packing of linear mesopore arrays.

    PubMed

    Schaefer, Christof; Hofmann, Tommy; Wallacher, Dirk; Huber, Patrick; Knorr, Klaus

    2008-05-01

    Freezing and melting of Ar condensed in a granular packing of template-grown arrays of linear mesopores (SBA-15, mean pore diameter 8 nm) has been studied by specific heat measurements C as a function of fractional filling of the pores. While interfacial melting leads to a single melting peak in C, homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the pores result in a complex freezing mechanism explainable only by a consideration of regular adsorption sites (in the cylindrical mesopores) and irregular adsorption sites (in niches of the rough external surfaces of the grains and at points of mutual contact of the powder grains). The tensile pressure release upon reaching bulk-liquid-vapor coexistence quantitatively accounts for an upward shift of the melting and freezing temperature observed while overfilling the mesopores. PMID:18518308

  9. 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

  10. 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

  11. Electrooxidation of formaldehyde based on nickel-palladium modified ordered mesoporous silicon.

    PubMed

    Miao, Fengjuan; Tao, Bairui

    2013-04-01

    Nickel and palladium nanoparticles were finely dispersed on ordered mesoporous silicon microchannels plate (MCP) by electroless plating. The structure and composition of the resulting Ni-Pd/Si MCP were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). The electrocatalystic properties of Ni-Pd/Si MCP electrode for formaldehyde oxidation have been investigated by cyclic voltammetry. The results show that Ni-Pd/Si MCP has a higher catalytic activity and better steady-state behavior for formaldehyde oxidation. This may be attributed to the synergistic property of high dispersion of Nickel and Palladium nanoparticles and particular properties of mesoporous Si MCP. The present study shows a promising choice of Ni-Pd nanoparticles supported by mesoporous silicon as effective electrocatalyst for formaldehyde electrooxidation in alkaline medium. The results imply that the Ni-Pd/Si MCP nanocomposite has good potential application in formaldehyde fuel cells and sensors. PMID:23763207

  12. Hierarchical Zeolites with Amine-Functionalized Mesoporous Domains for Carbon Dioxide Capture.

    PubMed

    Nguyen, Tien Hoa; Kim, Sungjune; Yoon, Minyoung; Bae, Tae-Hyun

    2016-03-01

    To prepare materials with high CO2 adsorption, a series of hierarchical LTA zeolites possessing various mesopore spaces that are decorated with alkylamines was designed and synthesized. The highest CO2 uptake capacity was achieved when (3-aminopropyl)trimethoxysilane (APTMS) was grafted onto the hierarchical LTA zeolite having the largest mesopores. Owing to the contributions of both alkylamine groups grafted onto the mesopore surfaces and active sites in the LTA zeolites, the amount of CO2 that can be taken up on these materials is much higher than for conventional aminosilicas such SBA-15 and MCM-41. Furthermore, the adsorbent shows good CO2 uptake capacity and recyclability in dynamic flow conditions. PMID:26833434

  13. 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.

  14. A general strategy for the rational design of size-selective mesoporous catalysts.

    PubMed

    Zapilko, Clemens; Liang, Yucang; Nerdal, Willy; Anwander, Reiner

    2007-01-01

    A series of functionalized mesoporous silicas with cagelike pore topology has been synthesized and screened for size-selective catalytic transformations. The aluminum-catalyzed Meerwein-Ponndorf-Verley (MPV) reduction of differently sized aromatic aldehydes (benzaldehyde and 1-pyrenecarbox-aldehyde) has been investigated as a test reaction. The catalysts were synthesized in a two-step grafting sequence comprising pore-size engineering of mesoporous silicas (SBA-1, SBA-2, SBA-16) with long-chain alkyl dimethylaminosilanes and surface organoaluminum chemistry with triethylaluminum [{Al(CH(2)CH(3))3}2]. Size-selective reaction behavior was found for small pore SBA-1 materials, and the selectivity could be efficiently tuned by selecting a silylating reagent of appropriate size. The results are compared with the catalytic performance of a large-pore periodic mesoporous organosilica PMO[SBA-1] and the nonporous high-surface-area silicas Aerosil 300/380. PMID:17203494

  15. Synthesis and catalytic properties of hybrid mesoporous materials assembled from polyhedral and bridged silsesquioxane monomers.

    PubMed

    Díaz, Urbano; García, Teresa; Velty, Alexandra; Corma, Avelino

    2012-07-01

    A family of hybrid mesoporous materials with high temperature stability was obtained by the suitable covalent combination of two types of siloxane precursors. Specifically, cubic T(8) polyhedral oligomeric (POSS) and aryl bridged silsesquioxane monomers (1,4-bis(triethoxysilyl)benzene, BTEB) play the role of nanobuilders. An optimal molar ratio of the two precursors (5-25 mol% of total silicon content from the BTEB disilane) generated a homogenous, highly accessible, and well-defined mesoporous material with hexagonal symmetry and narrow pore-size distribution. Physicochemical, textural, and spectroscopic analysis corroborated the effective integration and preservation of the two different nanoprecursors, thereby confirming the framework of the mesoporous hybrid materials. A post-synthesis amination treatment allowed the effective incorporation of amino groups onto the aryl linkers, thereby obtaining a stable and recyclable basic catalyst for use in C-C bond-formation processes. PMID:22678926

  16. 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.

  17. 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

  18. Synthesis of mesoporous nanocomposites for their application in solid oxide electrolysers cells: microstructural and electrochemical characterization.

    PubMed

    Torrell, M; Almar, L; Morata, A; Tarancón, A

    2015-01-01

    Fabrication routes for new SOEC mesoporous nanocomposite materials as electrodes are presented in this paper. NiO-CGO and SDC-SSC are described as possible new materials and their synthesis and the cell fabrication are discussed. The obtained materials are microstructurally characterised by SEM, TEM and XRD, where the mesoporous structures are observed and analysed. The obtained samples are electrochemically analysed by I-V polarisation curves and EIS analysis, showing a maximum current density of 330 mA cm(-2) at 1.7 V. A degradation of the cell performance is evidenced after a potentiostatic test at 1.4 V after more than 40 hours. Oxygen electrode delaminating is detected, which is most probably the main cause of ageing. Even taking into account the lack of durability of the fabricated cells, the mesoporous electrodes do not seem to be altered, opening the possibility for further studies devoted to this high stability material for SOEC electrodes. PMID:26212761

  19. 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.

  20. Preparation and characterization of sulfur-modified mesoporous titania photocatalyst

    NASA Astrophysics Data System (ADS)

    Shi, Zhongliang; Liu, Guiqing; Sun, Na; Yao, Shuhua; Wang, Shaofeng

    2013-08-01

    Sulfur-modified mesoporous titania (S-MTiO2) was investigated as a potential photocatalyst under visible light. The photocatalyst was prepared by template method using thiourea and tetrabutyl titanate (Ti(OC4H9)4) as precursors and Pluronic P123 as template. The photoabsorbance of as-prepared photocatalyst was measured by UV-vis absorption spectroscopy, which confirmed the extension of absorption into the visible region. The microstructure of S-MTiO2 was characterized using X-ray diffraction (XRD) and N2 adsorption-desorption measurements. The micro crystal of the S-doped photocatalyst consisted of anatase phase and no significant influence on the nature of crystal formation. X-ray photoelectron spectroscopy (XPS) measurements indicated the presence of C in the prepared photocatalyst in addition to S. The photo-catalytic performance was studied by photodegradation methyl orange (MO) in water under visible light irradiation. The calcination temperature and the doping content influenced the photoactivity.