WorldWideScience

Sample records for sba-15 ordered mesoporous

  1. Physical properties of ordered mesoporous SBA-15 silica as immunological adjuvant

    Mariano-Neto, F.; Matos, J. R.; Cides da Silva, L. C.; Carvalho, L. V.; Scaramuzzi, K.; Sant'Anna, O. A.; Oliveira, C. P.; Fantini, M. C. A.

    2014-10-01

    This work reports a detailed analysis of the ordered mesoporous SBA-15 silica synthesis procedure that provides a matrix with mean pore diameter around 10 nm. The encapsulation of bovine serum albumin (BSA) by four different methods allowed the determination of the best imbibition condition, which is keeping the mixture under rest and solvent evaporation. Simulation of the in situ SAXS scattered intensity of the BSA release in potassium buffer solution, gastrointestinal fluids revealed a slow evolution of BSA content, independent of the media. Proton induced x-ray emission results obtained in calcined mouse organs revealed that silica is only present in the spleen after 35 days and is completely eliminated from all mouse organs after 10 weeks. Biological studies showed that Santa Barbara Amorphous-15 is an effective adjuvant when compared to the traditional Al(OH)3, and is non-toxic to mice, rats, dogs and even cells, such as macrophages and dendritic cells. Recent studies showed that the immunological response is improved by enhancing the inflammatory response and the recruitment of immune competent cells to the site of injection as by the oral route and, most importantly, by increasing the number of phagocytes of a particulate antigen by antigen presenting cells. This research is under the scope of the International Patent WO 07030901, IN248654,ZA2008/02277, KR 1089400, MX297263, JP5091863, CN101287491B.

  2. Physical state of poorly water soluble therapeutic molecules loaded into SBA-15 ordered mesoporous silica carriers: a case study with itraconazole and ibuprofen.

    Mellaerts, Randy; Jammaer, Jasper A G; Van Speybroeck, Michiel; Chen, Hong; Van Humbeeck, Jan; Augustijns, Patrick; Van den Mooter, Guy; Martens, Johan A

    2008-08-19

    The ordered mesoporous silica material SBA-15 was loaded with the model drugs itraconazole and ibuprofen using three different procedures: (i) adsorption from solution, (ii) incipient wetness impregnation, and (iii) heating of a mixture of drug and SBA-15 powder. The location of the drug molecules in the SBA-15 particles and molecular interactions were investigated using nitrogen adsorption, TGA, DSC, DRS UV-vis, and XPS. The in vitro release of hydrophobic model drugs was evaluated in an aqueous environment simulating gastric fluid. The effectiveness of the loading method was found to be strongly compound dependent. Incipient wetness impregnation using a concentrated itraconazole solution in dichloromethane followed by solvent evaporation was most efficient for dispersing itraconazole in SBA-15. The itraconazole molecules were located on the mesopore walls and inside micropores of the mesopore walls. When SBA-15 was loaded by slurrying it in a diluted itraconazole solution from which the solvent was evaporated, the itraconazole molecules ended up in the mesopores that they plugged locally. At a loading of 30 wt %, itraconazole exhibited intermolecular interactions inside the mesopores revealed by UV spectroscopy and endothermic events traced with DSC. The physical mixing of itraconazole and SBA-15 powder followed by heating above the itraconazole melting temperature resulted in formulations in which glassy itraconazole particles were deposited externally on the SBA-15 particles. Loading with ibuprofen was successful with each of the three loading procedures. Ibuprofen preferably is positioned inside the micropores. In vitro release experiments showed fast release kinetics provided the drug molecules were evenly deposited over the mesoporous surface.

  3. Dissolution enhancement of a model poorly water-soluble drug, atorvastatin, with ordered mesoporous silica: comparison of MSF with SBA-15 as drug carriers.

    Maleki, Aziz; Hamidi, Mehrdad

    2016-01-01

    The purpose of this study was to develop mesoporous silica materials incorporated with poorly water-soluble drug atorvastatin calcium (AC) in order to improve drug dissolution, and intended to be orally administrated. A comparison between 2D-hexagonal silica nanostructured SBA-15 and mesocellular siliceous foam (MSF) with continuous 3D pore system on drug release rate was investigated. AC-loaded mesoporous silicas were characterized thorough N2 adsorption-desorption analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and dynamic light scattering (DLS). Results demonstrated a successful incorporation of AC into the silica-based hosts. The results taken from the drug release tests were also analyzed using different parameters, namely similarity factor (f2), difference factor (f1), dissolution efficiency (DE%), mean dissolution rate (MDR) and dissolution time (tm%). It confirmed a significant enhancement in the release profile of atorvastatin calcium with SBA-15, and MSF as drug carrier. Moreover, in comparison with SBA-15, MSF showed faster release rate of AC in enzyme-free simulated gastric fluid (pH 1.2). We believed that our findings can help the use of mesoporous silica materials in improving bioavailability of poorly water-soluble drugs.

  4. Adsorptive removal of selected pharmaceuticals by mesoporous silica SBA-15

    Bui, Tung Xuan; Choi, Heechul

    2009-01-01

    The removal of five selected pharmaceuticals, viz., carbamazepine, clofibric acid, diclofenac, ibuprofen, and ketoprofen was examined by batch sorption experiments onto a synthesized mesoporous silica SBA-15. SBA-15 was synthesized and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N 2 adsorption-desorption measurement, and point of zero charge (PZC) measurement. Pharmaceutical adsorption kinetics was rapid and occurred on a scale of minutes, following a pseudo-second-order rate expression. Adsorption isotherms were best fitted by the Freundlich isotherm model. High removal rates of individual pharmaceuticals were achieved in acidic media (pH 3-5) and reached 85.2% for carbamazepine, 88.3% for diclofenac, 93.0% for ibuprofen, 94.3% for ketoprofen, and 49.0% for clofibric acid at pH 3 but decreased with increase in pH. SBA-15 also showed high efficiency for removal of a mixture of 5 pharmaceuticals. Except for clofibric acid (35.6%), the removal of pharmaceuticals in the mixture ranged from 75.2 to 89.3%. Based on adsorption and desorption results, the mechanism of the selected pharmaceuticals was found to be a hydrophilic interaction, providing valuable information for further studies to design materials for the purpose. The results of this study suggest that mesoporous-silica-based materials are promising adsorbents for removing pharmaceuticals from not only surface water but also wastewater of pharmaceutical industrial manufactures.

  5. Adsorptive removal of selected pharmaceuticals by mesoporous silica SBA-15

    Bui, Tung Xuan, E-mail: bxtung@gist.ac.kr [Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea, Republic of); Choi, Heechul, E-mail: hcchoi@gist.ac.kr [Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea, Republic of)

    2009-09-15

    The removal of five selected pharmaceuticals, viz., carbamazepine, clofibric acid, diclofenac, ibuprofen, and ketoprofen was examined by batch sorption experiments onto a synthesized mesoporous silica SBA-15. SBA-15 was synthesized and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N{sub 2} adsorption-desorption measurement, and point of zero charge (PZC) measurement. Pharmaceutical adsorption kinetics was rapid and occurred on a scale of minutes, following a pseudo-second-order rate expression. Adsorption isotherms were best fitted by the Freundlich isotherm model. High removal rates of individual pharmaceuticals were achieved in acidic media (pH 3-5) and reached 85.2% for carbamazepine, 88.3% for diclofenac, 93.0% for ibuprofen, 94.3% for ketoprofen, and 49.0% for clofibric acid at pH 3 but decreased with increase in pH. SBA-15 also showed high efficiency for removal of a mixture of 5 pharmaceuticals. Except for clofibric acid (35.6%), the removal of pharmaceuticals in the mixture ranged from 75.2 to 89.3%. Based on adsorption and desorption results, the mechanism of the selected pharmaceuticals was found to be a hydrophilic interaction, providing valuable information for further studies to design materials for the purpose. The results of this study suggest that mesoporous-silica-based materials are promising adsorbents for removing pharmaceuticals from not only surface water but also wastewater of pharmaceutical industrial manufactures.

  6. Au and AuCu Nanoparticles Supported on SBA-15 Ordered Mesoporous Titania-Silica as Catalysts for Methylene Blue Photodegradation

    Isabel Barroso-Martín

    2018-05-01

    Full Text Available The photocatalytic degradation of methylene blue (MB dye has been performed under UV irradiation in aqueous suspension, employing photocatalysts based on Au (1.5 wt % and AuCu (Au/Cu = 1, 2.0 wt %, and supported on SBA-15-ordered mesoporous silica, with and without titania (Si/Ti = 3, in order to evaluate the versatility of this mesoporous support in this type of reaction of great impact from the environmental point of view. Samples were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption-desorption at −196 °C, and X-ray photoelectron spectroscopy (XPS, so as to study their structural, optical, and chemical properties. All the prepared catalysts were found to be active in the test reaction. The bimetallic AuCu-based catalysts attained very high MB degradation values, in particular AuCu/SBA-15 titania-silica sample reached 100% of dye oxidation after the monitored reaction period (120 min.

  7. Preparation of mesoporous silica films SBA-15 over different substrates

    Campos, V.O.; Sousa, E.M.B. de; Macedo, W.A.A.

    2010-01-01

    Mesoporous materials have been target of frequent interest due to its wide application possibilities, for example development of gas sensors, catalysis, molecules transportation, pharmaceuticals release, synthesis of auto-organized nanostructures, among others. The possibilities of application are enhanced when such materials are disposed in the form of thin and ultrathin films. In this work the preparation of mesoporous SBA-15 silica films is explored by means of the dipcoating technique of a sol-gel on different substrates (glass slides, stainless steel, copper), using the surfactant poly(ethylene glycol)-block-poly(propylene glycol)- block-poly(ethylene glycol), known as P123, a block copolymer. Synthesis parameters surfactant concentration, aging time and temperature were investigated. In this work we present the morphological and structural characterization of the prepared films, which were obtained using atomic force microscopy and x-ray fluorescence and diffraction. (author)

  8. Microstructure and Magnetic Properties of Highly Ordered SBA-15 Nanocomposites Modified with Fe2O3 and Co3O4 Nanoparticles

    P. F. Wang

    2012-01-01

    Full Text Available Owing to the unique order mesopores, mesoporous SBA-15 could be used as the carrier of the magnetic nanoparticles. The magnetic nanoparticles in the frame and the mesopores lead to the exchange-coupling interaction or other interactions, which could improve the magnetic properties of SBA-15 nanocomposites. Mesoporous Fe/SBA-15 had been prepared via in situ anchoring Fe2O3 into the frame and the micropores of SBA-15 using the sol-gel and hydrothermal processes. Co3O4 nanoparticles had been impregnated into the mesopores of Fe/SBA-15 to form mesoporous Fe/SBA-15-Co3O4 nanocomposites. XRD, HRTEM, VSM, and N2 physisorption isotherms were used to characterize the mesostructure and magnetic properties of the SBA-15 nanocomposites, and all results indicated that the Fe2O3 nanoparticles presented into the frame and micropores, while the Co3O4 nanoparticles existed inside the mesopores of Fe/SBA-15. Furthermore, the magnetic properties of SBA-15 could be conveniently adjusted by the Fe2O3 and Co3O4 magnetic nanoparticles. Fe/SBA-15 exhibited ferromagnetic properties, while the impregnation of Co3O4 nanoparticles greatly improved the coercivity with a value of 1424.6 Oe, which was much higher than that of Fe/SBA-15.

  9. Growth and physico-chemical properties of interconnected carbon nanotubes in FeSBA-15 mesoporous molecular sieves

    Ulka Suryavanshi

    2016-03-01

    Full Text Available Carbon nanotubes (CNTs with well-defined hollow interiors, and different morphologies have been grown inside the nanochannels of iron substituted SBA-15 (Santa Barbara Amorphous with different iron contents and well-ordered large mesopores by chemical vapour deposition method. This novel method requires only 3 min for the formation of high quality multiwalled CNTs inside the SBA-15. The physico-chemical characteristics of the prepared CNT/Fe-SBA-15 nanocomposite have been analysed with powder X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy and thermogravimetric analysis (TGA. XRD, Raman spectroscopy and TGA results confirm that the formed CNTs in SBA-15 nanochannels are highly pure and graphitic in nature, which can be altered by tuning the Fe content in the support matrix. SEM images show the interconnected network of SBA-15/CNT where CNT bridges the neighbouring SBA-15 nanoparticles. Interestingly, spring like CNTs and multi-terminal junctions such as Y and H junctions were also observed. The morphology of the CNTs inside the nanochannels of the SBA-15 support can also be controlled by the simple adjustment of the iron content in the SBA-15 framework. It has also been found that the content of Fe in the silica framework of SBA-15 plays a significant role in the formation of the CNTs and the amount of deposited CNTs in the nanochannels of SBA-15 increased with increasing the concentration of iron in framework. Among the materials studied, the FeSBA-15 with the nSi/nFe ratio of 2 showed the highest catalytic activity towards the formation of high quality CNTs.

  10. Selective Preparation of trans-Carveol over Ceria Supported Mesoporous Materials MCM-41 and SBA-15

    Nariman F. Salakhutdinov

    2013-05-01

    Full Text Available Ce-modified mesoporous silica materials MCM-41 and SBA-15, namely 32 wt % Ce–Si–MCM-41, 16 wt % Ce–H–MCM-41 and 20 wt % Ce–Si–SBA-15, were prepared, characterized and studied in the selective preparation of trans-carveol by α-pinene oxide isomerization. The characterizations of these catalysts were performed using scanning electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption and FTIR pyridine adsorption. Selective preparation of trans-carveol was carried out in the liquid phase in a batch reactor. The activity and the selectivity of catalyst were observed to be influenced by their acidity, basicity and morphology of the mesoporous materials. The formation of trans-carveol is moreover strongly influenced by the basicity of the used solvent and in order to achieve high yields of this desired alcohol it is necessary to use polar basic solvent.

  11. Mapping the location of grafted PNIPAAM in mesoporous SBA-15 silica using gas adsorption analysis

    Reichhardt, Nina Viola; Guillet-Nicolas, Rémy; Thommes, Matthias

    2012-01-01

    The thermoresponsive polymer poly-N-isopropylacrylamide (PNIPAAM) was grafted in mesoporous SBA-15 silica. The grafting process consists of three steps: (i) increasing the amount of surface silanol groups of SBA-15 by hydroxylation, (ii) attachment of an anchor (1-(trichlorosilyl)-2-(m/p- (chloro......The thermoresponsive polymer poly-N-isopropylacrylamide (PNIPAAM) was grafted in mesoporous SBA-15 silica. The grafting process consists of three steps: (i) increasing the amount of surface silanol groups of SBA-15 by hydroxylation, (ii) attachment of an anchor (1-(trichlorosilyl)-2-(m...

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

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Organically functionalized mesoporous SBA-15 as sorbents for removal of selected pharmaceuticals from water

    Bui, Tung Xuan [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea, Republic of); Kang, Seo-Young [International Environmental Research Center (IERC), Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea, Republic of); Lee, Sang-Hyup [Water Environment Center, Korea Institute of Science and Technology, Cheongryang, Seoul 130-650 (Korea, Republic of); Choi, Heechul, E-mail: hcchoi@gist.ac.kr [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu, Gwangju 500-712 (Korea, Republic of)

    2011-10-15

    Highlights: {yields} SBA-15 grafted with aminopropyl, hydroxymethyl, and trimethylsilyl groups as sorbents. {yields} Sorbents for removal of a mixture of 12 pharmaceuticals from water. {yields} Hydroxymethyl-SBA-15 shows similar adsorption efficiency like SBA-15. {yields} Aminopropyl-SBA-15 makes increase for clofibric acid, diclofenac, decrease for atenolol, estrone, trimethoprim. {yields} Trimethylsilyl-SBA-15 makes increase for 9 compounds; 7 compounds from 70.6% to 98.9%. - Abstract: Mesoporous silica SBA-15 and its postfunctionalized counterparts with hydroxymethyl (HM-SBA-15), aminopropyl (AP-SBA-15), and trimethylsilyl (TMS-SBA-15) were prepared and characterized by powder X-ray diffraction, N{sub 2} adsorption-desorption measurement, Fourier-transform infrared spectroscopy, and elemental analysis. The removal of a mixture of 12 selected pharmaceuticals was investigated by batch adsorption experiments onto SBA-15 and the grafted materials. SBA-15 showed to have moderate adsorption affinity with amino-containing (atenolol, trimethoprim) and hydrophobic pharmaceuticals, but it displayed minimal adsorption affinity toward hydrophilic compounds. HM-SBA-15 was analogous with SBA-15 in terms of the adsorption efficiency toward all pharmaceuticals. AP-SBA-15 exhibited an increase in the adsorption of two acidic compounds (clofibric acid, diclofenac) but a decrease in the adsorption of estrone and the two amino-containing compounds. Among the grafted materials, TMS-SBA-15 had the highest adsorption affinity toward most pharmaceuticals. Moreover, the adsorption of nine pharmaceuticals to TMS-SBA-15 was significantly higher than that to SBA-15; seven of which showed the removal percentages from 70.6% to 98.9% onto TMS-SBA-15. The number of pharmaceuticals showing high adsorption efficiency onto TMS-SBA-15 did not alter significantly as the pH changed in the range of 5.5-7.6. The results suggest that TMS-SBA-15 is a promising material for the removal of pharmaceuticals

  14. Organically functionalized mesoporous SBA-15 as sorbents for removal of selected pharmaceuticals from water

    Bui, Tung Xuan; Kang, Seo-Young; Lee, Sang-Hyup; Choi, Heechul

    2011-01-01

    Highlights: → SBA-15 grafted with aminopropyl, hydroxymethyl, and trimethylsilyl groups as sorbents. → Sorbents for removal of a mixture of 12 pharmaceuticals from water. → Hydroxymethyl-SBA-15 shows similar adsorption efficiency like SBA-15. → Aminopropyl-SBA-15 makes increase for clofibric acid, diclofenac, decrease for atenolol, estrone, trimethoprim. → Trimethylsilyl-SBA-15 makes increase for 9 compounds; 7 compounds from 70.6% to 98.9%. - Abstract: Mesoporous silica SBA-15 and its postfunctionalized counterparts with hydroxymethyl (HM-SBA-15), aminopropyl (AP-SBA-15), and trimethylsilyl (TMS-SBA-15) were prepared and characterized by powder X-ray diffraction, N 2 adsorption-desorption measurement, Fourier-transform infrared spectroscopy, and elemental analysis. The removal of a mixture of 12 selected pharmaceuticals was investigated by batch adsorption experiments onto SBA-15 and the grafted materials. SBA-15 showed to have moderate adsorption affinity with amino-containing (atenolol, trimethoprim) and hydrophobic pharmaceuticals, but it displayed minimal adsorption affinity toward hydrophilic compounds. HM-SBA-15 was analogous with SBA-15 in terms of the adsorption efficiency toward all pharmaceuticals. AP-SBA-15 exhibited an increase in the adsorption of two acidic compounds (clofibric acid, diclofenac) but a decrease in the adsorption of estrone and the two amino-containing compounds. Among the grafted materials, TMS-SBA-15 had the highest adsorption affinity toward most pharmaceuticals. Moreover, the adsorption of nine pharmaceuticals to TMS-SBA-15 was significantly higher than that to SBA-15; seven of which showed the removal percentages from 70.6% to 98.9% onto TMS-SBA-15. The number of pharmaceuticals showing high adsorption efficiency onto TMS-SBA-15 did not alter significantly as the pH changed in the range of 5.5-7.6. The results suggest that TMS-SBA-15 is a promising material for the removal of pharmaceuticals from aqueous phase

  15. Microwave radiation hydrothermal synthesis and characterization of micro- and mesoporous composite molecular sieve Y/SBA-15

    Wenyuan Wu

    2017-05-01

    Full Text Available A microwave radiation hydrothermal method to control synthesis of micro- and mesoporous Y/SBA-15 composite molecular sieves was reported. The synthesized SBA-15 and Y/SBA-15 were characterized by scanning electron microscopy (SEM and N2 adsorption–desorption. The three kinds of different concentrations of hydrochloric acid (0.75 M, 2 M and 3.25 M were used to investigate the effect on Y/SBA-15. The analysis results of the composite products indicated that the optimization synthesis condition employed zeolite type Y and TEOS as silicon sources under 0.75 M hydrochloric acid by the microwave radiation hydrothermal synthesis method. The N2 adsorption–desorption test results of micro–mesoporous composite molecular sieve type Y/SBA-15 in mesoporous extent indicated that SBET is 355.529 m2/g, D‾BET is 4.050 nm, and mesoporous aperture focuses on the distribution region of 5.3 nm. It was found that the received composite product has an appropriate proportion of smaller size, larger size pore structure and the thicker pore wall. In addition, its internal channels have a high degree of order and smooth flow in long-range channels.

  16. Characterization and comprehension of zeolite NaY/mesoporous SBA-15 composite as adsorbent for paraquat

    Osakoo, Nattawut, E-mail: natawut.work@gmail.com [School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000 (Thailand); Pansakdanon, Chaianun [School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000 (Thailand); Department of Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Sosa, Narongrit; Deekamwong, Krittanun; Keawkumay, Chalermpan; Rongchapo, Wina [School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000 (Thailand); Chanlek, Narong [Synchrotron Light Research Institute, Nakhon Ratchasima, 30000 (Thailand); Jitcharoen, Juthamas [Department of Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Prayoonpokarach, Sanchai [School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000 (Thailand); Wittayakun, Jatuporn, E-mail: jatuporn@g.sut.ac.th [School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000 (Thailand)

    2017-06-01

    NaY was synthesized from fumed silica and further modified to form a composite with SBA-15. Textural properties and basicity of the composite NaY-SBA-15 were between those of the parent materials. Paraquat adsorption on NaY was 204.1 mg/g, higher than that on NaY synthesized with rice husk silica from the previous work. SBA-15 was a poor adsorbent for paraquat. Based on the weight of NaY, the adsorption capacity of analytical-grade paraquat on the NaY-SBA-15 composite was 241.5 mg/g-NaY. Moreover, the composite adsorbed blue dye from a commercial grade paraquat. Interaction between the NaY-SBA-15 and paraquat could be from C and N atoms in paraquat with oxygen atom on NaY-SBA-15. - Highlights: • Zeolite NaY/mesoporous SBA-15 composite was synthesized with a simple method. • NaY and SBA-15 coexisted in the composite confirmed by FTIR, CO{sub 2}-TPD and XPS. • Adsorption capacity of paraquat (mg/g-NaY) was improved by NaY and SBA-15 composite. • C and N atoms in paraquat could interact with oxygen atom on NaY-SBA-15 composite.

  17. Selective Preparation of Furfural from Xylose over Sulfonic Acid Functionalized Mesoporous Sba-15 Materials

    Panpan Li

    2011-04-01

    Full Text Available Sulfonic acid functionalized mesoporous SBA-15 materials were prepared using the co-condensation and grafting methods, respectively, and their catalytic performance in the dehydration of xylose to furfural was examined. SBA-15-SO3H(C prepared by the co-condensation method showed 92–95% xylose conversion and 74% furfural selectivity, and 68–70% furfural yield under the given reaction conditions. The deactivation and regeneration of the SBA-15-SO3H(C catalyst for the dehydration of xylose was also investigated. The results indicate that the used and regeneration catalysts retained the SBA-15 mesoporous structure, and the S content of SBA-15-SO3H(C almost did not change. The deactivation of the catalysts is proposed to be associated with the accumulation of byproducts, which is caused by the loss reaction of furfural. After regeneration by H2O2, the catalytic activity of the catalyst almost recovered.

  18. Development of efficient amine-modified mesoporous silica SBA-15 for CO2 capture

    Zhang, Xiaoyun; Qin, Hongyan; Zheng, Xiuxin; Wu, Wei

    2013-01-01

    Graphical abstract: - Highlights: • A secondary amine AN-TEPA is used to modify the SBA-15. • CO 2 adsorption capacity (180.1 mg g −1 -adsorbent for 70% amine loading) is high. • The sorbent exhibits a high stability after 12 cycling runs. • The modified SBA-15 achieves complete desorption at low temperature (100 °C). - Abstract: A novel CO 2 sorbent was prepared by impregnating mesoporous silica, SBA-15, with acrylonitrile (AN)-modified tetraethylenepentamine (TEPA) in order to increase CO 2 adsorption capacity and improve cycling stability. The mesoporous silica with pre- and post-surface modification was investigated by X-ray diffraction characterization (XRD), N 2 adsorption–desorption test (N 2 -BET), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The adsorption/desorption performance of S-TN (TN: AN modified TEPA) and S-TEPA was studied by dynamic adsorption. Test results showed that the solid base-impregnated SBA-15 demonstrated high CO 2 adsorption capacity (180.1 mg g −1 -adsorbent for 70% amine loading level). Compared to S-TEPA (24.1% decrease of initial capacity), S-TN with 50% amine loading exhibited improved cycling stability, 99.9% activity reserved (from initial 153.0 mg g −1 to 151.3 mg g −1 ) after 12 cycles of adsorption/desorption at 100 °C. A mechanism of molecular structure of the loaded amine was attributed to the improved performance

  19. Development of TREN dendrimers over mesoporous SBA-15 for CO2 adsorption

    Bhagiyalakshmi, Margandan; Park, Sang Do; Cha, Wang Seog; Jang, Hyun Tae

    2010-01-01

    Mesoporous SBA-15 was synthesized using rice husk ash (RHA) as the silica source and their defective Si-OH groups were grafted with tris(2-aminoethyl) amine (TREN) dendrimers generation through step-wise growth technique. The X-ray diffraction (XRD) and nitrogen adsorption/desorption results of parent SBA-15 obtained from RHA, suggests its resemblance with SBA-15 synthesized using conventional silica sources. Furthermore, the nitrogen adsorption/desorption results of SBA-15/TREN dendrimer generations (G1-G3) illustrates the growth of dendrimer inside the mesopores of SBA-15 and their CO 2 adsorption capacity was determined at 25 deg. C. The maximum CO 2 adsorption capacity of 5-6 and 7-8 wt% over second and third dendrimer generation was observed which is discernibly higher than the reported melamine and PAMAM dendrimers. The experimental CO 2 adsorption capacity was found to be less than theoretically calculated CO 2 adsorption capacity due to inter and intra molecular amidation as result of steric hindrance during the dendrimer growth. These SBA-15/TREN dendrimer generations also exhibit thermal stability up to 350 deg. C and CO 2 adsorption capacity remains unaltered upon seven consecutive runs.

  20. Fe3O4@mesoporous SBA-15: A magnetically recoverable catalyst for photodegradation of malachite green

    Aliyan, Hamid; Fazaeli, Razieh; Jalilian, Rahil

    2013-01-01

    Surface of mesostructured silica (SBA-15) was modified by immobilizing Fe 3 O 4 . This modified-nanosized mesoporous silica Fe 3 O 4 @SBA-15 was characterized by FTIR, XRD, BET and SEM. A comparison of the photoefficiency of Fe 3 O 4 @SBA-15 toward photodegradation of malachite green (MG) was investigated in a photocatalytic reactor using UV lamp as a light source. The effect of various experimental parameters on the degradation performance of the process was evaluated by examining catalyst dosage, initial dye concentration and pH of the dye solution in the presence of Fe 3 O 4 @SBA-15 as photocatalyst. It was found that the photocatalyst exhibited significantly high catalytic stability, and the activity loss is negligible after five MG degradation cycles.

  1. TiO2 supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

    Li, Yanjuan; Li, Nan; Tu, Jinchun; Li, Xiaotian; Wang, Beibei; Chi, Yue; Liu, Darui; Yang, Dianfan

    2011-01-01

    Highlights: ► Rod-like SBA-15 and normal SBA-15 were used to prepare TiO 2 /SBA-15 composites. ► TiO 2 /SBA-15 composites were studied as catalysts for methyl orange photodegradation. ► TiO 2 /Rod-SBA-15 exhibited higher photocatalytic activity than TiO 2 /Nor-SBA-15. ► The higher catalytic activity was a result of the controlled morphology of SBA-15. -- Abstract: TiO 2 nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N 2 -sorption and UV–Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO 2 /SBA-15 composite was prepared by loading TiO 2 nanoparticles on uniform rod-like SBA-15 of 1 μm length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.

  2. Highly selective epoxidation of styrene over mesoporous Au-Ti-SBA-15 via photocatalysis process: Synthesis, characterization, and catalytic application

    Guo Yajie; Liu Zhengwang [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China); Wang Guangjian, E-mail: wgj2260@chnu.edu.cn [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China); Huang Yanhog; Kang Fangfang [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China)

    2011-11-15

    Highly ordered Au-Ti-SBA-15 mesoporous molecular sieves were successfully synthesized by one-pot hydrothermal synthesis in acid medium, and were characterized by XRD, UV-vis, SEM, element-mapping, HRTEM, N{sub 2} adsorption, XPS, {sup 29}Si MAS NMR, NH{sub 3}-TPD and FT-IR. The as-prepared Au-Ti-SBA-15 samples were possessed of highly ordered mesostructures with larger pore diameter, pore volume and uniform mesopore size distribution. In the oxidation of styrene with H{sub 2}O{sub 2} as the oxidant over Au-Ti-SBA-15 catalyst under photo-irradiation, reaction parameters, such as molar ratio of H{sub 2}O{sub 2} to styrene, reaction time, solvent, the amount of catalyst, catalyst species, and the amount of 3% NaOH, were conditioned at length. As a result, highly selective epoxidation of styrene over catalyst was carried out perfectly for 10 min with high TOF of 4.75 Multiplication-Sign 10{sup 3} min{sup -1}.

  3. Covalent Anchoring of Chloroperoxidase and Glucose Oxidase on the Mesoporous Molecular Sieve SBA-15

    Martin Hartmann

    2010-02-01

    Full Text Available Functionalization of porous solids plays an important role in many areas, including heterogeneous catalysis and enzyme immobilization. In this study, large-pore ordered mesoporous SBA-15 molecular sieves were synthesized with tetraethyl orthosilicate (TEOS in the presence of the non-ionic triblock co-polymer Pluronic P123 under acidic conditions. These materials were grafted with 3 aminopropyltrimethoxysilane (ATS, 3-glycidoxypropyltrimethoxysilane (GTS and with 3 aminopropyltrimethoxysilane and glutaraldehyde (GA-ATS in order to provide covalent anchoring points for enzymes. The samples were characterized by nitrogen adsorption, powder X-ray diffraction, solid-state NMR spectroscopy, elemental analysis, diffuse reflectance fourier transform infrared spectroscopy and diffuse reflectance UV/Vis spectroscopy. The obtained grafted materials were then used for the immobilization of chloroperoxidase (CPO and glucose oxidase (GOx and the resulting biocatalysts were tested in the oxidation of indole. It is found that enzymes anchored to the mesoporous host by the organic moieties can be stored for weeks without losing their activity. Furthermore, the covalently linked enzymes are shown to be less prone to leaching than the physically adsorbed enzymes, as tested in a fixed-bed reactor under continuous operation conditions.

  4. Ascorbyl Tetraisopalmitate Inclusion into Υ-Cyclodextrin and Mesoporous SBA-15: Preparation, Characterization and In Vitro Release Study

    Maria Bastianini

    2017-07-01

    Full Text Available Ascorbic acid or vitamin C is a strong antioxidant widely used in cosmetic and food fields. This vitamin is very unstable and rapidly undergoes degradation. In order to solve this problem and to obtain a stable ascorbic acid, Nikkol Group has developed ascorbyltetraisopalmitate (VC-IP. This raw material is an oil phase, already well-known and employed in the cosmetic market. The objective of this study is to obtain VC-IP in micro-powder form, in order to produce a new raw material that is easily dispersible in oil and water phases and useful for make-up and color cosmetic applications. Various types of drug carriers were studied and considered in order to support VC-IP and obtain the conversion in powder. Υ-cyclodextrin and mesoporous silica SBA-15 were chosen as the best candidates. A white powder of supported VC-IP was obtained with each carrier (VC-IP@cyclodextrin, VC-IP@SBA-15. The systems underwent physicochemical characterization and in vitro release tests were carried out. Based on the conducted study, it can be concluded that by supporting VC-IP on Υ-cyclodextrin and SBA-15, it is feasible to obtain a new raw material in powder form. The two carriers possess different release profiles, adding the possibility to finely tune the release of the active component in smart formulations.

  5. Modification of mesoporous silica SBA-15 with different organic molecules to gain chemical sensors: a review

    Negar Lashgari

    2016-01-01

    Full Text Available The recognition of the biologically and environmentally important ions is of great interest in the field of chemical sensors in recent years. The fluorescent sensors as a powerful optical analytical technique for the detection of low level of various analytes such as anions and metal cations have been progressively developed due to the simplicity, cost effective, and selectivity for monitoring specific analytes in various systems. Organic-inorganic hybrid nanomaterials have important advantages as solid chemosensors and various innovative hybrid materials modified by fluorescence molecules were recently prepared. On the other hand, the homogeneous porosity and large surface area of mesoporous silica make it a promising inorganic support. SBA-15 as a two-dimensional hexagonal mesoporous silica material with stable structure, thick walls, tunable pore size, and high specific surface area is a valuable substrate for modification with different organic chelating groups. This review highlights the fluorescent chemosensors for ionic species based on modification of the mesoporous silica SBA-15 with different organic molecules, which have been recently developed from our laboratory.

  6. Synthesis of lithium superionic conductor by growth of a nanoglass within mesoporous silica SBA-15 template

    Chatterjee, Soumi; Miah, Milon; Saha, Shyamal Kumar; Chakravorty, Dipankar

    2018-04-01

    Nanodimensional silica based glasses containing alkali ions have recently been grown using suitable templates. These have shown electrical properties drastically different from those of their bulk counterpart. We have synthesized silicophosphate glasses having lithium ions with concentrations of 15-35 mole% Li2O within mesoporous silica SBA-15 (Santa Barbara amorphous-15) comprising of pores of diameter ~5 nm. The nanoglasses are characterized by electrical conductivities 5-6 orders of magnitude higher than those of the corresponding bulk glasses. These properties are attributed to the presence of a larger free volume in the nanoglasses as compared to their bulk states. The nanocomposites with 35 mole% Li2O exhibit an electrical conductivity of ~3 × 10-4 S · cm-1 at around room temperature. The activation energy for Li+ ion migration has been estimated from the conductivity-temperature variation to be 0.078 eV. These nanocomposites are believed to be ideally suited for the fabrication of solid state lithium ion batteries. We have also explored the efficiency of silicophosphate glass powders as possible electrode materials. Glass of composition 70SiO2/30P2O5 was prepared by using Pluronic P-123 tri-block copolymer along with suitable precursor sols. Cyclic voltammetric and galvanostatic charge/discharge measurements were carried out on the samples prepared in combination with suitable conductive fillers using a two-electrode system. These exhibited a high specific capacitance of 356 F g-1 making them ideally suitable as electrode materials for making a lithium ion solid state battery system.

  7. Determination of Thallium(I by Hybrid Mesoporous Silica (SBA-15 Modified Electrode

    Geeta Rani

    2016-01-01

    Full Text Available Chemically modified mesoporous silica material (SBA-15 was used for the construction of Tl(I selective carbon paste electrode. The best response was found with the electrode containing 10% modifier as electrode material. The electrode has a lower detection limit of 6.0 × 10−9 M in a working concentration range of 1.0 × 10−8–1.0 × 10−1 M. The selectivity coefficient calculated by match potential method (MPM shows the high selectivity of electrode towards Tl(I over other tested ions. The electrode was successfully applied as an indicator electrode for the titration of 0.01 M TlNO3 solution with standards EDTA solution and for sequential titration of mixture of different anions.

  8. Direct hydrothermal synthesis of iron-containing mesoporous silica SBA-15 : potential as a support for gold nanoparticles

    Li, Y.; Guan, Y.; Santen, van R.A.; Kooyman, P.J.; Dugulan, A.I.; Li, C.; Hensen, E.J.M.

    2009-01-01

    The preparation of mesoporous silica SBA-15 with high iron loadings (14-90 wt % Fe2O3) as a suitable support for gold nanoparticles to be used in CO oxidation catalysis has been investigated. The support materials were prepared by a direct hydrothermal two-step pH adjusting method which consisted of

  9. Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method.

    Selvaraj, M; Park, D-W; Kim, I; Kawi, S; Ha, C S

    2012-08-28

    Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).

  10. Enhanced photocatalytic performance of mesoporous TiO{sub 2} coated SBA-15 nanocomposites fabricated through a novel approach: supercritical deposition aided by liquid-crystal template

    Liu, Chen; Lin, Xiao; Li, Youji, E-mail: bcclyj@163.com; Xu, Peng; Li, Ming; Chen, Feitai

    2016-03-15

    Highlights: • Highly uniform mesoporous TiO{sub 2} nanopartices were coated SBA-15. • MT showed smaller crystallite size, higher hydroxyl content and surface area. • MT/SBA-15 show enhanced photocatalytic activity and high reused activity. • The optimum MT loading rate and calcination temperature were obtained to be 15% and 400 °C, respectively. • Photocatalytic behaviors are discussed in terms of the Langmuir–Hinshelwood model. - Abstract: Mesoporous TiO2 coated SBA-15 (MT@S) nanocomposites were fabricated through supercritical CO{sub 2} deposition aided by liquid-crystal template. The as-prepared samples were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy and so on. The results reveal that MT uniformly deposited onto silica with titania incorporated in SBA-15 channels, showed smaller crystallite size, higher hydroxyl content and surface area than nonporous TiO{sub 2} coated SBA-15 (NT@S) obtained by a similar route without template. With TiO{sub 2} loading ratio of 15 wt% and calcination temperature of 400 °C, 15%MT@S-400 showed the enhanced degradation efficiency for azo dyes (methylene blue, methyl orange, and rhodamine B) and phenol in comparsion with 15%NT@S-400, due to those improved textural and physicochemical properties. Meanwhile, the reused MT@S also showed high photoactivity. Additionally, the effects of MT content and calcination temperature have been examined as operational parameters. Photocatalytic reactions followed pseudo-first-order kinetics and are discussed in terms of the Langmuir–Hinshelwood model.

  11. The structure heterogeneity of silica mesopores of Sba-15 in respect to the pluronic 123 template concentration

    Dhaneswara, D.; Fatriansyah, J. F.; Putranto, D. A.; Utami, S. A. A.; Delayori, F.

    2018-01-01

    The analysis of structure heterogeneity factor of silica mesoporous SBA-15 has been conducted. The structure factor has been found to be different for low and high concentration of Pluronic-123 template. The structure heterogeneity of high concentration of Pluronic-123 has been found less than 1 while for low concentration, the structure heterogeneity was found to be larger than 1. This indicates the dissimilarity of the structure and can be used as a probe to detect the formation of large mesopores. It also was found that the system exhibits type IV and H1 adsorption type which indicates the capillary condensation and interconnected pores.

  12. Iron-functionalized Al-SBA-15 for benzene hydroxylation

    Li, Y.; Xia, H.; Fan, F.; Feng, Z.; Santen, van R.A.; Hensen, E.J.M.; Li, Can

    2008-01-01

    For the first time an ordered mesoporous silica (Fe–Al-SBA-15) with catalytically active isolated Fe surface species for the hydroxylation of benzene with nitrous oxide is prepared by introduction of Fe3+ in the synthesis gel of Al-SBA-15. Graphical abstract image for this article (ID: b717079c)

  13. Heat storage properties of organic phase-change materials confined in the nanospace of mesoporous SBA-15 and CMK-3.

    Kadoono, Tomosuke; Ogura, Masaru

    2014-03-28

    A novel type of material encapsulating phase-change materials (PCMs) is reported concerning their implication for use as thermal energy storage devices. The composites of siliceous SBA-15 or carbonaceous CMK-3 mesoporous assemblies and organic PCMs could be used to make leak-free devices that retain their capabilities over many thermal cycles for heat storage/release. A confinement effect was observed that alters the thermal properties of the encapsulated PCM, especially in CMK-3 without any similar effects in other carbon materials.

  14. Self-immobilization of acidogenic mixed consortia on mesoporous material (SBA-15) and activated carbon to enhance fermentative hydrogen production

    Mohan, S. Venkata; Mohanakrishna, G.; Sarma, P.N. [Bioengineering and Environmental Centre, Indian Institute of Chemical Technology, Hyderabad 500607 (India); Reddy, S. Sreevardhan; Raju, B. David; Rao, K.S. Rama [Catalysis and Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500607 (India)

    2008-11-15

    The influence of self-immobilization of enriched acidogenic mixed consortia on fermentative hydrogen (H{sub 2}) production was studied on different supporting materials [SBA-15 (mesoporous) and activated carbon (granular; GAC and powder; PAC)] using chemical wastewater as substrate. Batch fermentation experiments were performed with same substrate at different organic loading rates (OLRs) under acidophilic microenvironment (pH 5.5) and room temperature (28 {+-} 2 C). Experimental data evidenced the effectiveness of attached growth on both the H{sub 2} yields and substrate degradation efficiency, particularly at higher loading rates. Among the three materials evaluated, immobilization on SBA-15 material showed comparatively effective performance in enhancing both H{sub 2} yield and substrate degradation. Suspended growth (SG-control) culture showed inhibition in terms of both H{sub 2} production and substrate degradation especially at applied higher loading rates. Immobilization on SBA-15 resulted in nine times higher H{sub 2} production (7.29 mol/kg COD{sub R}-day at OLR of 0.83 kg COD/m{sup 3}-day) than the lowest yield observed (suspended growth at OLR of 2.55 kg COD/m{sup 3}-day). Maximum substrate degradation rate (SDR) of 0.96 kg COD/m{sup 3}-day (OLR 2.55 kg COD/m{sup 3}-day) was also observed with SBA-15 immobilization, which is 1.62 times higher than the lowest substrate degradation observed with SG-control experiments with the same OLR. Attached growth on GAC and PAC also showed remarkable improvement in the process performance at higher OLRs compared to SG-control. (author)

  15. Efficient solid-phase microextraction of triazole pesticides from natural water samples using a Nafion-loaded trimethylsilane-modified mesoporous silica coating of type SBA-15

    Abolghasemi, Mir Mahdi; Hassani, Sona; Bamorowat, Mehdi

    2016-01-01

    A mesoporous silica surface of type SBA-15 was made more hydrophobic by modification with ethoxytrimethylsilane to obtain a hybrid organic–inorganic mesoporous nanocomposite, which then was impregnated with Nafion. The resulting nanocomposite was used as a fiber coating for solid-phase microextraction (SPME). The trimethylsilyl-modified Nafion/SBA-15 nanocomposite with high surface area was characterized by SEM and FTIR. It was immobilized on a stainless steel wire in order to fabricate a fiber for SPME. This fiber was evaluated for its suitability for extracting triazolic agrochemicals from water samples before their quantification through a combination of gas chromatography and mass spectrometry. Experimental conditions for fiber coating, extraction time, stirring rate, ionic strength, pH value, desorption temperature and desorption time were optimized. Under optimum conditions, the repeatability for one fiber (for n = 3) ranges from 4.3 to 5.6 % (relative standard deviation). The detection limits are between 50 and 90 pg⋅mL −1 . The method is simple, fast, low-cost (in terms of equipment), and the fiber used for SPME has high thermal stability and good recovery. (author)

  16. Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

    Werghi, Baraa; Pump, Eva; Tretiakov, Mykyta; Abou-Hamad, Edy; Gurinov, Andrei; Doggali, Pradeep; Anjum, Dalaver H.; Cavallo, Luigi; Bendjeriou-Sedjerari, Anissa; Basset, Jean-Marie

    2018-01-01

    Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

  17. Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

    Werghi, Baraa

    2018-03-05

    Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

  18. Preparation and characterization of glycidyl methacrylate organo bridges grafted mesoporous silica SBA-15 as ibuprofen and mesalamine carrier for controlled release

    Rehman, Fozia; Rahim, Abdur; Airoldi, Claudio; Volpe, Pedro L.O.

    2016-01-01

    Mesoporous silica SBA-15 was synthesized and functionalized with bridged polysilsesquioxane monomers obtained by the reaction of 3-aminopropyltriethoxy silane with glycidyl methacrylate in 2:1 ratio. The synthesized mesoporous silica materials were characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, nitrogen adsorption, X-ray diffraction, thermogravimetry and scanning electron microscopy. The nuclear magnetic resonance in the solid state is in agreement with the sequence of carbon distributed in the attached organic chains, as expected for organically functionalized mesoporous silica. After functionalization with organic bridges the BET surface area was reduced from 1311.80 to 494.2 m 2 g −1 and pore volume was reduced from 1.98 to 0.89 cm 3 g −1 , when compared to original precursor silica. Modification of the silica surface with organic bridges resulted in high loading capacity and controlled release of ibuprofen and mesalamine in biological fluids. The Korsmeyer–Peppas model better fits the release data indicating Fickian diffusion and zero order kinetics for synthesized mesoporous silica. The drug release rate from the modified silica was slow in simulated gastric fluid, (pH 1.2) where less than 10% of mesalamine and ibuprofen were released in initial 8 h, while comparatively high release rates were observed in simulated intestinal (pH 6.8) and simulated body fluids (pH 7.2). The preferential release of mesalamine at intestinal pH suggests that the modified silica could be a simple, efficient, inexpensive and convenient carrier for colon targeted drugs, such a mesalamine and also as a controlled drug release system. - Highlights: • Modified SBA-15 silica with long hydrophobic chains was evaluated as drug carrier. • This silica showed improved loading capacity and controlled release of ibuprofen. • Compared to gastric pH high release rate of mesalamine was observed at colonic pH. • Modified silica

  19. NiMo Catalysts Supported on the Nb Modified Mesoporous SBA-15 and HMS: Effect of Thioglycolic Acid Addition on HDS.

    Palcheva, R.; Kaluža, Luděk; Dimitrov, L.; Tyuliev, G.; Avdeev, G.; Jirátová, Květa; Spojakina, A.

    2016-01-01

    Roč. 50, JUN 25 (2016), s. 24-34 ISSN 0926-860X R&D Projects: GA ČR GAP106/11/0902 Institutional support: RVO:67985858 Keywords : HDS * mesoporous SBA-15 and HMS * thioglycolic acid Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.339, year: 2016

  20. Fluorescence properties of riboflavin-functionalized mesoporous silica SBA-15 and riboflavin solutions in presence of different metal and organic cations

    Lewandowski, Dawid; Schroeder, Grzegorz; Sawczak, Mirosław; Ossowski, Tadeusz

    2015-10-01

    Riboflavin was covalently linked to mesoporous SBA-15 silica surface via grafting technique. Then fluorescence properties of the system obtained were analyzed in the presence of several metal and organic cations. Both quenching and strengthening of fluorescence as well as significant changes in the maximum fluorescence wavelength were observed. The results were compared with absorption and fluorescence data obtained for riboflavin water solutions.

  1. One-Pot Synthesis of Mesoporous SBA-15 Containing Protonated 3- Aminopropyl Groups

    Sliesarenko, V.V.; Dudarko, O.A.; Zub, Y.L.; Seisenbaeva, G.A.; Kessler, V.G.; Topka, Pavel; Šolcová, Olga

    2013-01-01

    Roč. 20, č. 5 (2013), s. 1315-1321 ISSN 1380-2224 R&D Projects: GA TA ČR TA01020804 Grant - others:NATO SPSP(US) SfP-984398 Institutional support: RVO:67985858 Keywords : mesoporous silica * molybdophosphoric acid immobilization * alkyl ammonium group Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.316, year: 2013

  2. Applying Mesoporous Silica SBA-15 in Electrochemical Detection of DNA Hybridization

    Josypčuk, Oksana; Fojta, Miroslav; Daňhel, Aleš; Josypčuk, Bohdan

    2016-01-01

    Roč. 28, č. 8 (2016), s. 1860-1864 ISSN 1040-0397 R&D Projects: GA ČR GAP206/11/1638 Institutional support: RVO:68081707 ; RVO:61388955 Keywords : voltammetry * sensor DNA hybridization * mesoporous silica Subject RIV: CG - Electrochemistry Impact factor: 2.851, year: 2016

  3. One-Pot Synthesis of Mesoporous SBA-15 Containing Protonated 3- Aminopropyl Groups

    Sliesarenko, V.V.; Dudarko, O.A.; Zub, Y.L.; Seisenbaeva, G.A.; Kessler, V.G.; Topka, Pavel; Šolcová, Olga

    2013-01-01

    Roč. 20, č. 5 (2013), s. 1315-1321 ISSN 1380-2224 R&D Projects: GA TA ČR TA01020804 Grant - others: NATO SPSP(US) SfP-984398 Institutional support: RVO:67985858 Keywords : mesoporous silica * molybdophosphoric acid immobilization * alkyl ammonium group Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.316, year: 2013

  4. Preparation and characterization of glycidyl methacrylate organo bridges grafted mesoporous silica SBA-15 as ibuprofen and mesalamine carrier for controlled release

    Rehman, Fozia, E-mail: fozia@iqm.unicamp.br [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil); Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS Institute of Information Technology, Lahore (Pakistan); Rahim, Abdur [Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS Institute of Information Technology, Lahore (Pakistan); Airoldi, Claudio; Volpe, Pedro L.O. [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil)

    2016-02-01

    Mesoporous silica SBA-15 was synthesized and functionalized with bridged polysilsesquioxane monomers obtained by the reaction of 3-aminopropyltriethoxy silane with glycidyl methacrylate in 2:1 ratio. The synthesized mesoporous silica materials were characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, nitrogen adsorption, X-ray diffraction, thermogravimetry and scanning electron microscopy. The nuclear magnetic resonance in the solid state is in agreement with the sequence of carbon distributed in the attached organic chains, as expected for organically functionalized mesoporous silica. After functionalization with organic bridges the BET surface area was reduced from 1311.80 to 494.2 m{sup 2} g{sup −1} and pore volume was reduced from 1.98 to 0.89 cm{sup 3} g{sup −1}, when compared to original precursor silica. Modification of the silica surface with organic bridges resulted in high loading capacity and controlled release of ibuprofen and mesalamine in biological fluids. The Korsmeyer–Peppas model better fits the release data indicating Fickian diffusion and zero order kinetics for synthesized mesoporous silica. The drug release rate from the modified silica was slow in simulated gastric fluid, (pH 1.2) where less than 10% of mesalamine and ibuprofen were released in initial 8 h, while comparatively high release rates were observed in simulated intestinal (pH 6.8) and simulated body fluids (pH 7.2). The preferential release of mesalamine at intestinal pH suggests that the modified silica could be a simple, efficient, inexpensive and convenient carrier for colon targeted drugs, such a mesalamine and also as a controlled drug release system. - Highlights: • Modified SBA-15 silica with long hydrophobic chains was evaluated as drug carrier. • This silica showed improved loading capacity and controlled release of ibuprofen. • Compared to gastric pH high release rate of mesalamine was observed at colonic pH.

  5. Facile fabrication of mesoporous Fe-Ti-SBA15 silica with enhanced visible-light-driven simultaneous photocatalytic degradation and reduction reactions

    Chang, Fei; Jiao, Mingzhi; Xu, Quan; Deng, Baoqing; Hu, Xuefeng

    2018-03-01

    A series of mesoporous iron-titanium-containing silica Fe-TiO2-SBA15 (FTS) were constructed via a facile one-pot hydrothermal route and subsequently characterized by X-ray diffraction patterns, UV-vis diffuse reflection spectroscopy, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption-desorption, X-ray photoelectron spectroscopy, and X-ray energy dispersion spectroscopy. By analyses, these samples possessed ordered two-dimensional hexagonal mesoporous structures, mainly involving mixed dual-phases of anatase and rutile TiO2, like commercial titania P25. The UV-vis diffuse reflection spectra demonstrated the presence of Fe species that was further confirmed by the X-ray photoelectron spectra and X-ray energy dispersion spectrum. The existence of Fe species in form of Fe3+ cations played an important role on the phase composition and electronic structure of these samples. With structural and morphological merits, these samples exhibited relatively high photocatalytic efficiency toward the degradation of dye methylene blue (MB) and reduction of Cr(VI) under visible-light irradiation, comparing with P25. In addition, among all candidates, the sample with a Fe/Si molar ratio of 0.03 showed the highest catalytic performance under optimal conditions, especially in the coexistence of both MB and Cr(VI), revealing an obviously synergistic effect when the consumption of both contaminants occurred. Finally, a primary catalytic mechanism was speculated on basis of active species capture experiments.

  6. Controlled and localized delivery of c-myc AS-ODN to cells by 3-aminopropyl-trimethoxylsilane modified SBA-15 mesoporous silica

    Zhang, Juan; Chen, Minmin; Zhao, Xiqiu; Zhang, Min; Mao, Jinxiang; Cao, Xichuan; Zhang, Zhuoqi

    2018-01-01

    SBA-15 mesoporous silicate was synthesized and functionalized with 3-aminopropyl organic groups through a post-synthesis method. The materials were characterized consecutively by powder X-ray diffraction (XRD), N2 adsorption/desorption analysis and solid-state magic-angle spinning 29Si nuclear magnetic resonance (MAS NMR). Human c-myc anti-sense oligodeoxyneucleotide (AS-ODN) was selected as a model molecule to be loaded onto the surface of bare and functionalized SBA-15 via different loading conditions. It has been found that the amount of AS-ODN incorporated into the porous matrix is strongly dependent on the surface properties, pH of the loading solvent and AS-ODN concentration. The release behaviour of AS-ODN from modified SBA-15 materials was also investigated and depended on conditions chosen. Cellular uptake of the eluted AS-ODN into Hela cells was observed by fluorescent microscopy. The materials showed excellent cytocompatibility. The AS-ODN keeps full transfection and expression activities indicating its structural integrity. The functionalized SBA-15 is an excellent prospect as a biomedical material candidate for the future.

  7. Preparation and characterization of catalyst 20% Co/SBA-15

    Lima, L.A.; Nogueira, A.C.; Rodrigues, J.J.; Rodrigues, M.G.F.

    2012-01-01

    The utilization of molecular sieves as supports for cobalt catalysts are promising. SBA-15 is a class of mesoporous silicate with a high thermal stability and high degree of structural order, which confers an important feature for the catalytic process. It was prepared SBA-15 molecular sieve with molar composition: 1.0 TEOS: 0017P123: 5.7 HCl: 193 H2O. The deposition of cobalt on the substrate SBA-15 was performed by wet impregnation, using a solution of 0.1M cobalt nitrate. The materials were characterized by the techniques of X-Ray Diffraction (XRD), chemical analysis by X-Ray Spectrometry by Energy Dispersive (EDX), and nitrogen adsorption (BET). By XRD and BET verified the formation of SBA-15, and after the impregnation there was no change in the structure, with EDX showed that the impregnation method is efficient, the sample showed cobalt content close to the nominal value. (author)

  8. Effects of carbon coating and pore corrugation on capillary condensation of nitrogen in SBA-15 mesoporous silica.

    Morishige, Kunimitsu

    2013-09-24

    To examine the origin of an ink-bottle-like structure in SBA-15 formed by carbon coating and the effects of pore corrugation on capillary condensation and evaporation of a vapor in the cylindrical pores, we measured the adsorption isotherms of nitrogen at 77 K on 10 kinds of SBA-15 samples before and after a carbon coating process by the exposure to acetylene at 1073 K, as well as desorption scanning curves and subloops on the untreated samples. These SBA-15 samples were synthesized under the different conditions of initial SiO2/P123 ratio and hydrothermal treatment. SBA-15 with relatively large microporosity tends to form easily constrictions inside the main channels by the carbon coating. This strongly suggests that the rough pore walls of SBA-15 may induce the incomplete wetting of carbon layers on the pore walls to form the constrictions inside the cylindrical pores. A comparison of two subloops implies that the pores of SBA-15 synthesized with a SiO2/P123 ratio of 75 consist of an assembly of connecting domains of different diameters; that is, the pores are highly corrugated. For SBA-15 synthesized with a SiO2/P123 ratio of 60, the amplitude of the pore corrugation is significantly decreased by the prolonged hydrothermal treatment at 373 K. On the other hand, for SBA-15 synthesized with a SiO2/P123 ratio of 45, the amplitude of the corrugation is negligibly small, although the cylindrical pores are interconnected through narrow necks with each other. It is found that the smaller the amplitude of the pore corrugation, the smaller the width of the hysteresis loop.

  9. Effect of silica/titania ratio on enhanced photooxidation of industrial hazardous materials by microwave treated mesoporous SBA-15/TiO{sub 2} nanocomposites

    Mehta, Akansha; Mishra, Amit; Sharma, Manisha; Singh, Satnam; Basu, Soumen, E-mail: soumen.basu@thapar.edu [Thapar University, School of Chemistry and Biochemistry (India)

    2016-07-15

    In this study microwave assisted technique has been adopted for the synthesis of different weight ratios of TiO{sub 2} dispersed on Santa barbara amorphous-15 (SBA-15) support. Morphological study revealed TiO{sub 2} particles (4–10 nm) uniformly distributed on SBA-15 while increases in SBA-15 content results in higher specific surface area (524–237 m{sup 2}/g). The diffraction intensity of 101 plane of anatase polymorph was seen increasing with increase in TiO{sub 2} ratio. All the photocatalysts were having a mesoporous nature and follow the Langmuir IV isotherm, SBA-15 posses the highest pore volume (0.93 cm{sup 3} g{sup −1}) which consistently decreased with TiO{sub 2} content and was lowest (0.50 cm{sup 3} g{sup −1}) in case of 5 wt% of TiO{sub 2} followed by P25 (0.45 cm{sup 3} g{sup −1}) while pore diameter increased after TiO{sub 2} incorporation due to pore strain. The photocatalytic activity of the nanocomposites were analysed for the photodegradation of alizarin dye and pentachlorophenol under UV light irradiation. The reaction kinetics suggested the highest efficiency (98 % for alizarin and 94 % for PCP) of 5 wt% TiO{sub 2} compared to other photocatalysts, these nanocomposites were reused for several cycles, which is most important for heterogeneous photocatalytic degradation reaction.Graphical abstractThis study demonstrates the synthesis of silica embedded TiO{sub 2} nanocomposites by microwave assisted technique and their catalytic influence on degradation of organic dyes and pollutants. Higher loading of titania (SBA-15/TiO{sub 2}, 1:5) results better catalytic performance than commercial nano TiO{sub 2} (P25).

  10. Preparation, characterization and catalytic activity of mesoporous Ag2HPW12O40/SBA-15 and Ag2HPW12O40/TiO2 composites

    Holclajtner-Antunović, Ivanka; Bajuk-Bogdanović, Danica; Popa, Alexandru; Sasca, Viorel; Nedić Vasiljević, Bojana; Rakić, Aleksandra; Uskoković-Marković, Snežana

    2015-01-01

    The current study reports the synthesis and characterization of tungstophosphoric acid and its acid silver salt supported on mesoporous molecular sieve SBA-15 and TiO 2 . Because silver salts are partially insoluble, the SBA-15 and TiO 2 supported silver acid salts were prepared by two step sequential impregnations. The synthesized catalysts were characterized by various physicochemical methods such as Fourier transform infrared and Raman spectroscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and nitrogen physisorption at −196 °C. It is observed that both active phases keep their Keggin-type structure after being supported on the supports while their specific surface area is considerably increased by deposition on mesoporous substrates. The results also indicated that the synthesized catalysts retained the morphology specific for each of the supports, while their thermal stability is increased in comparison with their active phases. The catalytic activity of the prepared catalysts was probed for the vapor phase dehydration of ethanol at 300 °C. Results revealed that all the catalysts show considerably improved catalytic activity in comparison to the bulk active phases. - Highlights: • SBA-15 and TiO 2 supported Ag 2 HPW 12 O 40 and H 3 PW 12 O 40 were prepared. • Active phases are uniformly dispersed without changing morphology of the substrates. • Composites are more thermally stable than active phases. • Composites exhibit high catalytic activity for gas phase ethanol dehydration

  11. Highly Sensitive Fluorescence Probe Based on Functional SBA-15 for Selective Detection of Hg2+

    Wang Xiaoyu

    2010-01-01

    Full Text Available Abstract An inorganic–organic hybrid fluorescence chemosensor (DA/SBA-15 was prepared by covalent immobilization of a dansylamide derivative into the channels of mesoporous silica material SBA-15 via (3-aminopropyltriethoxysilane (APTES groups. The primary hexagonally ordered mesoporous structure of SBA-15 was preserved after the grafting procedure. Fluorescence characterization shows that the obtained inorganic–organic hybrid composite is highly selective and sensitive to Hg2+ detection, suggesting the possibility for real-time qualitative or quantitative detection of Hg2+ and the convenience for potential application in toxicology and environmental science.

  12. Intermediate-range order in mesoporous silicas investigated by a high-energy X-ray diffraction technique

    Wakihara, Toru; Fan, Wei; Ogura, Masaru; Okubo, Tatsuya; Kohara, Shinji; Sankar, Gopinathan

    2008-01-01

    We perform a high-energy X-ray diffraction study comparing bulk amorphous silica with MCM-41 and SBA-15 that are representative mesoporous silicas prepared in basic and acidic conditions, respectively. It is revealed that mesoporous silicas, especially SBA-15, have less ordered structures and contain larger fractions of three- and four-membered rings than does bulk amorphous silica. (author)

  13. Metathesis of 2-pentene over Mo and W supported mesoporous molecular sieves MCM-41 and SBA-15

    Ibrahim, M. A.; Akhtar, M. N.; Čejka, Jiří; Montanari, E.; Balcar, Hynek; Kubů, Martin; Al-Khattaf, S. S.

    2017-01-01

    Roč. 53, SEP 2017 (2017), s. 119-126 ISSN 1226-086X R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : metathesis * MCM-41 * SBA-15 Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.421, year: 2016

  14. 无外加酸体系中AlSBA¯15为模板,有序介孔炭材料CMK¯3的合成与表征%Synthesis and characterization of ordered mesoporous carbons CMK_3 produced by tailoring the mesopores of an AlSBA_15 hard template synthesized without acid

    石磊; 徐艳; 邢立淑; 李湘萍; 杨成; 林森

    2014-01-01

    在无外加酸体系中改变晶化温度合成AlSBA¯15介孔材料,并以此为刚性模板,蔗糖为碳源,合成出一系列具有不同孔结构的有序介孔炭材料CMK¯3,系统考察晶化温度对AlSBA¯15和其反相复制结构CMK¯3孔道结构的影响。结果显示在无外加酸合成体系中改变晶化温度可对AlSBA¯15的孔道结构进行有效调控,通过结构复制技术可制备出具有不同结构的CMK¯3。控制刚性模板AlSBA¯15的晶化温度为90益,所得介孔炭材料CMK¯3(CMK¯3(90))结构最佳,除介孔排列高度有序外,还具有高比表面积(1688 m2·g-1)和大孔容(0.95 cm3·g-1)。另外,对CMK¯3的微孔性质与刚性模板孔壁中的次级介孔结构的内在联系进行研究,发现调变刚性模板的晶化温度可以有效改善有序介孔炭材料CMK¯3的结构性质。%Highly ordered mesoporous carbons ( OMCs) designated CMK¯3 were synthesized using mesoporous Al¯SBA¯15 with different textural properties as hard templates and sucrose as a carbon source. Al¯SBA¯15 is an ordered mesoporous alumina¯silica synthesized with a soft template, P123. The effect of the aging temperature for the hard templates on the pore structure of CMK¯3 was investigated. X¯ray diffraction, N2 adsorption and transmission electron microscopy were used to characterize the pore structures of the hard templates and the resultant CMK¯3. Result indicates that CMK¯3 with different pore structures can be obtained by tailor¯ ing the pore structures of the hard templates bysimply controlling the aging temperature in an acid¯free medium. The best CMK¯3 possessed a highly¯ordered pore structure, and a very high BET surface area (1 688 m2 ·g-1 ) and pore volume (0. 95 cm3 ·g-1 ) when the hard template was aged at 90 ℃. The microporous character of the CMK¯3 was related to the thickness of the mesopore wall of the hard templates. The textural characteristics of the resultant CMK¯3 can be improved by simply

  15. Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

    Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

    2015-02-01

    A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties. Copyright © 2014. Published by Elsevier B.V.

  16. A well-defined mesoporous amine silica surface via a selective treatment of SBA-15 with ammonia

    Bendjeriou-Sedjerari, Anissa; Pelletier, Jeremie; Abou-Hamad, Edy; Emsley, Lyndon; Basset, Jean-Marie

    2012-01-01

    2D double-quantum 1H- 1H NMR unambiguously shows that the "isolated" Si-OH surface silanols of dehydroxylated SBA-15 are converted upon treatment with ammonia into single silylamine surface site Si-NH 2. The "gem" di-silanols (Si(OH) 2) remain intact. Treatment using HMDS produces (Si(OSiMe 3) 2) but leaves Si-NH 2 untouched. The resulting surface is hydrophobic and stable. © The Royal Society of Chemistry 2012.

  17. Functionalized SBA-15 materials for bilirubin adsorption

    Tang, Tao; Zhao, Yanling; Xu, Yao; Wu, Dong; Xu, Jun; Deng, Feng

    2011-05-01

    To investigate the driving force for bilirubin adsorption on mesoporous materials, a comparative study was carried out between pure siliceous SBA-15 and three functionalized SBA-15 mesoporous materials: CH 3-SBA-15 (MS), NH 2-SBA-15 (AS), and CH 3/NH 2-SBA-15 (AMS) that were synthesized by one-pot method. The obtained materials exhibited large surface areas (553-810 m 2/g) and pore size (6.6-7.1 nm) demonstrated by XRD and N 2-ad/desorption analysis. The SEM images showed that the materials had similar fiberlike morphology. The functionalization extent was calculated according to 29Si MAS NMR spectra and it was close to the designed value (10%). The synthesized mesoporous materials were used as bilirubin adsorbents and showed higher bilirubin adsorption capacities than the commercial active carbon. The adsorption capacities of amine functionalized samples AMS and AS were larger than those of pure siliceous SBA-15 and MS, indicating that electrostatic interaction was the dominant driving force for bilirubin adsorption on mesoporous materials. Increasing the ionic strength of bilirubin solution by adding NaCl would decrease the bilirubin adsorption capacity of mesoporous material, which further demonstrated that the electrostatic interaction was the dominant driving force for bilirubin adsorption. In addition, the hydrophobic interaction provided by methyl groups could promote the bilirubin adsorption.

  18. SBA-15 mesoporous silica free-standing thin films containing copper ions bounded via propyl phosphonate units - preparation and characterization

    Laskowski, Lukasz, E-mail: lukasz.laskowski@kik.pcz.pl [Czestochowa University of Technology, Institute of Computational Intelligence, Unit of Microelectronics and Nanotechnology, Al. Armii Krajowej 36, 42–201 Czestochowa (Poland); Laskowska, Magdalena, E-mail: magdalena.laskowska@onet.pl [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, 31-342 Krakow, ul. Radzikowskiego 152 (Poland); Jelonkiewicz, Jerzy, E-mail: jerzy.jelonkiewicz@kik.pcz.pl [Czestochowa University of Technology, Institute of Computational Intelligence, Unit of Microelectronics and Nanotechnology, Al. Armii Krajowej 36, 42–201 Czestochowa (Poland); Dulski, Mateusz, E-mail: mateusz.dulski@us.edu.pl [University of Silesia, Faculty of Computer Science and Materials Science, Institute of Materials Science, Silesian Center for Education and Interdisciplinary Research, ul. 75 Pułku Piechoty 1A, 41–500 Chorzów (Poland); Wojtyniak, Marcin, E-mail: marcin.wojtyniak@us.edu.pl [University of Silesia, Institute of Physics, Silesian Center for Education and Interdisciplinary Research, ul. 75 Pułku Piechoty 1A, 41–500 Chorzów (Poland); Fitta, Magdalena, E-mail: magdalena.fitta@ifj.edu.pl [H. Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, 31–342 Krakow, ul. Radzikowskiego 152 (Poland); Balanda, Maria, E-mail: Maria.Balanda@ifj.edu.pl [H. Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, 31–342 Krakow, ul. Radzikowskiego 152 (Poland)

    2016-09-15

    The SBA-15 silica thin films containing copper ions anchored inside channels via propyl phosphonate groups are investigated. Such materials were prepared in the form of thin films, with hexagonally arranged pores, laying rectilinear to the substrate surface. However, in the case of our thin films, their free standing form allowed for additional research possibilities, that are not obtainable for typical thin films on a substrate. The structural properties of the samples were investigated by X-ray reflectometry, atomic force microscopy (AFM) and transmission electron microscopy (TEM). The molecular structure was examined by Raman spectroscopy supported by numerical simulations. Magnetic measurements (SQUID magnetometry and EPR spectroscopy) showed weak antiferromagnetic interactions between active units inside silica channels. Consequently, the pores arrangement was determined and the process of copper ions anchoring by propyl phosphonate groups was verified in unambiguous way. Moreover, the type of interactions between magnetic atoms was determined. - Highlights: • Functionalized free-standing SBA-15 thin films were synthesized for a first time. • Thin films synthesis procedure was described in details. • Structural properties of the films were thoroughly investigated and presented. • Magnetic properties of the novel material was investigated and presented.

  19. Research on the Ordered Mesoporous Silica for Tobacco Harm Reduction

    Wang, Y.; Y Li, Z.; Ding, J. X.; Hu, Z. J.; Liu, Z.; Zhou, G.; Huang, T. H.

    2017-12-01

    For reducting tobacco harm, this paper prepared an ordered mesoporous silica by using triblock copolymer Pluronic P123 as template. The property of this material was characterized by the X-ray scattering spectrum(XRD), Transmission electron microscopy(TEM), Scanning electron microscopy (SEM) and Nitrogen adsorption/desorption. Then this ordered mesoporous silica was added into the cigarette filter in order to researching its effect of cigarette harm index. The result shows that the feature of SBA-15 was grain morphology, ordered arrangement, tubular porous 2-D hexagonal structure. The application of SBA-15 in cigarette filter can selectively reduce harmful components in cigarette smoke such as crotonaldehyde, hydrogen cyanide, benzo pyrene and tar. The synthesized SBA-15 could properly reduce cigarette harm index.

  20. Synthesis and structure of pyridine-functionalized mesoporous SBA-15 organosilicas and their application for sorption of diclofenac

    Barczak, Mariusz

    2018-02-01

    A series of pyridine-functionalized mesoporous silicas have been prepared for the first time via direct co-condensation of tetraethoxysilane (TEOS) and 2-(2-pyridyl)ethyltrimethoxysilane (PETS) using the block copolymer Pluronic P123 as a structure-directing agent. The obtained materials were fully characterized by a wide range of instrumental techniques and employed as adsorbents for the removal of a diclofenac which is considered a priority hazardous drug. The synthesized materials exhibit a high adsorption capacities and rapid adsorption rates. The structural and adsorption properties depend largely on the relative amount of PETS/TEOS ratio: the gradual degradation of ordered structure and porosity was observed with the increasing amount of PETS. However due to the highest loading of pyridine units the most structurally degraded material had the highest adsorption uptake (631 mg g-1) indicating that the surface chemistry plays - along with porosity - an important role in governing the adsorption process. The experimental adsorption data were modelled using the Langmuir, Freundlich and Langmuir-Freundlich isotherms - among them the Langmuir-Freundlich model turned out to be the most suitable for describing adsorption behaviour of diclofenac onto the materials. The collected data show that the pyridine-functionalized mesoporous silicas can be a promising absorbent of pharmaceuticals.

  1. Enthalpy and interfacial free energy changes of water capillary condensed in mesoporous silica, MCM-41 and SBA-15.

    Kittaka, Shigeharu; Ishimaru, Shinji; Kuranishi, Miki; Matsuda, Tomoko; Yamaguchi, Toshio

    2006-07-21

    The effect of confinement on the solid-liquid phase transitions of water was studied by using DSC and FT-IR measurements. Enthalpy changes upon melting of frozen water in MCM-41 and SBA-15 were determined as a function of pore size and found to decrease with decreasing pore size. The melting point also decreased almost monotonically with a decrease in pore size. Analysis of the Gibbs-Thomson relation on the basis of the thermodynamic data showed that there were two stages of interfacial free energy change after the constant region, i.e., below a pore size of 6.0 nm: a gradual decrease down to 3.4 nm and another decrease after a small jump upward. This fact demonstrates that the simple Gibbs-Thomson relation, i.e., a linear relation between the melting point change and the inverse pore size, is limited to the range not far from the melting point of bulk water. FT-IR measurements suggest that the decrease in enthalpy change and interfacial free energy change with decreasing pore size reflect the similarity of the structures of both liquid and solid phases of water in smaller pores at lower temperatures.

  2. Synthesis of ordered mesoporous uranium dioxide by a nanocasting route

    Zhao, Ran; Wang Lin; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center

    2016-11-01

    Ordered mesoporous UO{sub 2} with 3-D structure (for UO{sub 2}-KIT-6) and nanowire bundles (for UO{sub 2}-SBA-15) was synthesized for the first time by a nanocasting route using different ordered mesoporous silica (KIT-6 and SBA-15, respectively) as templates and uranyl nitrate hexahydrate as the metal precursor. The uranyl nitrate was impregnated into the mesopore of the silica template and was converted to U{sub 3}O{sub 8} after the first step. The synthesis of ordered UO{sub 2} mesostructure was achieved by reducing the mesoporous U{sub 3}O{sub 8} with silica composites under 5% H{sub 2}/Ar atmosphere at 700 C, followed by a template removal process. The as-prepared UO{sub 2}-KIT-6 had a particle size of several millimeters, and was constructed with uncoupled subframework mesostructure and crystalline walls, while UO{sub 2}-SBA-15 possessed a rope-like morphology and consisted of nanowire arrays. The surface area and pore volume of ordered UO{sub 2} mesostructure are 47.2 m{sup 2} g{sup -1} and 0.23 cm{sup 3} g{sup -1} for the UO{sub 2}-KIT-6, and 54.4 m{sup 2} g{sup -1} and 0.28 cm{sup 3} g{sup -1} for the UO{sub 2}-SBA-15, respectively.

  3. Hydroxyapatite/MCM-41 and SBA-15 Nano-Composites: Preparation, Characterization and Applications

    Anunziata, Oscar A.; Martínez, Maria L.; Beltramone, Andrea R.

    2009-01-01

    Composites of hydroxyapatite (HaP) and highly ordered large pore mesoporous silica molecular sieves such as, Al-SBA-15 and Al-MCM-41 (denoted as SBA-15 and MCM-41, respectively) were developed, characterized by XRD, BET, FTIR, HRTEM and NMR-MAS, and applied to fluoride retention from contaminated water. The proposed procedure by a new route to prepare the HaP/SBA-15 and HaP/MCM-41, composites generates materials with aluminum only in tetrahedral coordination, according to the 27Al NMR-MAS results. Free OH- groups of HaP nanocrystals, within the hosts, allowed high capacity fluoride retention. The activity of fluoride retention using HaP/MCM-41 or HaP/SBA-15 was 1-2 orders of magnitude greater, respectively, than with pure HaP.

  4. Study on the adsorption of heavy metal ions from aqueous solution on modified SBA-15

    Liliana Giraldo

    2013-01-01

    Full Text Available Amino-functionalized SBA-15 mesoporous silica was prepared, characterized, and used as an adsorbent for heavy metal ions. The organic - inorganic hybrid material was obtained by a grafting procedure using SBA-15 silica with 3-aminopropyl-triethoxysilane and bis(2,4,4-trimethylpentyl phosphinic acid (Cyanex 272, respectively. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD, nitrogen adsorption - desorption, thermogravimetric analysis, FTIR spectroscopy and immersion calorimetry. The organic functional groups were successfully grafted onto the SBA-15 surface and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids was investigated for the adsorption of heavy metal ions from aqueous solutions. The hybrid materials showed high adsorption capacity and high selectivity for zinc ions. Other ions, such as cooper and cobalt were absorbed by the modified SBA-15 material.

  5. Controllable Fabrication of Ordered Mesoporous Bi2WO6 and Its High Photocatalytic Activity under Visible Light

    Xueming Dang

    2014-01-01

    Full Text Available Ordered mesoporous Bi2WO6 was fabricated by nanocasting technique using SBA-15 as the template. The effect of the dosage of SBA-15 on the formation of the ordered structure and the photocatalytic ability of mesoporous Bi2WO6 was discussed. It was confirmed that the ordered mesoporous structure was obtained as the dosage of SBA-15 was 0.3 g. It was found that, compared to Bi2WO6, the RhB degradation rate with ordered mesoporous Bi2WO6 was enhanced under visible light (λ>400 nm by the photocatalytic measurements. The enhanced photocatalytic performance of ordered mesoporous Bi2WO6 was attributed to its particular ordered mesoporous structure which could increase the light-harvesting efficiency, reduce the recombination of the photogenerated charge carriers, and promote the surface reaction.

  6. Aminopropyl-modified mesoporous silica SBA-15 as recovery agents of Cu(II)-sulfate solutions: Adsorption efficiency, functional stability and reusability aspects

    Lombardo, M.V.; Videla, M.; Calvo, A.; Requejo, F.G.; Soler-Illia, G.J.A.A.

    2012-01-01

    Highlights: ► We produce mesoporous amino-silica as Cu(II) adsorbent (1.15–1.75 mmol Cu(II) g −1 ). ► Elemental analysis and XPS demonstrate that amino groups concentrate at the material surface. ► The integrity of the adsorbent through the adsorption, desorption and recycling processes is assessed. ► These materials can be regenerated by exposure to acidic media. ► A careful thermal processing of the material is central to better durability during reprocessing. - Abstract: Hybrid mesoporous materials are potentially useful for metal ion scavenging and retrieval because of their high surface areas, controlled accessibility and tailored functionalization. Some aspects that are linked to the performance of HMM include pore accessibility, stability of the organic functions and reusability. Knowledge of these aspects is critical in the design of adsorption–desorption protocols. In this work we produce and characterize propylamino-substituted large pore silica (SBA-15-N), which is submitted to Cu(II) adsorption from copper sulfate solutions, followed by desorption in acid media and material regeneration. We find that the hybrid material is an efficient adsorbent (1.15–1.75 mmol Cu(II) g −1 ), although a fraction of the organic groups is lost during the adsorption process. An X-ray photoelectron spectroscopy (XPS) study demonstrates that the contents of amino groups are higher in the material surface, leading to different behaviors in Cu(II) complexation along the material. These materials can be regenerated by exposure to acidic media. Thermal processing of the hybrid materials leads to better durability in aqueous solutions during reprocessing, due to enhanced polycondensation of the inorganic framework. Thermally treated samples, once regenerated, are efficient adsorbents in a second step of Cu(II) adsorption. We discuss the materials processing factors involved in the improved adsorption of Cu(II), its quantitative release and reusability of the

  7. Propene epoxidation over Au/Ti-SBA-15 catalysts

    Sacaliuc, E.; Beale, A.M.; Weckhuysen, B.M.; Nijhuis, T.A.

    2007-01-01

    Highly dispersed gold nanoparticles were synthesized within the channels of a mesoporous Ti-SBA-15 support, followed by thorough catalyst characterization and testing in the selective epoxidation of propene to propene oxide. For this purpose, two series of Ti-SBA-15 materials differing in their Ti

  8. Aminopropyl-modified mesoporous silica SBA-15 as recovery agents of Cu(II)-sulfate solutions: Adsorption efficiency, functional stability and reusability aspects

    Lombardo, M.V. [Gerencia Quimica, Centro Atomico Constituyentes, CNEA, Av. General Paz 1499 (B1650KNA), San Martin, Buenos Aires (Argentina); Videla, M. [Rhein Chemie Argentina, Luis Maria Drago 1555 - (B1852LGS) Burzaco, Buenos Aires (Argentina); Calvo, A.; Requejo, F.G. [INIFTA-CONICET, Universidad Nacional de La Plata, CC 16 Sucursal 4 (1900), La Plata (Argentina); Soler-Illia, G.J.A.A., E-mail: gsoler@cnea.gov.ar [Gerencia Quimica, Centro Atomico Constituyentes, CNEA, Av. General Paz 1499 (B1650KNA), San Martin, Buenos Aires (Argentina); DQIAyQF, FCEN, Universidad de Buenos Aires, Ciudad Universitaria, Pab. II (C1428EHA), Buenos Aires (Argentina)

    2012-07-15

    Highlights: Black-Right-Pointing-Pointer We produce mesoporous amino-silica as Cu(II) adsorbent (1.15-1.75 mmol Cu(II) g{sup -1}). Black-Right-Pointing-Pointer Elemental analysis and XPS demonstrate that amino groups concentrate at the material surface. Black-Right-Pointing-Pointer The integrity of the adsorbent through the adsorption, desorption and recycling processes is assessed. Black-Right-Pointing-Pointer These materials can be regenerated by exposure to acidic media. Black-Right-Pointing-Pointer A careful thermal processing of the material is central to better durability during reprocessing. - Abstract: Hybrid mesoporous materials are potentially useful for metal ion scavenging and retrieval because of their high surface areas, controlled accessibility and tailored functionalization. Some aspects that are linked to the performance of HMM include pore accessibility, stability of the organic functions and reusability. Knowledge of these aspects is critical in the design of adsorption-desorption protocols. In this work we produce and characterize propylamino-substituted large pore silica (SBA-15-N), which is submitted to Cu(II) adsorption from copper sulfate solutions, followed by desorption in acid media and material regeneration. We find that the hybrid material is an efficient adsorbent (1.15-1.75 mmol Cu(II) g{sup -1}), although a fraction of the organic groups is lost during the adsorption process. An X-ray photoelectron spectroscopy (XPS) study demonstrates that the contents of amino groups are higher in the material surface, leading to different behaviors in Cu(II) complexation along the material. These materials can be regenerated by exposure to acidic media. Thermal processing of the hybrid materials leads to better durability in aqueous solutions during reprocessing, due to enhanced polycondensation of the inorganic framework. Thermally treated samples, once regenerated, are efficient adsorbents in a second step of Cu(II) adsorption. We discuss the

  9. The synthesis of novel hybrid thiol-functionalized nano-structured SBA-15

    Hoang, Van Duc; Dang, Tuyet Phuong; Dinh, Quang Khieu; Vu, Anh Tuan; Nguyen, Huu Phu

    2010-01-01

    Mesoporous thiol-functionalized SBA-15 has been directly synthesized by co-condensation of tetraethyl orthosilicate (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) with triblock copolymer P123 as-structure-directing agent under hydrothermal conditions. Surfactant removal was performed by Soxhlet ethanol extraction. These materials have been characterized by powder x-ray diffraction (XRD), nitrogen adsorption/desorption (BET model), transmission electron microscopy (TEM), thermal analysis, infrared spectroscopy (IR) and energy-dispersive x-ray spectroscopy (EDX). The main parameters, such as the initial molar ratio of MPTMS to TEOS, the time of adding MPTMS to synthesized gel and the Soxhlet ethanol extraction on the thiol functionalized SBA-15 with high thiol content and highly ordered hexagonal mesostructure, were investigated and evaluated. The adsorption capacity of the thiol-functionalized and non-functionalized SBA-15 materials for Pb 2+ ion from aqueous solution was tested. It was found that the Pb 2+ adsorption capacity of the thiol functionalized SBA-15 is three times higher than that of non-functionalized SBA-15

  10. Preparation, characterization and catalytic activity of mesoporous Ag{sub 2}HPW{sub 12}O{sub 40}/SBA-15 and Ag{sub 2}HPW{sub 12}O{sub 40}/TiO{sub 2} composites

    Holclajtner-Antunović, Ivanka; Bajuk-Bogdanović, Danica [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade (Serbia); Popa, Alexandru; Sasca, Viorel [Institute of Chemistry Timişoara, Bl. Mihail Viteazul 24, 300223 Timişoara (Romania); Nedić Vasiljević, Bojana; Rakić, Aleksandra [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade (Serbia); Uskoković-Marković, Snežana, E-mail: snezaum@pharmacy.bg.ac.rs [Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, 11221 Belgrade (Serbia)

    2015-06-15

    The current study reports the synthesis and characterization of tungstophosphoric acid and its acid silver salt supported on mesoporous molecular sieve SBA-15 and TiO{sub 2}. Because silver salts are partially insoluble, the SBA-15 and TiO{sub 2} supported silver acid salts were prepared by two step sequential impregnations. The synthesized catalysts were characterized by various physicochemical methods such as Fourier transform infrared and Raman spectroscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and nitrogen physisorption at −196 °C. It is observed that both active phases keep their Keggin-type structure after being supported on the supports while their specific surface area is considerably increased by deposition on mesoporous substrates. The results also indicated that the synthesized catalysts retained the morphology specific for each of the supports, while their thermal stability is increased in comparison with their active phases. The catalytic activity of the prepared catalysts was probed for the vapor phase dehydration of ethanol at 300 °C. Results revealed that all the catalysts show considerably improved catalytic activity in comparison to the bulk active phases. - Highlights: • SBA-15 and TiO{sub 2} supported Ag{sub 2}HPW{sub 12}O{sub 40} and H{sub 3}PW{sub 12}O{sub 40} were prepared. • Active phases are uniformly dispersed without changing morphology of the substrates. • Composites are more thermally stable than active phases. • Composites exhibit high catalytic activity for gas phase ethanol dehydration.

  11. Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

    Basset, Jean-Marie

    2016-06-09

    The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest for heterogeneous catalysis. Herein, we report a method to obtain a majority bifunctional acid-base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si-N surface bond and confirm the design of vicinal acid-base pairs. This approach was successfully applied to the design of a series of aniline derivatives bifunctional SBA15. A correlation of the substituents effects on the aromatic ring (Hammet parameters) on the kinetics of the model reaction of Knoevenagel is observed.

  12. Inclusion of cefalexin in SBA-15 mesoporus material and release property

    Zhai, Qing-Zhou

    2012-01-01

    SBA-15 (Santa Barbara Amorphous-15) is a high ordered mesoporous material. It has the advantages of a non-toxic property, good hydrothermal stability and thermal stability, etc. Inside inner surface a lot of silanols exist. Pore diameter size is uniform and pore size distribution is narrow. This structural feature makes SBA-15 have a higher loading drug amount and be able to effectively extend the drug release cycle. In this paper, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol was used as template and tetraethyl orthosilicate was used as silica source to prepare SBA-15 by hydrothermal synthesis method. Cefalexin was included in SBA-15 and the included cefalexin drug content was 158.72 mg/g. The composite materials were characterized by using chemical analysis, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared (IR) spectroscopy, and low temperature nitrogen adsorption–desorption. The results showed that cefalexin had been successfully included in host SBA-15 pore channels. Rational analyses of the release processes of cefalexin drug from the pores of SBA-15 to the simulated body fluid, simulated gastric juice and simulated intestinal fluid were made and sustained-release effects of the drug in complex system were studied. The results showed that in simulated body fluid within 1–5 h cefalexin was fast released and the cumulative release reached 50.00% at 5 h. In 15–20 h, the sustained release speed of cefalexin drug in the composite material decreased and the sustained-release cumulative amount reached 99.87% at 20 h. The release of cefalexin was basically complete. In simulated gastric fluid, composite material sustained-release ended at 4 h, the cumulative sustained release ratio reaching 26.10%. In simulated gastric fluid, the sustained-release was complete at 7 h, the cumulative sustained release ratio reaching 32.46%. The composite material of SBA-15 and cefalexin

  13. Hydrodeoxygenation of Guaiacol Over Pt/Al-SBA-15 Catalysts.

    Yu, Mi Jin; Park, Sung Hoon; Jeon, Jong-Ki; Ryu, Changkook; Sohn, Jung Min; Kim, Sang Chai; Park, Young-Kwon

    2015-01-01

    Upgrading of bio-oil through catalytic hydrodeoxygenation (HDO) reaction was investigated for guaiacol as a model compound. A batch reactor was used for the reaction condition of 40 bar and 250 degrees C. The target product was cyclohexane. Pt/Al-SBA-15 with the Si/Al ratios of 20, 40, and 80 and Pt/HZSM-5 were used as the catalyst. The SBA-15 catalysts were characterized by N2 adsorption-desorption, X-ray diffraction analysis, and temperature programmed desorption of ammonia. The order of cyclohexane yield was Pt/Al-SBA-15 (Si/Al = 20) > Pt/Al-SBA-15(40) > Pt/Al-SBA-15 (80), indicating that the quantity of acid sites plays an important role in the HDO reaction. On the other hand, Pt/HZSM-5 led to a very low cyclohexane yield, in spite of its abundant strong acid sites, due to its small pore size.

  14. Highly ordered mesoporous cobalt oxide nanostructures: synthesis, characterisation, magnetic properties, and applications for electrochemical energy devices.

    Wang, Guoxiu; Liu, Hao; Horvat, Josip; Wang, Bei; Qiao, Shizhang; Park, Jinsoo; Ahn, Hyojun

    2010-09-24

    Highly ordered mesoporous Co(3)O(4) nanostructures were prepared using KIT-6 and SBA-15 silica as hard templates. The structures were confirmed by small angle X-ray diffraction, high resolution transmission electron microscopy, and N(2) adsorption-desorption isotherm analysis. Both KIT-6 cubic and SBA-15 hexagonal mesoporous Co(3)O(4) samples exhibited a low Néel temperature and bulk antiferromagnetic coupling due to geometric confinement of antiferromagnetic order within the nanoparticles. Mesoporous Co(3)O(4) electrode materials have demonstrated the high lithium storage capacity of more than 1200 mAh g(-1) with an excellent cycle life. They also exhibited a high specific capacitance of 370 F g(-1) as electrodes in supercapacitors.

  15. Preparation and thermal properties of mesoporous silica/phenolic resin nanocomposites via in situ polymerization

    J. Lv

    2012-10-01

    Full Text Available In order to enhance the adhesion between inorganic particles and polymer matrix, in this paper, the mesoporous silica SBA-15 material was synthesized by the sol-gel method. The surface of SBA-15 was modified using γ-glycidyloxypropyltrimethoxysilane (GOTMS as a coupling agent, and then mesoporous silica/phenolic resin (SBA-15/PF nanocomposites were prepared via in situ polymerization. The structural parameters and physical properties of SBA-15, SBA-15-GOTMS (SBA-15 surface treated using GOTMS as coupling agents and E-SBA-15/PF (SBA-15/PF nanocomposites extracted using ethanol as solvent were characterized by X-ray diffraction (XRD, N2 adsorption-desorption, Fourier transform infrared spectroscopy (FTIR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and thermogravimetric analysis (TGA. The thermal properties of the nanocomposites were studied by differential scanning calorimetry (DSC and thermogravimetric analysis (TGA. The results demonstrated that the GOTMS were successfully grafted onto the surface of SBA-15, and chemical bonds between PF and SBA-15-GOTMS were formed after in situ polymerization. In addition, it is found that the in situ polymerization method has great effects on the textural parameters of SBA-15. The results also showed that the glass transition temperatures and thermal stability of the PF nanocomposites were obviously enhanced as compared with the pure PF at silica contents between 1–3 wt%, due to the uniform dispersion of the modified SBA-15 in the matrix.

  16. Preparation of Pd-Diimine@SBA-15 and Its Catalytic Performance for the Suzuki Coupling Reaction

    Jiahuan Yu

    2016-11-01

    Full Text Available A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent catalytic performance for the Suzuki coupling reaction of electronically diverse aryl halides and phenylboronic acid under mild conditions with an ultralow amount of Pd (0.05 mol % Pd. When the catalyst amount was increased, it could catalyze the coupling reaction of chlorinated aromatics with phenylboronic acid. Compared with the catalytic performances of Pd/SBA-15 and Pd-diimine@SiO2 catalysts, the Pd-diimine@SBA-15 catalyst exhibited higher hydrothermal stability and could be repeatedly used four times without a significant decrease of its catalytic activity.

  17. Catalytic Synthesis of n-Butyl Oleate by Cerium Complex Doped Y/SBA-15 Composite Molecular Sieve

    Shi, Chunwei; Bian, Xue; Wu, Yongfu; Cong, Yufeng; Pei, Mingyuan

    2018-01-01

    Cerium ion was successfully incorporated into Y/SBA-15 micro-mesoporous molecular sieves via the hydrothermal synthesis method to give a series of composite materials. The prepared materials were thoroughly characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and differential thermo gravimetric analysis (TG-DTG). The results showed that the prepared composite materials retained the highly ordered mesoporous two-dimensional hexagonal structure of SBA-15 and the octagonal structure of Y. The catalyst Ce-Y/SBA-15 was prepared and characterized, then the esterification of n-butanol and oleic acid was studied with bismuth phosphotungstate as a catalyst. Using this model reaction, the effects of Ce-HY/SBA-15, molar ratio of alcohol to oleic acid, amount of catalysts, reaction time and reaction temperature were investigated. The experimental results show that the optimal reaction conditions were: 1.8:1 molar ratio of alcohol to acid, 5 % catalyst amount (based on weight of oleic acid), 4 h reaction time and reflux conditions. Under these conditions, the yield of esterification was 90.6 %. The results suggest that the addition of Ce can effectively improve the catalytic properties of composite molecular sieves.

  18. High surface area TiO2/SBA-15 nanocomposites: Synthesis, microstructure and adsorption-enhanced photocatalysis

    Wei, J. Q.; Chen, X. J.; Wang, P. F.; Han, Y. B.; Xu, J. C.; Hong, B.; Jin, H. X.; Jin, D. F.; Peng, X. L.; Li, J.; Yang, Y. T.; Ge, H. L.; Wang, X. Q.

    2018-06-01

    Mesoporous SBA-15 was used to anchor TiO2 nanoparticles into the mesopores to form high surface area TiO2/SBA-15 nanocomposites, and then the influence of mesoporous-structure on the photocatalytic performance was investigated. TiO2/SBA-15 nanocomposites possessed the high specific surface area and appropriate pore size, indicating the excellent adsorption performance. TiO2/SBA-15 nanocomposites exhibited the higher photocatalytic activity to degrade dyes (methylene blue: MB) than TiO2 (removing SBA-15), which should attributed to the excellent adsorption performance of the nanocomposites. MB was absorbed to form the higher concentration near TiO2/SBA-15 photocatalysts, and the photocatalytic degradation for MB was improved.

  19. Desidratação de etanol sobre material nanoestruturado do tipo LaSBA-15 Ethanol dehydration over LaSBA-15 nanostrutured material

    Geraldo E. Luz Jr

    2010-01-01

    Full Text Available La-incorporated SBA-15 mesopourous molecular sieves (LaSBA-15 were directly synthesized with aim to convert ethanol to ethylene. The samples were characterized by XRD, XRF, nitrogen sorption and acidity, by thermodesorption of n-buthylamine. The results have indicated that all the samples have showed high ordered mesostructure with a large average pore size, and that the lanthanum incorporation has caused an increase in the acidity of the SBA-15. The LaSBA-15 samples have improved, with low deactivation rate, the conversion of the ethanol to water, ether, acetaldehyde and ethylene. In addition, they have increased the ethylene selectivity.

  20. Ordered Mesoporous Carbons as Novel and Efficient Adsorbent for Dye Removal from Aqueous Solution

    Phuong T. Dang; Hoa T. H. Nguyen; Canh D. Dao; Giang H. Le; Quang K. Nguyen; Kien T. Nguyen; Hoa T. K. Tran; Tuyen V. Nguyen; Tuan A. Vu

    2016-01-01

    Ordered mesoporous carbons (OMCs) were successfully synthesized by using hard template and soft template methods. These materials were characterized by XRD, TEM, and N2 adsorption-desorption Brunauer-Emmett-Teller (BET). From the obtained results, it is revealed that the obtained OMCs samples showed high surface area (>1000 m2/g) with high pore volume, mainly mesopore volume (1.2–2.4 cm3/g). Moreover, OMCs samples had similar structure of the SBA-15 silica and exhibited high MB adsorption cap...

  1. Preparation of SBA-15-PAMAM as a Nano Adsorbent for Removal of Acid Red 266 from Aqueous Media: Batch Adsorption and Equilibrium Studies

    Maryam Mirzaie

    2017-12-01

    Full Text Available The purpose of the present study was to increase the adsorption capacity of SBA-15 for acidic dyes. Ordered mesoporous silica SBA-15 was successfully synthesized and functionalized by polyamidoamine (PAMAM dendrimer to develop an efficient anionic dye adsorbent. The prepared materials were characterized by field emission scanning electron microscope (FE-SEM, Fourier transforms infrared spectroscope (FT-IR and N2 adsorption–desorption analysis. The study was concocted in the Science and Research Branch of Islamic Azad University of Tehran, Iran in 2016. The produced adsorbent (SBA-15-Den was applied for the removal of Acid Red 266 (AR266 from aqueous media. The effects of various operational parameters including solution pH, adsorbent dosage, contact time, and temperature on removal of AR266 using SBA-15-Den were investigated in batch adsorption mode. Within the optimum conditions, SBA-15-Den exhibited an excellent adsorptive capability of 1111.11 mg/g. Equilibrium data were best described by Langmuir model (R2 > 0.98 completely.

  2. A dansyl group modified SBA-15 INHIBIT logic gate with [Hg2+ and Cl-] or [Hg2+ and Br-] as inputs

    Wang, Xiaoyu; Yang, Honglei

    2013-07-01

    We developed a SBA-15-based INHIBIT logic gate (DA-SBA-15) which was prepared by covalent immobilization of a dansylamide derivative into the channels of the mesoporous silica material (SBA-15) via (3-aminopropyl)triethoxysilane (APTES) groups. A series of characteristic results proved that the fluorescent ligand was successfully grafted into the mesopores of SBA-15. The fluorescent characterization revealed excellent selectivity of DA-SBA-15 to the Hg2+ ion. Moreover, DA-SBA-15 can be considered as a selective fluorescent probe for Cl- and Br-. The fluorescent changes of DA-SBA-15 upon the addition of ions (Hg2+, Cl- and Br-) were utilized as an INH logic gate at the molecular level, using [Hg2+ and Cl-] or [Hg2+ and Br-] as chemical inputs and the fluorescence intensity signal as output.

  3. Highly stable and regenerable Mn-based/SBA-15 sorbents for desulfurization of hot coal gas

    Zhang, F.M.; Liu, B.S.; Zhang, Y.; Guo, Y.H.; Wan, Z.Y.; Subhan, Fazle

    2012-01-01

    Highlights: ► A series of mesoporous Cu x Mn y O z /SBA-15 sorbents were fabricated for hot coal gas desulfurization. ► 1Cu9Mn/SBA-15 sorbent with high breakthrough sulfur capacity is high stable and regenerable. ► Utilization of SBA-15 constrained the sintering and pulverization of sorbents. - Abstract: A series of mesoporous xCuyMn/SBA-15 sorbents with different Cu/Mn atomic ratios were prepared by wet impregnation method and their desulfurization performance in hot coal gas was investigated in a fixed-bed quartz reactor in the range of 700–850 °C. The successive nine desulfurization–regeneration cycles at 800 °C revealed that 1Cu9Mn/SBA-15 presented high performance with durable regeneration ability due to the high dispersion of Mn 2 O 3 particles incorporated with a certain amount of copper oxides. The breakthrough sulfur capacity of 1Cu9Mn/SBA-15 observed 800 °C is 13.8 g S/100 g sorbents, which is remarkably higher than these of 40 wt%LaFeO 3 /SBA-15 (4.8 g S/100 g sorbents) and 50 wt%LaFe 2 O x /MCM-41 (5.58 g S/100 g sorbents) used only at 500–550 °C. This suggested that the loading of Mn 2 O 3 active species with high thermal stability to SBA-15 support significantly increased sulfur capacity at relatively higher sulfidation temperature. The fresh and used xCuyMn/SBA-15 sorbents were characterized by means of BET, XRD, XPS, XAES, TG/DSC and HRTEM techniques, confirmed that the structure of the sorbents remained intact before and after hot coal gas desulfurization.

  4. Adsorptive performance of chromium-containing ordered mesoporous silica on volatile organic compounds (VOCs

    Jianwei Fan

    2017-09-01

    Full Text Available Volatile organic compounds (VOCs are the primary poisonous emissions into the atmosphere in natural gas exploitation and disposing process. The adsorption method has been widely applied in actual production because of its good features such as low cost, low energy consumption, flexible devices needed, etc. The commonly used adsorbents like activated carbon, silicon molecular sieves and so on are not only susceptible to plugging or spontaneous combustion but difficult to be recycled. In view of this, a new adsorbent (CrSBA15 was made by the co-assembly method to synthesize the ordered mesoporous silica materials with different amounts of chromium to eliminate VOCs. This new adsorbent was characterized by small-angle-X-ray scattering (SAXS, nitrogen adsorption/desorption, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. Its adsorption performance to eliminate VOCs (toluene, benzene, cyclohexane and ethyl acetate used as typical pollutants was also tested systematically. Research results indicate that this new adsorbent of CrSBA-15(30, with the silicon/chromium ration being 30, owns the maximum micropore volume, and shows a higher adsorption performance in eliminating toluene, benzene, cyclohexane and ethyl acetate. Besides, it is cost-effective and much easier to be recycled than the activated carbon. In conclusion, CrSBA-15(30 is a good adsorbent to eliminate VOCs with broad application prospects. Keywords: Mesoporous materials, Silicon dioxide, Synthesis, Adsorption, Volatile organic compounds (VOCs, Recyclability, Energy saving

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

    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.

  6. Phosphoryl functionalized mesoporous silica for uranium adsorption

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

    2017-01-01

    Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N_2 adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG"0, ΔH"0 and ΔS"0) confirmed that the adsorption process was endothermic and spontaneous.

  7. Phosphoryl functionalized mesoporous silica for uranium adsorption

    Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Hongyu, Gong, E-mail: gong_hongyu@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Yujun, Zhang, E-mail: yujunzhangcn@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China)

    2017-04-30

    Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N{sub 2} adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG{sup 0}, ΔH{sup 0} and ΔS{sup 0}) confirmed that the adsorption process was endothermic and spontaneous.

  8. Study of DDT and its derivatives DDD, DDE adsorption and degradation over Fe-SBA-15 at low temperature

    Hailin Wang; Hua Tian; Zhengping Hao

    2012-01-01

    Mesoporous SBA-15 with different Fe2O3 loading were synthesized by an in-situ coating progress for removals of dichlorodiphenyltrichloroethane(DDT)and its derivatives,i.e.,1,1-dichloro-2,2-bis-(p-chlorophenyl)ethane(DDD)and 1,l-dichloro-2,2-bis-(4-chloro -phenyl)ethane(DDE).The results from XRD(X-ray diffractometer),TEM(transmission electron microscopy)indicated that the iron could be well dispersed on SBA-15 within 6 wt.% Fe2O3 loading.Nitrogen adsorption-desorption tests indicated that the synthesized materials were characterized by ordered meso-structure,high surface area and large pore volume.DDTs were removed from aqueous media in 12-hr treatment and high removal efficiency of DDTs was achieved at over 94%.DDTs could be completely degraded at 350℃ under the existence of SBA-15 with 4 wt.% Fe2O3 loading.The final degradation products of DDT were dichlorobenzophenone (DCB)and bis-(4-chloro-phenyl)methane(DDM),suggesting a complete dechlorination from trichloromethyl.

  9. Surface functionalization of SBA-15 by the solvent-free method

    Wang Yimeng; Zheng Yingwu; Zhu Jianhua

    2004-01-01

    A solvent-free technique was employed for fast modification of mesoporous materials. Copper, chromium and iron oxide species could be highly dispersed in SBA-15 by manually grinding the corresponding precursor salts and the host, followed by calcinations for the first time. This method is more effective to spontaneously disperse oxide species onto SBA-15 than impregnation, probably forming monolayer or submonolayer dispersion of salts or oxides. Besides, Cr(VI) species dominate in the mixing sample while Cr(III) species dominate in the impregnation one. In the temperature programmed surface reaction of nitrosamines, the sample prepared by solvent-free method showed a higher catalytic activity than the impregnation one

  10. Ordered Mesoporous Carbons as Novel and Efficient Adsorbent for Dye Removal from Aqueous Solution

    Phuong T. Dang

    2016-01-01

    Full Text Available Ordered mesoporous carbons (OMCs were successfully synthesized by using hard template and soft template methods. These materials were characterized by XRD, TEM, and N2 adsorption-desorption Brunauer-Emmett-Teller (BET. From the obtained results, it is revealed that the obtained OMCs samples showed high surface area (>1000 m2/g with high pore volume, mainly mesopore volume (1.2–2.4 cm3/g. Moreover, OMCs samples had similar structure of the SBA-15 silica and exhibited high MB adsorption capacity with qm of 398 mg·g−1 for OMCs synthesis with hard template and 476 mg·g−1 for OMCs synthesis with soft template, respectively. From kinetics investigation, it is confirmed that MB adsorption from aqueous solution obeys the pseudo-second-order kinetic equation.

  11. Improved antimicrobial property and controlled drug release kinetics of silver sulfadiazine loaded ordered mesoporous silica

    Suman Jangra

    2016-09-01

    Full Text Available The present study deals with the loading of silver sulfadiazine into ordered mesoporous silica material by post-impregnation method and its effect on the in vitro release kinetics and antimicrobial property of the drug. The formulated SBA-15 silica material with rope-like morphology and SBA-15-silver sulfadiazine (SBA-AgSD were characterized by UV–visible spectrophotometer, small and wide-angle powder X-ray diffraction (PXRD, field emission scanning electron microscope (FESEM and high resolution transmission electron microscope (HRTEM. Thermo-gravimetric analysis of SBA-AgSD revealed a high loading amount of 52.87%. Nitrogen adsorption–desorption analysis confirmed the drug entrapment into host material by revealing a reduced surface area (214 m2/g and pore diameter (6.7 nm of the SBA-AgSD. The controlled release of silver sulfadiazine drug from the mesoporous silica to simulated gastric, intestinal and body fluids was evaluated. The Korsmeyer–Peppas model fits the drug release data with the non-Fickian diffusion model and zero order kinetics of SBA-AgSD. The antibacterial performance of the SBA-AgSD was evaluated with respect to Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa. The controlled drug delivery of the SBA-AgSD revealed improved antibacterial activity, thus endorsing its applicability in effective wound dressing.

  12. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    Bahrami, Zohreh; Badiei, Alireza; Ziarani, Ghodsi Mohammadi

    2015-01-01

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N 2 adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples

  13. Effect of amine functionalization of spherical MCM-41 and SBA-15 on controlled drug release

    Szegedi, A.; Popova, M.; Goshev, I.; Mihaly, J.

    2011-01-01

    MCM-41 and SBA-15 silica materials with spherical morphology and different particle sizes were synthesized and modified by post-synthesis method with 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, were carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N 2 physisorption, thermal analysis, elemental analysis and FT-IR spectroscopy. Surface modification with amino groups resulted in high degree of ibuprofen loading and slow rate of release for MCM-41, whereas it was the opposite for SBA-15. The adsorbed drug content and the delivery rate can be predetermined by the choice of mesoporous material with the appropriate structural characteristics and surface functionality. -- Graphical Abstract: Ibuprofen delivery from the parent and amino-modified spherical MCM-41 materials with 100 nm (small) and 500 nm (large) particle sizes. Display Omitted Highlights: → Spherical type MCM-41 and SBA-15 with different particle sizes were modified by APTES. → Adsorption and release rate of ibuprofen were compared. → High degree of ibuprofen loading, slow release rate for MCM-41, the opposite for SBA-15. → MCM-41 with 100 nm particles was more stable and showed slower release rate

  14. Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15

    Appell, Michael; Jackson, Michael A.; Dombrink-Kurtzman, Mary Ann

    2011-01-01

    Propylthiol functionalized SBA-15 silica was investigated to detoxify aqueous solutions contaminated with the regulated mycotoxin patulin. Micelle templated silicas with a specific pore size were synthetically modified to possess propylthiol groups, a functional group known to form Michael reaction products with the conjugated double bond system of patulin. BET surface area analysis indicated the propylthiol functionalized SBA-15 possesses channels with the pore size of 5.4 nm and a surface area of 345 m 2 g -1 . Elemental analysis indicates the silicon/sulfur ratio to be 10:1, inferring one propylthiol substituent for every ten silica residues. The propylthiol modified SBA-15 was effective at significantly reducing high levels of patulin from aqueous solutions (pH 7.0) in batch sorption assays at room temperature. The material was less effective at lower pH; however heating low pH solutions and apple juice to 60 deg, C in the presence of propylthiol functionalized SBA-15 significantly reduced the levels of patulin in contaminated samples. Composite molecular models developed by semi-empirical PM3 and empirical force field methods support patulin permeation through the mesoporous channels of propylthiol functionalized SBA-15. Density functional study at the B3LYP/6-31G(d,p) level predicts the proposed patulin adducts formed by reaction with the thiol residues exhibit less electrophilic properties than patulin. It is demonstrated the use of propylthiol functionalized SBA-15 is a viable approach to reduce patulin levels in aqueous solutions, including contaminated apple juice.

  15. Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15

    Appell, Michael, E-mail: michael.appell@ars.usda.gov [Bacterial Foodborne Pathogens and Mycology Research Unit, United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University St., Peoria, IL 61604 (United States); Jackson, Michael A.; Dombrink-Kurtzman, Mary Ann [Renewable Product Technology Research Unit, United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University St., Peoria, IL 61604 (United States)

    2011-03-15

    Propylthiol functionalized SBA-15 silica was investigated to detoxify aqueous solutions contaminated with the regulated mycotoxin patulin. Micelle templated silicas with a specific pore size were synthetically modified to possess propylthiol groups, a functional group known to form Michael reaction products with the conjugated double bond system of patulin. BET surface area analysis indicated the propylthiol functionalized SBA-15 possesses channels with the pore size of 5.4 nm and a surface area of 345 m{sup 2} g{sup -1}. Elemental analysis indicates the silicon/sulfur ratio to be 10:1, inferring one propylthiol substituent for every ten silica residues. The propylthiol modified SBA-15 was effective at significantly reducing high levels of patulin from aqueous solutions (pH 7.0) in batch sorption assays at room temperature. The material was less effective at lower pH; however heating low pH solutions and apple juice to 60 deg, C in the presence of propylthiol functionalized SBA-15 significantly reduced the levels of patulin in contaminated samples. Composite molecular models developed by semi-empirical PM3 and empirical force field methods support patulin permeation through the mesoporous channels of propylthiol functionalized SBA-15. Density functional study at the B3LYP/6-31G(d,p) level predicts the proposed patulin adducts formed by reaction with the thiol residues exhibit less electrophilic properties than patulin. It is demonstrated the use of propylthiol functionalized SBA-15 is a viable approach to reduce patulin levels in aqueous solutions, including contaminated apple juice.

  16. Facile functionalized of SBA-15 via a biomimetic coating and its application in efficient removal of uranium ions from aqueous solution

    Gao, Jun-Kai [School of Environmental Science and Engineering, Tianjin University, Tianjin 300072 (China); School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401 (China); Hou, Li-An; Zhang, Guang-Hui [School of Environmental Science and Engineering, Tianjin University, Tianjin 300072 (China); Gu, Ping, E-mail: guping@tju.edu.cn [School of Environmental Science and Engineering, Tianjin University, Tianjin 300072 (China)

    2015-04-09

    Highlights: • Dopamine-functionalized SBA-15 (DMS) was developed via a biomimetic coating. • The modification approach was simple, facile and cost-effective. • The DMS was firstly used to remove U(VI) from aqueous solution. • Large adsorption capacity and rapid separation were obtained. - Abstract: A novel dopamine-functionalized mesoporous silica (DMS), synthesized by grafting dopamine onto a mesoporous molecular sieve (SBA-15), was developed as a sorbent to extract U(VI) from aqueous solution. The method used to modify SBA-15 was simple, facile and cost-effective. The DMS was characterized by SEM, TEM, XRD and BET, showing that the material had an ordered mesoporous structure and a large surface area. The effect of contact time, pH, ionic strength, temperature, and solid–liquid ratio on the sorption process was investigated. It was demonstrated that the adsorption of U(VI) by DMS was fast and that it can be described by the pseudo-second order-equation where the equilibrium time was 20 min. Additionally, the adsorption isotherm data were fitted well by the Langmuir model with the maximum adsorption capacity of DMS of 196 mg/g at pH 6.0. Furthermore, the influence of the K{sup +} and Na{sup +} concentrations and solid-to-liquid ratio on the sorption was very weak, and the values of the thermodynamic parameters revealed that the sorption process was exothermic and spontaneous. All the results suggested that the DMS could be used as an excellent adsorbent to remove U(VI) from aqueous solution.

  17. Facile functionalized of SBA-15 via a biomimetic coating and its application in efficient removal of uranium ions from aqueous solution.

    Gao, Jun-Kai; Hou, Li-An; Zhang, Guang-Hui; Gu, Ping

    2015-04-09

    A novel dopamine-functionalized mesoporous silica (DMS), synthesized by grafting dopamine onto a mesoporous molecular sieve (SBA-15), was developed as a sorbent to extract U(VI) from aqueous solution. The method used to modify SBA-15 was simple, facile and cost-effective. The DMS was characterized by SEM, TEM, XRD and BET, showing that the material had an ordered mesoporous structure and a large surface area. The effect of contact time, pH, ionic strength, temperature, and solid-liquid ratio on the sorption process was investigated. It was demonstrated that the adsorption of U(VI) by DMS was fast and that it can be described by the pseudo-second order-equation where the equilibrium time was 20 min. Additionally, the adsorption isotherm data were fitted well by the Langmuir model with the maximum adsorption capacity of DMS of 196 mg/g at pH 6.0. Furthermore, the influence of the K(+) and Na(+) concentrations and solid-to-liquid ratio on the sorption was very weak, and the values of the thermodynamic parameters revealed that the sorption process was exothermic and spontaneous. All the results suggested that the DMS could be used as an excellent adsorbent to remove U(VI) from aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

    Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

    2007-01-01

    A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

  19. Synthesis of novel magnetic iron metal-silica (Fe-SBA-15) and magnetite-silica (Fe{sub 3}O{sub 4}-SBA-15) nanocomposites with a high iron content using temperature-programed reduction

    Yiu, H H P [Department of Chemistry, University of Liverpool, Liverpool, Merseyside L69 7ZD (United Kingdom); Keane, M A [Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Lethbridge, Z A D [Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL (United Kingdom); Lees, M R [Department of Physics, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL (United Kingdom); Haj, A J El; Dobson, J [Institute of Science and Technology in Medicine, Keele University, Thornburrow Drive, Hartshill, Stoke-on-Trent ST4 7QB (United Kingdom)], E-mail: j.p.dobson@keele.ac.uk

    2008-06-25

    Magnetic iron metal-silica and magnetite-silica nanocomposites have been prepared via temperature-programed reduction (TPR) of an iron oxide-SBA-15 (SBA: Santa Barbara Amorphous) composite. TPR of the starting SBA-15 supported Fe{sub 2}O{sub 3} generated Fe{sub 3}O{sub 4} and FeO as stepwise intermediates in the ultimate formation of Fe-SBA-15. The composite materials have been characterized by means of x-ray diffraction, high resolution transmission electron microscopy and SQUID (superconducting quantum interference device) magnetometry. The Fe oxide and metal components form a core, as nanoscale particles, that is entrapped in the SBA-15 pore network. Fe{sub 3}O{sub 4}-SBA-15 and Fe-SBA-15 exhibited superparamagnetic properties with a total magnetization value of 17 emu g{sup -1}. The magnetite-silica composite (at an Fe{sub 3}O{sub 4} loading of 30% w/w) delivered a magnetization that exceeded values reported in the literature or obtained with commercial samples. Due to the high pore volume of the mesoporous template, the magnetite content can be increased to 83% w/w with a further enhancement of magnetization.

  20. Mesostructured Au/C materials obtained by replication of functionalized SBA-15 silica containing highly dispersed gold nanoparticles

    Kerdi, Fatmé

    2011-04-01

    The preparation and characterization of highly dispersed gold nanoparticles in ordered mesoporous carbons CMK-3 are reported. These carbons were obtained using gold-containing functionalized SBA-15 silicas as hard templates. Two series of Au/SiO2 templates were prepared, depending on the nature of the functionalization molecule. While ammonium-functionalized silicas gave gold particles with a size determined by the pores of the silica support, the use of mercaptopropyltrimethoxysilane as grafting molecule afforded the possibility to control the particle size inside the mesopores. Both series gave highly ordered mesoporous carbons with gold particles incorporated in the carbon nanorods. However, the gold particle size in mesoporous carbons was the same for both series and apparently did not depend on the nature of the silica template. Both Au/SiO2 templates and their corresponding Au/CMK-3 materials have been characterized by X-ray diffraction, nitrogen adsorption/desorption, chemical analysis, solid-state nuclear magnetic resonance and transmission electron microscopy. They were also used as catalysts in the aerobic oxidation of cyclohexene and trans-stilbene in the liquid phase. © 2010 Elsevier Inc. All rights reserved.

  1. IR spectroscopy study of SBA-15 silicas functionalized with the ethylthiocarbamidepropyl groups and their interactions with Ag(I) and Hg(II) ions

    Melnyk, Inna V.; Nazarchuk, Galyna I.; Václavíková, Miroslava; Zub, Yuriy L.

    2018-04-01

    Mesoporous structure of silica is determined by the type of template, but the introduction of functional groups during the synthesis has additional influence. The structure of SBA-15 may be violated by the introduction of long functions, such as ≡Si(CH2)3NHC(=S)NHC2H5. These ethylthiocarbamidepropyl groups can form complexes with metal ions in thiol or thione tautomeric forms. We determined that the 2D hexagonal p6 mm structure is preserved for SBA-15 with thiourea groups at maximal TEOS:trifunctional silane ratio (mol) = 10:2, which was confirmed by TEM and by the presence of an intense reflex in the small-angle region of diffractograms of the final product. It was shown that the obtained sorbents possess high kinetic characteristics. The experimental data fit pseudo-second-order kinetic equation, but the rate constants depend on the content of functional groups in the surface layer. Template Pluronic P-123 defines the porosity of functional mesoporous silica materials even at increasing content of trifunctional silane in the initial solution. Infrared spectroscopy analysis showed that thione form of thiourea ligand is prevalent on the surface of pores of mesoporous samples. However, during the sorption of silver(I) ions, there are both thione and thiol forms on the surface. Thione form is transformed into thiol with increasing concentration of mercury(II) ions in the sorption solution. Adsorption experiments showed that the SBA-15 silicas functionalized with ethylthiocarbamidepropyl groups had high selectivity for silver(I) ions and could concentrate Ag(I) ions from metal ions mixture at pH 2.

  2. Ordered mesoporous polymer-silica hybrid nanoparticles as vehicles for the intracellular controlled release of macromolecules.

    Kim, Tae-Wan; Slowing, Igor I; Chung, Po-Wen; Lin, Victor Shang-Yi

    2011-01-25

    A two-dimensional hexagonal ordered mesoporous polymer-silica hybrid nanoparticle (PSN) material was synthesized by polymerization of acrylate monomers on the surface of SBA-15 mesoporous silica nanoparticles. The structure of the PSN material was analyzed using a series of different techniques, including transmission electron microscopy, powder X-ray diffraction, and N(2) sorption analysis. These structurally ordered mesoporous polymer-silica hybrid nanoparticles were used for the controlled release of membrane-impermeable macromolecules inside eukaryotic cells. The cellular uptake efficiency and biocompatibility of PSN with human cervical cancer cells (HeLa) were investigated. Our results show that the inhibitory concentration (IC(50)) of PSN is very high (>100 μg/mL per million cells), while the median effective concentration for the uptake (EC(50)) of PSN is low (EC(50) = 4.4 μg/mL), indicating that PSNs are fairly biocompatible and easily up-taken in vitro. A membrane-impermeable macromolecule, 40 kDa FITC-Dextran, was loaded into the mesopores of PSNs at low pH. We demonstrated that the PSN material could indeed serve as a transmembrane carrier for the controlled release of FITC-Dextran at the pH level inside live HeLa cells. We believe that further developments of this PSN material will lead to a new generation of nanodevices for intracellular controlled delivery applications.

  3. Substantially Stabilized Superacid Incorporated SBA-15 with Calcium Bridging for Selective Esterification of Glycerol

    Hoo, P. Y.; Abdullah, A. Z.; Shuit, S. H.; Teoh, Y. P.; Ng, Q. H.; Kunasundari, B.

    2018-03-01

    The exploitation of the super acidity of heteropolyacids incorporated heterogeneous catalysts was only feasible if the heterogeneity of these catalysts was assured. To maintain the catalyst heterogeneity in polar medium, a novel two-step modification method was proposed to synthesize the highly active, yet stable heterogeneous catalyst, catered for selective esterification of monoglyceride. The surficial, structural and acidity properties of the modified catalysts were investigated via crucial characterization methods (N2 BET, HRTEM, and FTIR). The collective evidences verified the predicted formation of calcium oxides (CaO) on the mesopores surfaces of the SBA-15 support after the first modification, and the successful subsequent 12-tungstophosphoric acid (HPW) functionalization. The superior stability of the synthesized catalysts (10wt%-HPW/CaSBA-15) was demonstrated (negligible change in both conversion – 75% and yield – 70%), without the need for catalyst regeneration. Such result was attributed to the strong interaction between HPW and SBA-15 via calcium bridging. Being alkaline in nature, calcium oxides in the inner pores readily reacted with highly acidic HPW introduced in the subsequent wetness incipient step, forming insoluble HPW acid sites on inner pore walls of SBA-15 via the calcium bridging. This modification deemed promising and other alkaline metals should be explored in the future.

  4. Ordered mesoporous silica materials with complicated structures

    Han, Yu

    2012-05-01

    Periodically ordered mesoporous silicas constitute one of the most important branches of porous materials that are extensively employed in various chemical engineering applications including adsorption, separation and catalysis. This short review gives an introduction to recently developed mesoporous silicas with emphasis on their complicated structures and synthesis mechanisms. In addition, two powerful techniques for solving complex mesoporous structures, electron crystallography and electron tomography, are compared to elucidate their respective strength and limitations. Some critical issues and challenges regarding the development of novel mesoporous structures as well as their applications are also discussed. © 2011 Elsevier Ltd.

  5. Iron oxide inside SBA-15 modified with amino groups as reusable adsorbent for highly efficient removal of glyphosate from water

    Fiorilli, Sonia; Rivoira, Luca; Calì, Giada; Appendini, Marta; Bruzzoniti, Maria Concetta; Coïsson, Marco; Onida, Barbara

    2017-07-01

    Iron oxide clusters were incorporated into amino-functionalized SBA-15 in order to obtain a magnetically recoverable adsorbent. The physical-chemical properties of the material were characterized by FE-SEM, STEM, XRD, TGA, XPS, FT-IR and acid-base titration analysis. Iron oxide nanoparticles were uniformly dispersed into the pore of mesoporous silica and that the adsorbent is characterized high specific surface area (177 m2/g) and accessible porosity. The sorbent was successfully tested for the removal of glyphosate in real water matrices. Despite the significant content of inorganic ions, a quantitative removal of the contaminant was found. The complete regeneration of the sorbent after the adsorption process through diluted NaOH solution was also proved.

  6. Synthesis and characterization of novel mesocomposites Co3O4 and CuO@OMS (ordered mesoporous silica) as active catalysts for hydrocarbon oxidation

    Comănescu, Cezar

    2014-03-01

    Novel metal nanoporous transition metal oxides M x O y (Co3O4, CuO) have been synthesized by thermal decomposition of inorganic salts precursors (acetates, nitrates) impregnated into hexagonal mesoporous silica (OMS, ordered mesoporous silica) of SBA-15 type (prepared in-house) at different precursor loadings, the mesocomposites thus obtained being monitored after each impregnation-calcination step by small and wide angle powder XRD. The pore size for the ordered silica host range from 5.08 to 7.06 nm. Retention of the hexagonal silica framework has been observed in spite of the temperatures up to 500 °C. Mesoporous Co3O4 has been obtained by leaching the silica through overnight HF dissolution, which partially preserved the small-range ordering found in the parent Co3O4@OMS composite prior to leaching. Both Co3O4 ( meso) and Co3O4@SBA-15 have been tested in methane oxidation and were found to be superior to the bulk Co3O4 performance, with mesoporous Co3O4 being able to fully oxidize methane to CO2 and H2O at 350 °C, while Co3O4@OMS exhibits a lower activity with 20 % conversion at 350 °C. CuO@OMS shows the lowest activity, with only 13 % conversion at 500 °C.

  7. Ordered mesoporous silica materials with complicated structures

    Han, Yu; Zhang, Daliang

    2012-01-01

    Periodically ordered mesoporous silicas constitute one of the most important branches of porous materials that are extensively employed in various chemical engineering applications including adsorption, separation and catalysis. This short review

  8. Highly crystalline mesoporous C{sub 60} with ordered pores. A class of nanomaterials for energy applications

    Benzigar, Mercy R.; Joseph, Stalin; Ilbeygi, Hamid [Future Industries Institute (FII), Division of Information Technology Energy and Environment (DivITEE), University of South Australia, Adelaide, SA (Australia); Park, Dae-Hwan; Talapaneni, Siddulu Naidu [Global Innovative Center for Advanced Nanomaterials (GICAN), Faculty of Engineering and Built Environment, The University of Newcastle, Callaghan, NSW (Australia); Sarkar, Sujoy; Chandra, Goutam; Umapathy, Siva; Srinivasan, Sampath [Department of Inorganic and Physical Chemistry and Department of Instrumentation and Applied Physics, Indian Institute of Science (IISc), Bangalore (India); Vinu, Ajayan [Future Industries Institute (FII), Division of Information Technology Energy and Environment (DivITEE), University of South Australia, Adelaide, SA (Australia); Global Innovative Center for Advanced Nanomaterials (GICAN), Faculty of Engineering and Built Environment, The University of Newcastle, Callaghan, NSW (Australia)

    2018-01-08

    Highly ordered mesoporous C{sub 60} with a well-ordered porous structure and a high crystallinity is prepared through the nanohard templating method using a saturated solution of C{sub 60} in 1-chloronaphthalene (51 mg mL{sup -1}) as a C{sub 60} precursor and SBA-15 as a hard template. The high solubility of C{sub 60} in 1-chloronaphthalene helps not only to encapsulate a huge amount of the C{sub 60} into the mesopores of the template but also supports the oligomerization of C{sub 60} and the formation of crystalline walls made of C{sub 60}. The obtained mesoporous C{sub 60} exhibits a rod-shaped morphology, a high specific surface area (680 m{sup 2} g{sup -1}), tuneable pores, and a highly crystalline wall structure. This exciting ordered mesoporous C{sub 60} offers high supercapacitive performance and a high selectivity to H{sub 2}O{sub 2} production and methanol tolerance for ORR. This simple strategy could be adopted to make a series of mesoporous fullerenes with different structures and carbon atoms as a new class of energy materials. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Carbon material formation on SBA-15 and Ni-SBA-15 and residue constituents during acetylene decomposition

    Chiang, Hung-Lung, E-mail: hlchiang@mail.cmu.edu.tw [Department of Risk Management, China Medical University, Taichung 40402, Taiwan (China); Wu, Trong-Neng [Department of Public Health, China Medical University, Taichung 40402, Taiwan (China); Ho, Yung-Shou [Department of Applied Chemistry and Materials Science, Fooyin University, Kaohsiung 831, Taiwan (China); Zeng, Li-Xuan [Department of Risk Management, China Medical University, Taichung 40402, Taiwan (China)

    2014-07-15

    Highlights: • Acetylene was decomposed on SBA-15 and Ni-SBA-15 at 650–850 °C. • Carbon spheres and filaments were formed after acetylene decomposition. • PAHs were determined in tar and residues. • Exhaust constituents include CO{sub 2}, H{sub 2}, NO{sub x} and hydrocarbon species. - Abstract: Carbon materials including carbon spheres and nanotubes were formed from acetylene decomposition on hydrogen-reduced SBA-15 and Ni-SBA-15 at 650–850 °C. The physicochemical characteristics of SBA-15, Ni-SBA-15 and carbon materials were analyzed by field emission scanning electronic microscopy (FE-SEM), Raman spectrometry, and energy dispersive spectrometry (EDS). In addition, the contents of polyaromatic hydrocarbons (PAHs) in the tar and residue and volatile organic compounds (VOCs) in the exhaust were determined during acetylene decomposition on SBA-15 and Ni-SBA-15. Spherical carbon materials were observed on SBA-15 during acetylene decomposition at 750 and 850 °C. Carbon filaments and ball spheres were formed on Ni-SBA-15 at 650–850 °C. Raman spectroscopy revealed peaks at 1290 (D-band, disorder mode, amorphous carbon) and 1590 (G-band, graphite sp{sup 2} structure) cm{sup −1}. Naphthalene (2 rings), pyrene (4 rings), phenanthrene (3 rings), and fluoranthene (4 rings) were major PAHs in tar and residues. Exhaust constituents of hydrocarbon (as propane), H{sub 2}, and C{sub 2}H{sub 2} were 3.9–2.6/2.7–1.5, 1.4–2.8/2.6–4.3, 4.2–2.4/3.2–1.7% when acetylene was decomposed on SBA-15/Ni-SBA-15, respectively, corresponding to temperatures ranging from 650 to 850 °C. The concentrations of 52 VOCs ranged from 9359 to 5658 and 2488 to 1104 ppm for SBA-15 and Ni-SBA-15 respectively, at acetylene decomposition temperatures from 650 to 850 °C, and the aromatics contributed more than 87% fraction of VOC concentrations.

  10. Summary different routes for procurement of molecular sieves type AL-SBA-15

    Figueiroa, D.S.; Santos, J.O.P.N.; Medeiros, C.D.; Sousa, B.V.

    2012-01-01

    The search for new materials to assist industrial development, especially in the chemical industry has been growing more and more. Molecular sieves are great examples of these materials that aim the improvement of various chemical processes. The present work aimed to synthesize the molecular sieve Al-SBA-15 by two different synthesis procedures. In procedure A was used a temperature of 40°C for 24 hours during stirring process. For B process the stirring procedure was done at room temperature. The molar composition of reactants was: 1.0 SiO 2 : 0.04 Al 2 O 3 :0.0168 EO 20 PO 70 EO 20 : 5.85 HCl: 160 H 2 O. The pH of the reaction gel was adjusted to 7 and after the gel was putted under 100 deg C for 48 hours for the heat treatment. Then the sample was calcined under flowing air at 500° C for 6 hours. By techniques such as XRD and SEM, it was confirmed the formation of the hexagonal mesoporous structure, with an orderly distribution of its pores, also indicating the successful incorporation of aluminum into the hexagonal structure of the catalyst support. (author)

  11. Preparation and physical characterization of calcium sulfate cement/silica-based mesoporous material composites for controlled release of BMP-2

    Tan H

    2015-07-01

    Full Text Available Honglue Tan,1 Shengbing Yang,2 Pengyi Dai,1 Wuyin Li,1 Bing Yue2 1Luoyang Orthopedics and Traumatology Institution, Luoyang Orthopedic-Traumatological Hospital, Luoyang, 2Shanghai Key Laboratory of Orthopedic Implants, Department of Orthopedic Surgery, Shanghai Ninth People’s Hospital, Shanghai Jiao Tong University School of Medicine, Shanghai, People’s Republic of China Abstract: As a commonly used implant material, calcium sulfate cement (CSC, has some shortcomings, including low compressive strength, weak osteoinduction capability, and rapid degradation. In this study, silica-based mesoporous materials such as SBA-15 were synthesized and combined with CSC to prepare CSC/SBA-15 composites. The properties of SBA-15 were characterized by X-ray diffraction, transmission electron microscopy, and nitrogen adsorption–desorption isotherms. SBA-15 was blended into CSC at 0, 5, 10, and 20 wt%, referred to as CSC, CSC-5S (5% mass ratio, CSC-10S (10% mass ratio, and CSC-20S (20% mass ratio, respectively. Fourier-transform infrared spectroscopy and compression tests were used to determine the structure and mechanical properties of the composites, respectively. The formation of hydroxyapatite on composite surfaces was analyzed using scanning electron microscopy and X-ray diffraction after soaking in simulated body fluid. BMP-2 was loaded into the composites by vacuum freeze-drying, and its release characteristics were detected by Bradford protein assay. The in vitro degradation of the CSC/SBA-15 composite was investigated by measuring weight loss. The results showed that the orderly, nanostructured, mesoporous SBA-15 possessed regular pore size and structure. The compressive strength of CSC/SBA-15 increased with the increase in SBA-15 mass ratio, and CSC-20S demonstrated the maximum strength. Compared to CSC, hydroxyapatite that formed on the surfaces of CSC/SBA-15 was uniform and compact. The degradation rate of CSC/SBA-15 decreased with increasing

  12. Synthesis of Pt-Sn core-shell nanoparticles deposited on SBA-15 modified

    Alvarez-Contreras, L.; Alonso-Lemus, I. [Centro de Investigacion en Materiales Avanzados S.C., Laboratorio Nacional de Nanotecnologia (Mexico); Botte, G. G. [Ohio University, Center for Electrochemical Engineering Research, Department of Chemical and Biomolecular Engineering (United States); Verde-Gomez, Y., E-mail: ysmaelverde@yahoo.com [Instituto Tecnologico de Cancun (Mexico)

    2013-07-15

    A novel one-step synthesis method to prepare Pt-Sn bimetallic nanoparticles supported on mesoporous silica with high surface area (SBA-15, 700 m{sup 2}/g) and narrow pore size distribution (around 9.5 nm) was developed. Tin incorporation plays an important dual role, to create active sites into the silica walls that serve as particles anchors center, and to grow Pt-Sn core-shell nanoparticles. High-resolution transmission and scanning electron microscopy, and X-ray diffraction pattern confirm the formation of the Pt-Sn core-shell type nanoparticles ( Almost-Equal-To 1-10 nm). The metal loading was 2.2 and 2.3 wt% for Pt and Sn, respectively. Electron microscopy results show that the metal nanoparticles were deposited not only on the matrix, but also inside of it. Structural, textural, and morphological features of the SBA-15 were slightly affected after the nanoparticles deposition, maintaining its high surface area. The results obtained suggest that Pt-Sn on SBA-15 could be attractive material for several catalytic applications, due to the narrow particle size distribution achieved (from 1 to 10 nm) the high dispersion on the support, as well as the Pt-Sn alloy developed.Graphical Abstract.

  13. Thermoresponsive copolymer-grafted SBA-15 porous silica particles for temperature-triggered topical delivery systems

    S. A. Jadhav

    2017-02-01

    Full Text Available A series of poly(N-isopropylacrylamide-co-acrylamide thermoresponsive random copolymers with different molecular weights and composition were synthesized and characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR, differential scanning calorimetry (DSC, size exclusion chromatography (SEC and proton nuclear magnetic resonance (NMR spectroscopy. The lower critical solution temperatures (LCST of the copolymers were tuned by changing the mole ratios of monomers. Copolymer with highest molecular weight and LCST (41.2 °C was grafted on SBA-15 type mesoporous silica particles by a two-step polymer grafting procedure. Bare SBA-15 and the thermoresponsive copolymergrafted (hybrid SBA-15 particles were fully characterized by scanning electron microscope (SEM, ATR-FTIR, thermogravimetric analysis (TGA and Brunauer-Emmett-Teller (BET analyses. The hybrid particles were tested for their efficiency as temperature-sensitive systems for dermal delivery of the antioxidant rutin (quercetin-3-O-rutinoside. Improved control over rutin release by hybrid particles was obtained which makes them attractive hybrid materials for drug delivery.

  14. MIL-53(Fe), MIL-101, and SBA-15 porous materials: potential platforms for drug delivery.

    Gordon, Jeff; Kazemian, Hossein; Rohani, Sohrab

    2015-02-01

    Conventional drug administration suffers from several drawbacks, including a lack of specificity for diseased tissue, the necessity of large and frequent doses, and adverse side effects. Great effort is currently being devoted to developing nanoparticle-based therapeutics capable of prolonging drug administration and providing better control. Here we demonstrate the use of flexible microporous MIL-53(Fe) and mesoporous MIL-101 and SBA-15 as matrices for the adsorption and in vitro drug delivery of acetaminophen, progesterone, and stavudine. A drug loading of 20 wt.% was achieved for each of the nanomaterials using an incipient wetness impregnation procedure. BET, DSC, and XRPD analyses indicated that the entire loaded amount of each of the model drugs had successfully been incorporated within the mesoporous channels of both MIL-101 and SBA-15. DSC analysis evidenced that a portion of each of the model drugs had deposited onto the outer surface of MIL-53(Fe) particles; however, the portion of each drug that had incorporated within the microporous channels was slowly delivered in a diffusion-controlled process, which occurred over a period of up to six days for acetaminophen. These results demonstrate the unique ability of MIL-53(Fe) to adapt its porosity and optimize drug-matrix interactions. Owing to its larger pore diameters and weaker host-guest interactions, MIL-101 release times were shorter, yet still prolonged, as evidenced by the complete release of stavudine after five days. Complete release of each of the drugs from SBA-15 occurred very quickly as a result of rapid drug dissolution and diffusion out of the mesopores. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Size and spatial distribution of micropores in SBA-15 using CM-SANS

    Pollock, Rachel A.; Walsh, Brenna R.; Fry, Jason A.; Ghampson, Tyrone; Centikol, Ozgul; Melnichenko, Yuri B.; Kaiser, Helmut; Pynn, Roger; Frederick, Brian G.

    2011-01-01

    Diffraction intensity analysis of small-angle neutron scattering measurements of dry SBA-15 have been combined with nonlocal density functional theory (NLDFT) analysis of nitrogen desorption isotherms to characterize the micropore, secondary mesopore, and primary mesopore structure. The radial dependence of the scattering length density, which is sensitive to isolated surface hydroxyls, can only be modeled if the NLDFT pore size distribution is distributed relatively uniformly throughout the silica framework, not localized in a 'corona' around the primary mesopores. Contrast matching-small angle neutron scattering (CM-SANS) measurements, using water, decane, tributylamine, cyclohexane, and isooctane as direct probes of the size of micropores indicate that the smallest pores in SBA-15 have diameter between 5.7 and 6.2 (angstrom). Correlation of the minimum pore size with the onset of the micropore size distribution provides direct evidence that the shape of the smallest micropores is cylinderlike, which is consistent with their being due to unraveling of the polymer template.

  16. Repeated sorption of water in SBA-15 investigated by means of in situ small-angle x-ray scattering

    Erko, M; Paris, O; Wallacher, D; Findenegg, G H

    2012-01-01

    The effect of repeated cycles of water adsorption/desorption on the structural stability of ordered mesoporous silica SBA-15 is studied by small-angle x-ray scattering (SAXS). In situ sorption measurements are conducted using a custom-built sorption apparatus in connection with a laboratory SAXS setup. Two striking irreversible changes are observed in the sorption isotherms as derived from the integrated SAXS intensity. First, the capillary condensation pressure shifts progressively to lower relative pressure values with increasing number of sorption cycles. This effect is attributed to chemisorption of water at the silica walls, resulting in a change of the fluid-wall interaction. Second, the sorption cycles do not close completely at vanishing vapour pressure, suggesting that progressively more water remains trapped within the porous material after each cycle. This effect is interpreted to be the result of an irreversible collapse of parts of mesopores, originating from pore wall deformation due to the large Laplace pressure of water acting on the pore walls at capillary condensation and capillary evaporation. (paper)

  17. Amine-modified ordered mesoporous silica: Effect of pore size on carbon dioxide capture

    V. Zelenak; M. Badanicova; D. Halamova; J. Cejka; A. Zukal; N. Murafa; G. Goerigk [P.J. Safarik University, Kosice (Slovak Republic)

    2008-10-15

    Three mesoporous silica materials with different pore sizes and pore connectivity were prepared and functionalized with aminopropyl (AP) ligands by post-synthesis treatment. The materials were characterized by small angle X-ray scattering (SAXS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and nitrogen adsorption/desorption experiments. The carbon dioxide sorption on modified mesoporous molecular sieves was investigated by using of microbalances at 25{sup o}C, and the influence of pore size and pore architecture on CO{sub 2} sorption was discussed. The large pore silica, SBA-15, showed the largest carbon dioxide sorption capacity (1.5 mmol/g), relating to highest amine surface density in this material. On the other hand, three-dimensional accessibility of amine sites inside the pores of SBA-12 silica resulted in a faster response to CO{sub 2} uptake in comparison with MCM-41 and SBA-15 molecular sieves

  18. Highly active and durable Ca-doped Ce-SBA-15 catalyst for biodiesel production

    Thitsartarn, Warintorn; Maneerung, Thawatchai; Kawi, Sibudjing

    2015-01-01

    In this work, Ca-doped Ce-incorporated SBA-15 (Ca/CeS) catalyst was successfully synthesized by using direct synthesis of Ce-incorporated SBA-15 followed by impregnation of CaO (calcium oxide). The maximum Si/Ce molar ratio that Ce atoms can be incorporated successfully into the mesoporous framework was found to be 5 (CeS-5). After the impregnation of 30 wt. % Ca, the obtained 30Ca/CeS-5 catalysts showed the superior catalytic performance for transesterification reaction of palm oil with methanol and also the higher catalytic activity as compared to other supported catalysts, i.e. CaO/CeO 2 and CaO–CeO 2 /SBA-15. This can be attributed to the well-dispersion of CaO on the CeS-5 support surface. Furthermore, it was found that the leaching of Si, Ce and Ca from the catalyst into biodiesel produced was negligible (i.e. <1 ppm after 7 cycles), indicating the strong interaction between CaO and CeS-5 support. As a result, the 30Ca/CeS-5 catalyst can be reused at least 15 cycles with insignificant decrease in catalytic activity, offering the efficient CaO-based catalyst for biodiesel production. - Highlights: • Mesoporous Ca-based catalyst was successfully developed for biodiesel production. • Catalyst exhibited high activity towards transesterification (FAME yield > 98%). • Catalyst can be effectively re-used at least 15 cycles. • Extremely low catalyst contaminant (<1 ppm) was presented

  19. Supercapacitors based on ordered mesoporous carbon derived from furfuryl alcohol: effect of the carbonized temperature.

    Li, Na; Xu, Jianxiong; Chen, Han; Wang, Xianyou

    2014-07-01

    Supercapacitors are successfully prepared from ordered mesoporous carbon (OMC) synthesized by employing the mesoporous silica, SBA-15 as template and furfuryl alcohol as carbon source. It is found that the carbonized temperature greatly influences the physical properties of the synthesized mesoporous carbon materials. The optimal carbonized temperature is measured to be 600 degrees C under which OMC with the specific surface area of 1219 m2/g and pore volume of 1.31 cm3/g and average pore diameter of - 3 nm are synthesized. The OMC materials synthesized under different carbonized temperature are used as electrode material of supercapacitors and the electrochemical properties of the OMC materials are compared by using cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge-discharge and self-discharge tests. The results show that the electrochemical properties of the OMC materials are directly related to the specific surface area and pore volume of the mesoporous carbon and the electrode prepared from the OMC synthesized under the carbonized temperature of 600 degrees C (OMC-600) exhibits the most excellent electrochemical performance with the specific capacitance of 207.08 F/g obtained from cyclic voltammetry at the scan rate of 1 mV/s, small resistance and low self-discharge rate. Moreover, the supercapacitor based on the OMC-600 material exhibits good capacitance properties and stable cycle behavior with the specific capacitance of 105 F/g at the current density of 700 mA/g, and keeps a specific capacitance of 98 F/g after 20000 consecutive charge/discharge cycles.

  20. Template occluded SBA-15: An effective dissolution enhancer for poorly water-soluble drug

    Fu Tingming, E-mail: futingming@gmail.com [College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210029 (China); Guo Liwei; Le Kang; Wang Tianyao; Lu Jin [College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210029 (China)

    2010-09-15

    The aim of the present work was to improve the dissolution rate of piroxicam by inclusion into template occluded SBA-15. Our strategy involves directly introducing piroxicam into as-prepared SBA-15 occluded with P123 (EO{sub 20}PO{sub 70}EO{sub 20}) by self assembling method in acetonitrile/methylene chloride mixture solution. Ultraviolet spectrometry experiment and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) profiles show that the piroxicam and P123 contents in the inclusion compound are 12 wt% and 28 wt%, respectively. X-ray powder diffraction and DSC analysis reveal that the included piroxicam is arranged in amorphous form. N{sub 2} adsorption-desorption experiment indicates that the piroxicam has been introduced to the mesopores instead of precipitating at the outside of the silica material. The inclusion compound was submitted to in vitro dissolution tests, the results show that the piroxicam dissolve from template occluded inclusion compound more rapidly, than these from the piroxicam crystalline and template removed samples in all tested conditions. Thus a facile method to improve the dissolution rate of poorly water-soluble drug was established, and this discovery opens a new avenue for the utilization of templates used for the synthesis of mesoporous materials.

  1. Template occluded SBA-15: An effective dissolution enhancer for poorly water-soluble drug

    Fu Tingming; Guo Liwei; Le Kang; Wang Tianyao; Lu Jin

    2010-01-01

    The aim of the present work was to improve the dissolution rate of piroxicam by inclusion into template occluded SBA-15. Our strategy involves directly introducing piroxicam into as-prepared SBA-15 occluded with P123 (EO 20 PO 70 EO 20 ) by self assembling method in acetonitrile/methylene chloride mixture solution. Ultraviolet spectrometry experiment and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) profiles show that the piroxicam and P123 contents in the inclusion compound are 12 wt% and 28 wt%, respectively. X-ray powder diffraction and DSC analysis reveal that the included piroxicam is arranged in amorphous form. N 2 adsorption-desorption experiment indicates that the piroxicam has been introduced to the mesopores instead of precipitating at the outside of the silica material. The inclusion compound was submitted to in vitro dissolution tests, the results show that the piroxicam dissolve from template occluded inclusion compound more rapidly, than these from the piroxicam crystalline and template removed samples in all tested conditions. Thus a facile method to improve the dissolution rate of poorly water-soluble drug was established, and this discovery opens a new avenue for the utilization of templates used for the synthesis of mesoporous materials.

  2. Effect of ceria and zirconia promotors on Ni/SBA-15 catalysts for coking and sintering resistant steam reforming of propylene glycol in microreactors

    Shanmugam, V.; Zapf, R.; Neuberg, S.; Hessel, V.; Kolb, G.

    2017-01-01

    Highly dispersed and size controlled Ni nanoparticles in CeO2, ZrO2 and CeO2-ZrO2 promoted mesoporous SBA-15 silica were achieved with the aid of treatment by ultrasound. The catalysts were characterized systematically to investigate their morphological structure and surface properties. It was found

  3. Photo-Catalytic Properties of TiO2 Supported on MWCNTs, SBA-15 and Silica-Coated MWCNTs Nanocomposites.

    Ramoraswi, Nteseng O; Ndungu, Patrick G

    2015-12-01

    Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207-301 m(2)/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites, which had a significantly greater photo-catalytic activity than the TiO2/CNT nanocomposites in spite of the high electron-hole recombination phenomena observed with the photoluminescence results. Discussions in terms of morphological, textural and physical-chemical aspects to account for the result are presented.

  4. The enhancement of photoresponse of an ordered inorganic-organic hybrid architecture by increasing interfacial contacts

    Zhang Bin; Chen Xudong; Ma Shaohua; Yang Jin; Zhang Mingqiu; Chen Yujie

    2010-01-01

    A modified ZnO quantum dot/polythiophene (ZnO/PTh) inorganic-organic hybrid architecture was fabricated by using ordered mesoporous silica (SBA-15) as the retaining template. First, a two-step strategy was developed to synthesize an ordered organic conducting polymer composite (PTh/SBA-15). Then, ZnO quantum dots were in situ formed on the pore walls of the ordered PTh/SBA-15 composite. Photoresponse of the inorganic-organic hybrid was studied with respect to its incident photon to collected electron conversion efficiency (IPCE) and morphology. The presence of SBA-15 proved to be critical for controlling the interfacial morphology and hence enlarging the interfacial area of the inorganic-organic heterojunction. The proposed approach may act as a key method to open up potential applications in photovoltaic devices.

  5. The enhancement of photoresponse of an ordered inorganic-organic hybrid architecture by increasing interfacial contacts.

    Zhang, Bin; Chen, Xudong; Ma, Shaohua; Chen, Yujie; Yang, Jin; Zhang, Mingqiu

    2010-02-10

    A modified ZnO quantum dot/polythiophene (ZnO/PTh) inorganic-organic hybrid architecture was fabricated by using ordered mesoporous silica (SBA-15) as the retaining template. First, a two-step strategy was developed to synthesize an ordered organic conducting polymer composite (PTh/SBA-15). Then, ZnO quantum dots were in situ formed on the pore walls of the ordered PTh/SBA-15 composite. Photoresponse of the inorganic-organic hybrid was studied with respect to its incident photon to collected electron conversion efficiency (IPCE) and morphology. The presence of SBA-15 proved to be critical for controlling the interfacial morphology and hence enlarging the interfacial area of the inorganic-organic heterojunction. The proposed approach may act as a key method to open up potential applications in photovoltaic devices.

  6. Grafting of alumina on SBA-15: Effect of surface roughness

    Zukal, Arnošt; Šiklová, Helena; Čejka, Jiří

    2008-01-01

    Roč. 24, č. 17 (2008), s. 9837-9842 ISSN 0743-7463 R&D Projects: GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alumina-grafted materials * SBA-15 * Nitrogen adsorption Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.097, year: 2008

  7. Sulfated zirconia modified SBA-15 catalysts for cellobiose hydrolysis

    Degirmenci, V.; Uner, D.; Cinlar, B.; Shanks, B.H.; Yilmaz, A.; Santen, van R.A.; Hensen, E.J.M.

    2011-01-01

    Zirconia modified SBA-15 becomes a very active catalyst for the selective hydrolysis of cellobiose to glucose after sulfation. Spectroscopic investigations indicate the presence of Brønsted acid sites with similar properties to those present in conventional sulfated zirconia. Indications are found

  8. Influence of different structured channels of mesoporous silicate on the controlled ibuprofen delivery

    Gao, Lin; Sun, Jihong; Zhang, Li; Wang, Jinpeng; Ren, Bo

    2012-01-01

    The bimodal mesoporous silicas with short random mesoporous channels and MCM-41 with long ordered mesopores were synthesised and modified with 3-(2-aminoethylamino) propyltrimethoxysilane as ibuprofen carriers to study the influence of mesoporous structure on drug delivery property. For further comparing the different mesoporous channels, modified SBA-15 with relative large and long ordered mesopores was also synthesized as drug carriers. The resultant samples were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, N 2 adsorption–desorption isotherms, thermogravimetric analyses, solid-state 29 Si NMR spectra, elemental analysis, and UV–vis spectra. Meanwhile, the Korsmeyer–Peppas equation f t = kt n was employed to analyze the drug release profile and three release mediums including simulated fluid solution, distilled water and simulated gastric fluid were used. The results indicated that the modified BMMs with the bimodal mesopores leaded to the most drug loading amount of 25.0 mg/0.1 g, while the MCM-41 with the long and one-dimensional mesopores had the least loading amount around 20.3 mg/0.1 g. Meanwhile, the easier diffusion behavior of drug molecules in the bimodal mesopore channels of BMMs resulted in relatively faster drug release properties in comparison with MCM-41, while the release time maintained in SBF for about 12 h (release percent was about 90 wt%) and corresponding release constant k obtained from Korsmeyer–Peppas equation was around 4.10. Highlights: ► BMMs, MCM-41 and SBA-15 with different mesostructure channels were modified with amino groups via post-treatment procedure. ► Loading and release profiles of ibuprofen in modified BMMs, MCM-41 and SBA-15. ► BMMs presents more drug loading amount than MCM-41 as well as better controlled release than SBA-15.

  9. Influence of different structured channels of mesoporous silicate on the controlled ibuprofen delivery

    Gao, Lin [Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, 100 PingLeYuan, Chaoyang District, Beijing 100124 (China); Sun, Jihong, E-mail: jhsun@bjut.edu.cn [Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, 100 PingLeYuan, Chaoyang District, Beijing 100124 (China); Zhang, Li; Wang, Jinpeng; Ren, Bo [Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, 100 PingLeYuan, Chaoyang District, Beijing 100124 (China)

    2012-08-15

    The bimodal mesoporous silicas with short random mesoporous channels and MCM-41 with long ordered mesopores were synthesised and modified with 3-(2-aminoethylamino) propyltrimethoxysilane as ibuprofen carriers to study the influence of mesoporous structure on drug delivery property. For further comparing the different mesoporous channels, modified SBA-15 with relative large and long ordered mesopores was also synthesized as drug carriers. The resultant samples were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, N{sub 2} adsorption-desorption isotherms, thermogravimetric analyses, solid-state {sup 29}Si NMR spectra, elemental analysis, and UV-vis spectra. Meanwhile, the Korsmeyer-Peppas equation f{sub t} = kt{sup n} was employed to analyze the drug release profile and three release mediums including simulated fluid solution, distilled water and simulated gastric fluid were used. The results indicated that the modified BMMs with the bimodal mesopores leaded to the most drug loading amount of 25.0 mg/0.1 g, while the MCM-41 with the long and one-dimensional mesopores had the least loading amount around 20.3 mg/0.1 g. Meanwhile, the easier diffusion behavior of drug molecules in the bimodal mesopore channels of BMMs resulted in relatively faster drug release properties in comparison with MCM-41, while the release time maintained in SBF for about 12 h (release percent was about 90 wt%) and corresponding release constant k obtained from Korsmeyer-Peppas equation was around 4.10. Highlights: Black-Right-Pointing-Pointer BMMs, MCM-41 and SBA-15 with different mesostructure channels were modified with amino groups via post-treatment procedure. Black-Right-Pointing-Pointer Loading and release profiles of ibuprofen in modified BMMs, MCM-41 and SBA-15. Black-Right-Pointing-Pointer BMMs presents more drug loading amount than MCM-41 as well as better controlled release than SBA-15.

  10. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  12. Ordered mesoporous silica-based inorganic nanocomposites

    Wang Qingqing; Shantz, Daniel F.

    2008-01-01

    This article reviews the synthesis and characterization of nanoparticles and nanowires grown in ordered mesoporous silicas (OMS). Summarizing work performed over the last 4 years, this article highlights the material properties of the final nanocomposite in the context of the synthesis methodology employed. While certain metal-OMS systems (e.g. gold in MCM-41) have been extensively studied this article highlights that there is a rich set of chemistries that have yet to be explored. The article concludes with some thoughts on future developments and challenges in this area. - Graphical abstract: HAADF TEM image of gold nanoparticles in amine-functionalized MCM-41 (from Ref. [22])

  13. Fluid adsorption in ordered mesoporous solids determined by in situ small-angle X-ray scattering.

    Findenegg, Gerhard H; Jähnert, Susanne; Müter, Dirk; Prass, Johannes; Paris, Oskar

    2010-07-14

    The adsorption of two organic fluids (n-pentane and perfluoropentane) in a periodic mesoporous silica material (SBA-15) is investigated by in situ small-angle X-ray scattering (SAXS) using synchrotron radiation. Structural changes are monitored as the ordered and disordered pores in the silica matrix are gradually filled with the fluids. The experiments yield integrated peak intensities from up to ten Bragg reflections from the 2D hexagonal pore lattice, and additionally diffuse scattering contributions arising from disordered (mostly intrawall) porosity. The analysis of the scattering data is based on a separation of these two contributions. Bragg scattering is described by adopting a form factor model for ordered pores of cylindrical symmetry which accounts for the filling of the microporous corona, the formation of a fluid film at the pore walls, and condensation of the fluid in the core. The filling fraction of the disordered intrawall pores is extracted from the diffuse scattering intensity and its dependence on the fluid pressure is analyzed on the basis of a three-phase model. The data analysis introduced here provides an important generalisation of a formalism presented recently (J. Phys. Chem. C, 2009, 13, 15201), which was applicable to contrast-matching fluids only. In this way, the adsorption behaviour of fluids into ordered and disordered pores in periodic mesoporous materials can be analyzed quantitatively irrespective of the fluid density.

  14. In-situ infrared study of CO{sub 2} adsorption on SBA-15 grafted with {gamma}-(aminopropyl)triethoxysilane

    Alex C.C. Chang; Steven S.C. Chuang; McMahan Gray; Yee Soong [University of Akron, Akron, OH (United States). Chemical Engineering Department

    2003-04-01

    CO{sub 2} adsorption/desorption on SBA-15 grafted with {gamma}-(aminopropyl)triethoxysilane (APTS) has been studied by infrared spectroscopy coupled with temperature-programmed desorption. SBA-15, a mesoporous silica material with a uniform pore size of 21 nm and a surface area of 200-230 m{sup 2}/g, provides an OH functional group for grafting of {gamma}-(aminopropyl)triethoxysilane. The amine-grafted SBA-15 adsorbed CO{sub 2} as carbonates and bicarbonates with a total capacity of 200-400 {mu}mol/g. The heat of CO{sub 2} desorption was determined to be 3.2-4.5 kJ/mol in the presence of H{sub 2}O and 6.6-11.0 kJ/mol in the absence of H{sub 2}O during temperature-programmed desorption. Repeated CO{sub 2} adsorption/desorption CO{sub 2} cycles shifted the desorption peak temperature downward and decreased the heat of CO{sub 2} adsorption. 22 refs., 9 figs., 3 tabs.

  15. Efficient epoxidation over cyanocobalamine containing SBA-15 organic-inorganic nanohybrids

    Karimi, Z. [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mahjoub, A.R., E-mail: mahjouba@modares.ac.ir [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2010-05-01

    SBA-15 mesoporous silica is synthesized using triblock copolymer P123 surfactant and chemically modified by aminopropyl, thiol, ammonium and sulfonic acid functional groups. Functionalization is performed via post synthesize method using 3-aminopropyltriethoxysilane (APTES) or 3-mercatopropyl trimethoxysilane (MPTMS) precursor. The as synthesized mesoporous systems are applied for immobilization of cyanocobalamine. Functionalization effectively improves sorption properties of the supports, while different functional groups exert different effects. The organic-inorganic mesoporous materials are characterized via X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy (TEM), FT-IR and inductively coupled plasma-optical emission (ICP). The newly synthesized systems exhibit high catalytic activity for heterogeneous epoxidation of cyclooctene in presence of hydrogen peroxide. Reaction conditions are optimized, effect of functional groups on performance of the catalysts is taken into consideration and reusability of the designed heterogeneous systems is studied. Systems with chemically modified supports are shown to be more efficient and stable catalysts however; chemical nature of functional groups plays a crucial role.

  16. Optical oxygen sensing materials based on a novel dirhenium(I) complex assembled in mesoporous silica

    Liu Yanhong; Li Bin; Cong Yan; Zhang Liming; Fan Di; Shi Linfang

    2011-01-01

    A new dirhenium(I) complex fac-[{Re(CO) 3 (4,7-dinonadecyl-1,10-phenanthro -line)} 2 (4,4'-bipyridyl)] (trifluoromethanesulfonate) 2 (denoted as D-Re(I) ) is assembled in MCM-41 and SBA-15 type mesoporous silica support. The emission peaks of D-Re(I) in D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are observed at 522 and 517 nm, respectively. Their long excited lifetimes, which are of the order of microseconds, indicate the presence of phosphorescence emission arising from the metal to ligand charge-transfer (MLCT) transition. The luminescence intensities of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 decrease remarkably with increase in the oxygen concentration, meaning that they can be used as optical oxygen sensing materials based on luminescence quenching. The ratios I 0 /I 100 of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are estimated to be 5.6 and 20.1, respectively. The obtained Stern-Volmer oxygen quenching plots of the mesoporous sensing materials could be fitted well to the two-site Demas model and Lehrer model. - Research highlights: → Dirhenium(I) complex assembled in mesoporous molecular sieves for oxygen sensor design. → Large α-diimine ligand L used to improve oxygen sensing properties. → High sensitivity (I 0 /I 100 ) up to 20.1.

  17. Amperometric catechol biosensor based on laccase immobilized on nitrogen-doped ordered mesoporous carbon (N-OMC)/PVA matrix

    Guo, Meiqing; Wang, Hefeng; Huang, Di; Han, Zhijun; Wang, Xiaojun; Li, Qiang; Chen, Jing

    2014-01-01

    A functionalized nitrogen-containing ordered mesoporous carbon (N-OMC), which shows good electrical properties, was synthesized by the carbonization of polyaniline inside a SBA-15 mesoporous silica template. Based on this, through entrapping laccase onto the N-OMC/polyvinyl alcohol (PVA) film a facilely fabricated amperometric biosensor was developed. Laccase from Trametes versicolor was assembled on a composite film of a N-OMC/PVA modified Au electrode and the electrochemical behavior was investigated. The results indicated that the N-OMC modified electrode exhibits electrical properties towards catechol. The optimum experimental conditions of a biosensor for the detection of catechol were studied in detail. Under the optimal conditions, the sensitivity of the biosensor was 0.29 A*M −1 with a detection limit of 0.31 μM and a linear detection range from 0.39 μM to 8.98 μM for catechol. The calibration curve followed the Michaelis–Menten kinetics and the apparent Michaelis–Menten (K M app ) was 6.28 μM. This work demonstrated that the N-OMC/PVA composite provides a suitable support for laccase immobilization and the construction of a biosensor. (papers)

  18. Preparation of Al-SBA-15 Pellets with Low Amount of Additives: Effect of Binder Content on Texture and Mechanical Properties. Application to Friedel-Crafts Alkylation

    Topka, Pavel; Karban, Jindřich; Soukup, Karel; Jirátová, Květa; Šolcová, Olga

    2011-01-01

    Roč. 168, č. 1 (2011), s. 433-440 ISSN 1385-8947 R&D Projects: GA ČR GA104/09/0694; GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40720504 Keywords : mesoporous aluminosilicates * pellets * Al-SBA-15 Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.461, year: 2011

  19. Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

    Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

    2017-07-03

    Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

  20. Insight into the adsorption of tetracycline onto amino and amino-Fe3+ gunctionalized mesoporous silica: Effect of functionalized groups.

    Zhang, Ziyang; Li, Haiyan; Liu, Huijuan

    2018-03-01

    In order to study the influences of functionalized groups onto the adsorption of tetracycline, we prepared a series of amino and amino-Fe 3+ complex mesoporous silica adsorbents with diverse content of amino and Fe 3+ groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR) and N 2 adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe 3+ groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe 3+ increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe 3+ content increased from 3.93% to 8.26%, the Q max of the adsorbents increased from 102 to 188mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications. Copyright © 2017. Published by Elsevier B.V.

  1. Evaluation of bi-functionalized mesoporous silicas as reversed phase/cation-exchange mixed-mode sorbents for multi-residue solid phase extraction of veterinary drug residues in meat samples.

    Casado, Natalia; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Sierra, Isabel

    2017-04-01

    A SBA-15 type mesoporous silica was synthesized and bi-functionalized with octadecylsilane (C18) or octylsilane (C8), and sulfonic acid (SO 3 - ) groups in order to obtain materials with reversed-phase/strong cation-exchange mixed-mode retention mechanism. The resulting hybrid materials (SBA-15-C18-SO 3 - and SBA-15-C8-SO 3 - ) were comprehensively characterized. They showed high surface area, high pore volume and controlled porous size. Elemental analysis of the materials revealed differences in the amount of C18 and C8. SBA-15-C18-SO 3 - contained 0.19mmol/g of C18, while SBA-15-C8-SO 3 - presented 0.54mmol/g of C8. The SO 3 - groups anchored to the silica surface of the pore walls were 0.20 and 0.09mmol/g, respectively. The bi-functionalized materials were evaluated as SPE sorbents for the multi-residue extraction of 26 veterinary drug residues in meat samples using ultra-high-performance liquid chromatography coupled to mass spectrometry detector (UHPLC-MS/MS). Different sorbent amounts (100 and 200mg) and organic solvents were tested to optimize the extraction procedure. Both silicas showed big extraction potential and were successful in the extraction of the target analytes. The mixed-mode retention mechanism was confirmed by comparing both silicas with SBA-15 mesoporous silica mono-functionalized with C18 and C8. Best results were achieved with 200mg of SBA-15-C18-SO 3 - obtaining recoveries higher than 70% for the majority of analytes. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

    Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

    2017-06-01

    This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

  3. Modifying the Hierarchical Porosity of SBA-15 via Mild-Detemplation Followed by Secondary Treatments

    Zhang, Zheng; Melian-Cabrera, Ignacio

    2014-01-01

    Fenton-chemistry-based detemplation combined with secondary treatments offers options to tune the hierarchical porosity of SBA-15. This approach has been studied on a series of SBA-15 mesophases and has been compared to the conventional calcination. The as-synthesized and detemplated materials were

  4. Jet-Fuel Range Hydrocarbons from Biomass-Derived Sorbitol over Ni-HZSM-5/SBA-15 Catalyst

    Yujing Weng

    2015-12-01

    Full Text Available Aromatics and cyclic-hydrocarbons are the significant components of jet fuel with high energy-density. However, conventional technologies for bio-fuel production cannot produce these products without further aromatization and isomerization. In this work, renewable liquid fuel with high content of aromatics and cyclic-hydrocarbons was obtained through aqueous catalytic conversion of biomass sorbitol over Ni-HZSM-5/SBA-15 catalyst. Texture characteristics of the catalyst were determined by physisorption of N2, which indicated its bimodal pore structures were microporous (HZSM-5, pore width: 0.56 nm and mesoporous (SBA-15, pore width: 8 nm. The surface acidity included weak and strong acid sites, predominantly Lewis type, and was further confirmed by the NH3-TPD and Py-IR analysis. The catalytic performances were tested in a fixed-bed reactor under the conditions of 593 K, WHSV of 0.75 h−1, GHSV of 2500 h−1 and 4.0 MPa of hydrogen pressure, whereby oil yield of 40.4 wt. % with aromatics and cyclic-hydrocarbons content of 80.0% was obtained.

  5. Controlled drug release from bifunctionalized mesoporous silica

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

    2008-10-01

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

  6. Nanocasting of Periodic Mesoporous Materials as an Effective Strategy to Prepare Mixed Phases of Titania

    Luther Mahoney

    2015-12-01

    Full Text Available Mesoporous titanium dioxide materials were prepared using a nanocasting technique involving silica SBA-15 as the hard-template. At an optimal loading of titanium precursor, the hexagonal periodic array of pores in SBA-15 was retained. The phases of titanium dioxide could be easily varied by the number of impregnation cycles and the nature of titanium alkoxide employed. Low number of impregnation cycles produced mixed phases of anatase and TiO2(B. The mesoporous TiO2 materials were tested for solar hydrogen production, and the material consisting of 98% anatase and 2% TiO2(B exhibited the highest yield of hydrogen from the photocatalytic splitting of water. The periodicity of the pores was an important factor that influenced the photocatalytic activity. This study indicates that mixed phases of titania containing ordered array of pores can be prepared by using the nanocasting strategy.

  7. 新型靛红衍生化β-环糊精键合SBA-15液相色谱固定相的制备与表征%Preparation and Characterization of a Novel Isatin Derivative of β-Cyclodextrin-bonded SBA-15 Stationary Phase for HPLC

    张杨; 李来生; 程彪平; 周仁丹; 聂桂珍

    2014-01-01

    利用靛红的羰基与β-环糊精单取代乙二胺的缩合反应,合成得到一种靛红衍生化β-环糊精Schiff碱类化合物。以3-异氰酸丙基三乙氧基硅烷为偶联剂,将其键合到自制的有序介孔二氧化硅材料SBA-15表面,制得一种新型的靛红衍生化β-环糊精键合SBA-15液相色谱固定相( ISCDP)。分别对β-环糊精衍生物、SBA-15及固定相进行必要的结构表征。在反相色谱条件下,以卤代尿嘧啶类极性化合物和二取代苯位置异构体为探针,评价新固定相的基本色谱性能。在极性有机溶剂和反相模式下,将新固定相分别用于β-受体阻滞剂药物和丹磺酰化氨基酸对映体的拆分,探讨了相关色谱分离机理。实验表明,靛红吲哚环的引入,增强了环糊精类固定相对卤代尿嘧啶的反相色谱分离能力,分析时间小于7 min。固定相分离硝基苯胺、氨基苯酚和苯二酚的位置异构体时也表现出较高的立体选择性,其中对位异构体均最后被洗脱,这与包结作用相关;靛红衍生化β-环糊精配体也提高了固定相的手性分离能力,除疏水作用外,靛红衍生化β-环糊精配体还能提供偶极、氢键、π-π和包结等作用,多种协同作用力有利于提高新固定相的手性和非手性分离的选择性。 SBA-15作为键合基质,其有序的孔结构有利于保持色谱柱的良好渗透性和小的传质阻力,在快速高效分离分析中具有应用潜能。%An isatin derivative ofβ-cyclodextrin Schiff base was first synthesized by the condensation reaction between the carbonyl group of isatin and ethylenediamino group of the mono-substituted β-cyclodextrin. The Schiff base ligand was chemically linked to homemade ordered mesoporous SBA-15 silica gel via 3-( triethoxysilyl) propyl isocyanate coupling agent. In this way, a novel isatin derivative of β-cyclodextrin-bonded SBA-15 stationary phase ( ISCDP) was prepared

  8. Electrochemical Hydrogen Storage in a Highly Ordered Mesoporous Carbon

    Dan eLiu

    2014-10-01

    Full Text Available A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

  9. Silicon oxynitrides of KCC-1, SBA-15 and MCM-41 for CO 2 capture with excellent stability and regenerability

    Patil, Umesh

    2012-01-01

    We report the use of silicon oxynitrides as novel adsorbents for CO 2 capture. Three series of functionalized materials based on KCC-1, SBA-15 and MCM-41 with Si-NH 2 groups were prepared using a simple one-step process via thermal ammonolysis using ammonia gas, and they demonstrated excellent CO 2 capture capabilities. These materials overcome several limitations of conventional amine-grafted mesoporous silica. They offer good CO 2 capture capacity, faster adsorption-desorption kinetics, efficient regeneration and reuse, more crucially excellent thermal and mechanical stability even in oxidative environments, and a clean and green synthesis route, which allows the overall CO 2 capture process to be practical and sustainable. This journal is © The Royal Society of Chemistry 2012.

  10. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

    2015-09-01

    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  11. Interactions of NO{sub 2} at ambient temperature with cerium-zirconium mixed oxides supported on SBA-15

    Levasseur, Benoit; Ebrahim, Amani M. [The City College of New York and The Graduate School of CUNY 160 Convent Ave, New York, NY 10031 (United States); Burress, Jacob [NIST Center for Neutron Research, National Institute of Standards and Technology 100 Bureau Drive, Gaithersburg, MD 20899 (United States); Bandosz, Teresa J., E-mail: tbandosz@ccny.cuny.edu [The City College of New York and The Graduate School of CUNY 160 Convent Ave, New York, NY 10031 (United States)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Ce{sub 1-y}Zr{sub y}O{sub 2-x} mixed oxides were highly dispersed in mesoporous silica SBA-15. Black-Right-Pointing-Pointer A strong increase in the NO{sub 2} adsorption capacity was observed on composites. Black-Right-Pointing-Pointer The insertion of Zr{sup 4+} in ceria fluorite structure promotes the reduction of Ce{sup 4+} into Ce{sup 3+}. Black-Right-Pointing-Pointer Ce{sup 3+} and -OH groups were found to be the main active centers for NO{sub x} retention. Black-Right-Pointing-Pointer The structure remains quite stable after exposure to NO{sub 2} in ambient conditions. - Abstract: New silica-based composites were obtained using a slow precipitation of mixed oxide Ce{sub 1-x}Zr{sub x}O{sub 2} on the surface of mesoporous silica, SBA-15. The samples were tested as NO{sub 2} adsorbents in dynamic conditions at room temperature. The surface of the initial and exhausted materials was characterized using N{sub 2} sorption, XRD, TEM, potentiometric titration, and thermal analysis before and after exposure to NO{sub 2}. In comparison with unsupported Ce{sub 1-x}Zr{sub x}O{sub 2} mixed oxides, a significant increase in the NO{sub 2} adsorption capacity was observed. This is due to the high dispersion of active oxide phase on the surface of SBA-15. A linear trend was found between the NO{sub 2} adsorption capacity and the amount of Zr(OH){sub 4} added to the structure. Introduction of Zr{sup 4+} cations to ceria contributes to an increase in the amount of Ce{sup 3+}, which is the active center for the NO{sub 2} adsorption, and to an increase in the density of -OH groups. These groups are found to be involved in the retention of both NO{sub 2} and NO on the surface. After exposure to NO{sub 2}, an acidification of the surface caused by the oxidation of the cerium as well as the formation of nitrite and nitrates took place. The structure of the composites appears not to be affected by reactive adsorption of NO{sub 2}.

  12. Enhanced photocatalytic properties in well-ordered mesoporous WO3

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

    2010-01-01

    We used polyisoprene-block-ethyleneoxide copolymers as structure-directing agents to synthesise well-ordered and highly-crystalline mesoporous WO 3 architectures that possess improved photocatalytic properties due to enhanced dye-adsorption in absence of diffusion limitation. © 2010 The Royal Society of Chemistry.

  13. The Effect of Nitrogen Surface Ligands on Propane Metathesis: Design and Characterizations of N-modified SBA15-Supported Schrock-type Tungsten Alkylidyne

    Eid, Ahmed A.

    2014-04-01

    Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science[1]. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis[1]. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts[2]. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: -\\tOne with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, -\\tAnother\\tone\\twith\\tvicinal\\tbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15[3]. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials[4]. A fairly good

  14. Grafted chromium 13-membered dioxo-macrocyclic complex into aminopropyl-based nanoporous SBA-15

    Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Joharian, Monika; Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Muzart, Jacques [Institut de Chimie Moléculaire de Reims, CNRS-Université de Reims Champagne-Ardenne, BP 1039, 51687 Reims Cedex 2 (France); Fallah, Mahtab [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of)

    2013-07-15

    In a new approach, chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 after four step reactions by using coordinating ability of anchored amino functionalized SBA-15. After the termination of each step, the obtained product was characterized by FT-IR, low-angle X-ray diffraction (LA-XRD), N{sub 2} adsorption–desorption isotherms (Brunauer–Emmett–Teller (BET)–Barret–Joyner–Halenda (BJH)) and thermogravimetric analysis (TGA), and used as catalyst for the efficient and regioselective alcoholysis of styrene oxide to 2-alkoxy-1-phenylethanol product at ambient temperature. - Graphical abstract: Chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 using coordinating ability of anchored amino functionalized SBA-15. Preparation of the catalyst is depicted in Scheme 1. - Highlights: • Dioxo tetraazachromium macrocyclic complex grafted into the SBA-15-NH{sub 2} channels. • The bond is created by coordinating ability of anchored amino functionalized SBA-15. • The prepared nanocatalyst has superior activity in the alcoholysis of styrene oxide. • The catalyst is reusable at ambient temperature for the mentioned reaction.

  15. Fischer-Tropsch synthesis in slurry-phase reactors using Co/SBA-15 catalysts

    Rodrigues, J.J.; Lima, L.A.; Lima, W.S.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], e-mail: meiry@deq.ufcg.edu.br; Fernandes, F.A.N. [Universidade Federal do Ceara (UFCE), CE (Brazil). Dept. de Engenharia Quimica

    2011-07-15

    The objective of this work is to describe the production of bifunctional catalysts using the incipient humidity method, producing catalysts with 15 wt.% cobalt supported in SBA-15 molecular sieve, to be applied in the Fischer-Tropsch (FT) reaction. The originality of this work is its focus on the use of a 15 wt.% Co/SBA-15 catalyst in FT synthesis in slurry reactors. The deposition of cobalt over SBA-15 support was accomplished by impregnation with a 0.1-M aqueous solution of cobalt nitrate. The Fischer-Tropsch synthesis was carried out with the catalyst at 240 deg C and 20 atm, under a COH{sub 2} atmosphere (molar ratio= 1), in a slurry reactor for 8 hours. X-ray diffraction measurements showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co{sub 3}O{sub 4} in the catalyst. The addition of cobalt in the SBA-15 decreased the specific superficial area of the molecular sieve. The 15 wt.% Co/SBA-15 catalyst had a 40% CO conversion rate and a high selectivity towards the production of C{sub 5}{sup +} (53.9% after 8 hours). (author)

  16. VOx species supported on Al2O3-SBA-15 prepared by the grafting of alumina onto SBA-15: structure and activity in the oxidative dehydrogenation of ethane

    Botková, Š.; Čapek, L.; Setnička, M.; Bulánek, R.; Čičmanec, P.; Kalužová, A.; Pastva, Jakub; Zukal, Arnošt

    2016-01-01

    Roč. 119, č. 1 (2016), s. 319-333 ISSN 1878-5190 R&D Projects: GA ČR GAP106/10/0196 Institutional support: RVO:61388955 Keywords : Ethane * UV-Vis * VOx species * Al2O3-SBA-15 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.264, year: 2016

  17. Effects of ordered mesoporous structure and La-doping on the microwave absorbing properties of CoFe2O4

    Shang, Tao; Lu, Qingshan; Chao, Luomeng; Qin, Yanli; Yun, Yuehou; Yun, Guohong

    2018-03-01

    Low-density ordered mesoporous CoFe2O4 (Osbnd CFO) and CoLa0.12Fe1.88O4 (Osbnd CLFO) are prepared by nanocasting method using mesoporous silica SBA-15 as a hard-template. The crystal structure, surface chemical state, magnetic properties and electromagnetic parameters are characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption measurement, X-ray photoelectron spectroscopy, physical property measurement system and vector network analyzer. The results show that all the samples formed a single phase with cubic spinel structure. Meanwhile Osbnd CFO and Osbnd CLFO possess a highly ordered mesostructure. Comparing with particle CoFe2O4 (P-CFO), Osbnd CFO with high specific surface area exhibits lower magnetic saturation (Ms), higher imaginary part of complex permittivity (ε‧‧) and imaginary part of the complex permeability (μ‧‧). The minimum reflection loss (RL) of Osbnd CFO reaches -27.36 dB with a matching thickness of 3.0 mm. The enhancement of the microwave absorbing performances of Osbnd CFO can be mainly attributed to the good impedance matching, high electromagnetic wave attenuation and multiple reflections of electromagnetic wave originated from the ordered mesoporous structure. The Ms of Osbnd CLFO decreases after La3+ doping, while the specific surface area, coercivity value, ε‧‧ and μ‧‧ of Osbnd CLFO increase. The minimum RL of Osbnd CLFO reaches -46.47 dB with a thickness of 3.0 mm, and the effective absorption frequency bandwidth reaches 4.9 GHz.

  18. Ordered mesoporous carbon for electrochemical sensing: A review

    Ndamanisha, Jean Chrysostome [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Universite du Burundi, Institut de pedagogie appliquee, B.P. 5223, Bujumbura (Burundi); Guo Liping, E-mail: guolp078@nenu.edu.cn [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2012-10-17

    Highlights: Black-Right-Pointing-Pointer The preparation and functionalization of ordered mesoporous carbon. Black-Right-Pointing-Pointer Their applications as electrochemical sensors with high electrocatalytic activity. Black-Right-Pointing-Pointer A promising electrode material based on its interesting properties. - Abstract: With its well-ordered pore structure, high specific surface area and tunable pore diameters in the mesopore range, ordered mesoporous carbon (OMC) is suitable for applications in catalysis and sensing. We report recent applications of OMC in electrochemical sensors and biosensors. After a brief description of the electrochemical properties, the functionalization of the OMC for improvement of the electrocatalytic properties is then presented. We show how the ordered mesostructure of OMC is very important in those applications. The high density of edge plane-like defective sites (EDSs), oxygen-containing groups and a large surface area on OMC may provide many favorable sites for electron transfer to compounds, which makes OMC a potential novel material for an investigation of the electrochemical behavior of substances. Moreover, the structural capabilities of OMC at the scale of a few nanometers agree with immobilization of other electrocataytic substances. Interesting properties of this material may open up a new approach to study the electrochemical determination of other biomolecules.

  19. Silylated Co/SBA-15 catalysts for Fischer-Tropsch synthesis

    Jia Lihong; Jia Litao; Li Debao; Hou Bo; Wang Jungang; Sun Yuhan

    2011-01-01

    A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N 2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH 3 ) 3 species even after calcinations and H 2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH 3 ) 3 for the re-adsorption of α-olefins. -- Graphical abstract: The silylation of an SBA-15 before cobalt impregnation enhanced the reducibility of cobalt oxides on an SBA-15-supported cobalt catalyst and consequently increased the catalytic activity for Fischer-Tropsch synthesis. Display Omitted

  20. Immobilization of lipase and keratinase on functionalized SBA-15 nanostructured materials

    Le, Hy G.; Vu, Tuan A.; Tran, Hoa T. K.; Dang, Phuong T.

    2013-12-01

    SBA-15 nanostructured materials were synthesized via hydrothermal treatment and were functionalized with 3- aminopropyltriethoxysilane (APTES). The obtained samples were characterized by different techniques such as XRD, BET, TEM, IR and DTA. After functionalization, it showed that these nanostrucrured materials still maintained the hexagonal pore structure of the parent SBA-15. The model enzyms chosen in this study were lipase and keratinase. Lipase was a biocatalyst for hydrolyzation of long chain triglycerides or methyl esters of long chain alcohols and fatty acids; keratinase is a proteolytic enzyme that catalyzes the cleavage of keratin. The functionalized SBA-15 materials were used to immobilize lipase and keratinase, exhibiting higher activity than that of the unfunctionalized pure silica SBA-15 ones. This might be due to the enhancing of surface hydrophobicity upon functionalization. The surface functionalization of the nanostructured silicas with organic groups can favor the interaction between enzyme and the supports and consequently increasing the operational stability of the immobilized enzymes. The loading of lipase on functionalized SBA-15 materials was higher than that of keratinase. This might be rationalized by the difference in size of enzyms.

  1. Evidence for metalsupport interactions in Au modified TiO_{x}/SBA-15 materials prepared by photodeposition

    Mei, Bastian; Wiktor, Christian; Turner, Stuart; Pougin, Anna; Tendeloo, Van, Gustaaf; Fischer, Roland A.; Muhler, Martin; Strunk, Jennifer

    2013-01-01

    Abstract: Gold nanoparticles have been efficiently photodeposited onto titanate-loaded SBA-15 (Ti(x)/SBA-15) with different titania coordination. Transmission electron microscopy shows that relatively large Au nanoparticles are photodeposited on the outer surface of the Ti(x)/SBA-15 materials and that TiOx tends to form agglomerates in close proximity to the Au nanoparticles, often forming coreshell Au/TiOx structures. This behavior resembles typical processes observed due to strong-metal sup...

  2. A Pd/SBA-15 composite: synthesis, characterization and protein biosensing

    Liu Yuge; Zhang Jingjing; Hou Wenhua; Zhu Junjie [Key Laboratory of Mesoscopic Chemistry and Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)], E-mail: whou@nju.edu.cn, E-mail: jjzhu@nju.edu.cn

    2008-04-02

    In this paper, palladium (Pd) nanoparticles have been successfully encapsulated into the channels of modified SBA-15 in situ via a facile, ethylene glycol (EG)-assisted sonochemical method. The products were confirmed by x-ray diffraction, transmission electron microscopy (TEM) and nitrogen adsorption analysis. The Pd/SBA-15 composite was used for the realization of direct electron transfer of hemoglobin (Hb). Electrochemical results showed that the Pd nanoparticles in the channels of SBA-15 could enhance the direct electron transfer between Hb and the electrode surface. The composite modified electrode displayed excellent electrochemical behavior. The sensor fabricated by the composite showed an excellent response to the reduction of hydrogen peroxide (H{sub 2}O{sub 2}), and the linear range for the determination of H{sub 2}O{sub 2} was from 1.8 to 119.3 {mu}M with a detection limit of 0.8 {mu}M.

  3. Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

    Chunling Wei

    2016-10-01

    Full Text Available A series of vanadia catalysts supported on SBA-15 (V/SBA with a vanadia (V content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, and temperature-programmed reduction (TPR. It was found that these catalysts were effective for the dehydrogenation reaction, and the catalytic activity is correlated with the amount of dispersed vanadium species on the SBA-15 support. The 7% V/SBA catalyst shows the highest activity, which gives 40.8% isobutane conversion and 84.8% isobutene selectivity. The SBA-15-supported vanadia exhibits higher isobutane conversion and isobutene selectivity than the MCM-41-supported one.

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

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

    2015-01-01

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

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

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

    2015-01-15

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

  6. Ordered hierarchical mesoporous/microporous carbon derived from mesoporous titanium-carbide/carbon composites and its electrochemical performance in supercapacitor

    Liu, Hai-Jing; Wang, Jie; Wang, Cong-Xiao; Xia, Yong-Yao [Department of Chemistry and Shanghai Key Laboratory of Molecular, Catalysis and Innovative Materials, Institute of New Energy, Fudan University, Shanghai (China)

    2011-11-15

    Novel ordered hierarchical mesoporous/microporous carbon (OHMMC) derived from mesoporous titanium-carbide/carbon composites was prepared for the first time by synthesizing ordered mesoporous nanocrystalline titanium-carbide/carbon composites, followed by chlorination of titanium carbides. The mesostructure and microstructure can be conveniently tuned by controlling the TiC contents of mesoporous TiC/C composite precursor, and chlorination temperature. By optimal condition, the OHMMC has a high surface area (1917 m{sup 2}g{sup -1}), large pore volumes (1.24 cm{sup 3}g{sup -1}), narrow mesopore-size distributions (centered at about 3 nm), and micropore size of 0.69 and 1.25 nm, and shows a great potential as electrode for supercapacitor applications: it exhibits a high capacitance of 146 Fg{sup -1} in noaqueous electrolyte and excellent rate capability. The ordered mesoporous channel pores are favorable for retention and immersion of the electrolyte, providing a more favorable path for electrolyte penetration and transportation to achieve promising rate capability performance. Meanwhile, the micropores drilled on the mesopore-walls can increase the specific surface area to provide more sites for charge storage. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

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

    2010-01-15

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

  8. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15

    Sun, Qiangqiang; Wang, Yu; Li, Laisheng; Bing, Jishuai; Wang, Yingxin; Yan, Huihua

    2015-01-01

    Highlights: • Clofibric acid (CA) is efficiently mineralized by O 3 /MnO x /SBA-15. • Adsorption of CA and its intermediates on MnO x /SBA-15 is proved unimportant. • Initiation of hydroxyl radicals (·OH) is enhanced in O 3 /MnO x /SBA-15. • Uniformly distributed MnO x accounts for the high activity of MnO x /SBA-15. • Degradation routes of CA in ozonation alone and catalytic ozonation are proposed. - Abstract: Comparative experiments were conducted to investigate the catalytic ability of MnO x /SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O 3 /MnO x /SBA-15). Adsorption of CA and its intermediates by MnO x /SBA-15 was proved unimportant in O 3 /MnO x /SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO 3 ) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO x /SBA-15 facilitated the generation of hydroxyl radicals (·OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO x on SBA-15 were believed to be the main active component in MnO x /SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more ·OH

  9. Photocatalytic activity of Ce-modified SBA-15 for the degradation of ...

    transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and N2 adsorption/desorption analysis. ... water.7,8,18 Existence of different sites of cerium ions and ... hydrocarbons.21 In this study, Ce-SBA-15 and Ce-Al-SBA-.

  10. Thermogravimetric Analysis (TGA) Profile of Modified Sba-15 at Different Amount of Alkoxy silane Group

    Norhasyimi Rahmat; Nur Fathilah Mohd Yusof; Ezani Hafiza

    2014-01-01

    This study focused on meso porous silica SBA-15 modified with alkoxy silane functional group; phenyltriethoxysilane (PTES) and vinyltriethoxysilane (VTES) using direct synthesis and post-grafting methods. By direct synthesis method, SBA-15 template by triblock copolymer (P123) and functionalized with alkoxy silane groups at different amount of loadings were co-condensed with tetraethyl orthosilicate (TEOS) under acidic conditions. As for post-grafting method, different loadings of alkoxy silane groups were added after co-condensation of TEOS with P123 template. Both synthesis methods used calcination process to remove surfactant template at 550 degree Celsius for 5 hours. The derivatized SBA-15 was characterized by thermogravimetric analysis to evaluate the profile at different loadings of alkoxy silane groups with different synthesis method. At temperature range of 300-800 degree Celsius, post-grafting method displayed the highest weight loss of phenyl and vinyl groups. However, there was no significant difference of weight loss for different amount of organo silane groups. In this study, TGA has shown to be significant characterization means to determine the effects of different method used in synthesizing modified SBA-15. It was shown that different loading of phenyl and vinyl groups did not affect the efficiency of surfactant removal. (author)

  11. Controlling reaction pathways for alcohol dehydration and dehydrogenation over FeSBA-15 catalysts

    Guan, Y.; Li, Y.; Santen, van R.A.; Hensen, E.J.M.; Li, Can

    2007-01-01

    The iron location in FeSBA-15 strongly influences the selectivity to dehydrogenation and dehydration in ethanol conversion. At low iron loading, Fe is present as isolated species in the amorphous silica phase. At higher loading additional aggregated forms of iron oxide exist. Isolated species in the

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

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

    2015-01-01

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

  13. Pore-expanded SBA-15 sulfonic acid silicas for biodiesel synthesis.

    Dacquin, J P; Lee, A F; Pirez, C; Wilson, K

    2012-01-07

    Here we present the first application of pore-expanded SBA-15 in heterogeneous catalysis. Pore expansion over the range 6-14 nm confers a striking activity enhancement towards fatty acid methyl ester (FAME) synthesis from triglycerides (TAG), and free fatty acid (FFA), attributed to improved mass transport and acid site accessibility. This journal is © The Royal Society of Chemistry 2012

  14. Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

    Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

    2014-01-01

    Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    Bendjeriou-Sedjerari, Anissa

    2016-08-11

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  16. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  17. Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves MCM-41 and SBA-15

    Balcar, Hynek; Shinde, Tushar; Žilková, Naděžda; Bastl, Zdeněk

    2011-01-01

    Roč. 7, January (2011), s. 22-28 ISSN 1860-5397 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkene metathesis * catalyst immobilization * hybrid catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.517, year: 2011

  18. Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures

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

    2015-01-01

    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. 108 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. Oriented molecular rotors: Fluorinated molecular rotors (see picture) were engineered in mesoporous hybrid organosilica architectures with crystalline order in their walls. The rotor dynamics was established by magic angle spinning NMR and dielectric measurements, indicating a rotational correlation time as short as 10-9 s at 325 K. The dynamics was modulated by I2 vapors entering the pores.

  19. Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures

    Bracco, Silvia

    2015-02-16

    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. 108 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. Oriented molecular rotors: Fluorinated molecular rotors (see picture) were engineered in mesoporous hybrid organosilica architectures with crystalline order in their walls. The rotor dynamics was established by magic angle spinning NMR and dielectric measurements, indicating a rotational correlation time as short as 10-9 s at 325 K. The dynamics was modulated by I2 vapors entering the pores.

  20. Electrochemical detection of ultratrace nitroaromatic explosives using ordered mesoporous carbon

    Zang Jianfeng; Guo Chunxian; Hu Fengping [School of Chemical and Biomedical Engineering and Center for Advanced Bionanosystems, Nanyang Technological University, 70 Nanyang Drive, Singapore 637457 (Singapore); Yu Lei [Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, Storrs, CT 06269 (United States); Li Changming, E-mail: ecmli@ntu.edu.sg [School of Chemical and Biomedical Engineering and Center for Advanced Bionanosystems, Nanyang Technological University, 70 Nanyang Drive, Singapore 637457 (Singapore)

    2011-01-10

    A sensitive electrochemical sensor has been fabricated to detect ultratrace nitroaromatic explosives using ordered mesoporus carbon (OMC). OMC was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption measurements. Glassy carbon electrodes functionalized with OMC show high sensitivity of 62.7 {mu}A cm{sup -2} per ppb towards 2,4,6-trinitrotoluene (TNT). By comparison with other materials such as carbon nanotubes and ordered mesoporous silica, it is found that the high performance of OMC toward sensing TNT is attributed to its large specific surface area and fast electron transfer capability. As low as 0.2 ppb TNT, 1 ppb 2,4-dinitrotoluene and 1 ppb 1,3-dinitrobenzene can be detected on OMC based electrodes. This work renders new opportunities to detect ultratrace explosives for applications of environment protections and home securities against chemical warfare agents.

  1. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Yang, Jae Hwan [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of); Park, Hwan Seo; Ahn, Do-Hee [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Yim, Man-Sung, E-mail: msyim@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of)

    2016-11-15

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi{sub 2}O{sub 3} (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi{sub 2}O{sub 3} and the glass composition. It was confirmed that BiI{sub 3}, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi{sub 5}O{sub 7}I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10{sup −3}–10{sup −2} g/m{sup 2} day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of {sup 129}I. - Highlights: • Glass composite waste forms were developed to stabilize iodine confined in Bi-embedded SBA-15. • BiI{sub 3} within Bi-embedded SBA-15 was transformed to BiOI and Bi{sub 5}O{sub 7}I during sintering process. • Iodine volatility was significantly affected by glass composition and Bi{sub 2}O{sub 3} additive. • Iodine leaching rates were 10{sup −3}–10{sup −2} g/m{sup 2} day due to the stable iodine phases encapsulated by glassy networks. • Glass composite waste form of Bi-embedded SBA-15 is expected to be a candidate material for stable storage of {sup 129}I.

  2. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15.

    Sun, Qiangqiang; Wang, Yu; Li, Laisheng; Bing, Jishuai; Wang, Yingxin; Yan, Huihua

    2015-04-09

    Comparative experiments were conducted to investigate the catalytic ability of MnO(x)/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O3/MnO(x)/SBA-15). Adsorption of CA and its intermediates by MnO(x)/SBA-15 was proved unimportant in O3/MnO(x)/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO3) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO(x)/SBA-15 facilitated the generation of hydroxyl radicals (OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO(x) on SBA-15 were believed to be the main active component in MnO(x)/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more OH. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Stability and Catalytic Kinetics of Horseradish Peroxidase Confined in Nanoporous SBA-15

    Ikemoto, Hediki; Chi, Qijin; Ulstrup, Jens

    2010-01-01

    We have synthesized nanoporous silica, SBA-15 in the 1 m size range with the pore diameter of 7.6 nm. The redox enzyme horseradish peroxidase (HRP) was entrapped in the pores to form nanostructured hybrid materials. The catalytic activity of free and immobilized enzyme was first compared at room...... likely due to different hydrogen bonding of water and increased hydration strength of the protein inside the nanopores....

  4. Anchoring Tri(8-QuinolinolatoIron Onto Sba-15 for Partial Oxidation of Benzyl Alcohol Using Water as the Solvent

    Yang Xiaoyuan

    2014-09-01

    Full Text Available Tri(8-quinolinolatoiron complex immobilized onto SBA-15 catalyst has been synthesized through a stepwise procedure. The characterization results indicated that the BET surface area, total pore volume and average pore width decrease after stepwise modification of SBA-15, while the structure keeps intact. Catalytic tests showed that FeQ3-SBA-15 catalyzes the oxidation reaction well with 34.8% conversion of benzyl alcohol and 74.7% selectivity to benzaldehyde when water is used as the solvent after 1 h reaction. In addition, homogeneous catalyst tri(8-quinolinolatoiron exhibits very bad catalytic behavior using water as the solvent.

  5. Efficient low-temperature soot combustion by bimetallic Ag-Cu/SBA-15 catalysts.

    Wen, Zhaojun; Duan, Xinping; Hu, Menglin; Cao, Yanning; Ye, Linmin; Jiang, Lilong; Yuan, Youzhu

    2018-02-01

    In this study, the effects of copper (Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag-Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5Ag 1 -Cu 0.1 /SBA-15 catalyst, on which the soot combustion starts at T ig =225°C with a T 50 =285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C (Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag-Cu nanolloy particles, downsizing the mean particle size from 3.7nm in monometallic catalyst to 2.6nm in bimetallic Ag-Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance. Copyright © 2017. Published by Elsevier B.V.

  6. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Yang, Jae Hwan; Park, Hwan Seo; Ahn, Do-Hee; Yim, Man-Sung

    2016-11-01

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi2O3 (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi2O3 and the glass composition. It was confirmed that BiI3, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi5O7I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10-3-10-2 g/m2 day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of 129I.

  7. Utilization of rice husk ash as silica source for the synthesis of mesoporous silicas and their application to CO2 adsorption through TREN/TEPA grafting

    Bhagiyalakshmi, Margandan; Yun, Lee Ji; Anuradha, Ramani; Jang, Hyun Tae

    2010-01-01

    Mesoporous MCM-41, MCM-48 and SBA-15 were synthesized using Rice husk ash (RHA) as the silica source and their defective Si-OH sites were functionalized by 3-cholropropyltrimethoxysilane (CPTMS) which was subsequently grafted with amine compounds, Tris(2-aminoethyl)amine (TREN) and Tetraethylenepentamine (TEPA). X-ray powder diffraction (XRD) and BET results of the parent mesoporous silica suggested their closeness of structural properties to those obtained from conventional silica sources. CO 2 adsorption of branched amine TREN and straight chain amine TEPA at 25, 50 and 75 deg. C was obtained by Thermogravimetric Analyser (TGA) at atmospheric pressure. TREN grafted mesoporous silica showed 7% of CO 2 adsorption while TEPA grafted mesoporous silicas showed less CO 2 adsorption, which is due to the presence of isolated amine groups in TREN. TREN grafted mesoporous silicas were also observed to be selective towards CO 2 , thermally stable and recyclable. The order of CO 2 adsorption with respect to amount of amine grafting was observed to be MCM-48/TREN > MCM-41/TREN > SBA-15/TREN.

  8. Ordered mesoporous carbide-derived carbon as new high performance electrode material in supercapacitors

    Korenblit, Yair; Yushin, Gleb [Georgia Inst. of Technology, Atlanta, GA (United States); Rose, Marcus; Kockrick, Emanuel; Borchardt, Lars; Kaskel, Stefan [Technische Univ. Dresden (Germany); Kvit, Alexander [Wisconsin Univ., Madison, WI (United States)

    2010-07-01

    The preparation and application of templated ordered mesoporous CDC overcome the present limitations of slow intraparticle ion transport and poor control over the biomodal pore size distribution in the carbons currently used, and shows a route for further performance enhancement. The ordered mesoporous channels in SiC CDC serve as ion-highways and allow for very fast ionic transport into the bulk of the CDC particles, thus leading to an excellent frequency response and outstanding capacitance retention at high current densities. The ordered mesopores in SiC allow for a greatly increased specific surface area and specific capacitance of SiC CDC, nearly doubling the previously reported values. The use of CDC produced from other carbides, including mesoporous TiC or VC is expected to further enhance the energy storage characteristics of EDLC electrodes, while optimization of the mesopore size is expected to enhance the power characteristics of EDLC. (orig.)

  9. Mesoporous materials as fining agents in variety Cabernet Sauvignon wines

    Dumitriu Georgiana-Diana

    2016-01-01

    Full Text Available Innovative oenological products and techniques constantly need to be optimized in order to produce high quality wines that are able to fulfill the demanding consumers, with a pleasant colour, astringency, bitterness and a balanced organoleptic profile. New mesoporous materials with viability and environmental safety characteristics, might be a feasible alternative to the use of bentonite, while nowadays in the winemaking there is a major challenge caused by wastes derivate mainly from wine clarification stages. This study was aimed at investigating the influence of conventional (bentonite and activated coal and alternative (MCM-41, SBA-15, KIT-6 fining agents on enological parameters, colour, as well as on the antioxidant activity of a Cabernet Sauvignon wines. Our results show that mesoporous materials, KIT-6 and SBA-15 (6 g/L present the highest reduction on antioxidant activity with 23.08% and 24.41%, while bentonite and activated coal (1.5 g/L reduced with 20.72%, respectively 33.18%. Cluster analysis performed with the values of antioxidant activity differentiated wines treated with activated carbon from other wines.

  10. H2 formation by electron irradiation of SBA-15 materials and the effect of Cu(II) grafting

    Brodie-Linder, N.; Le Caer, S.; Shahdo Alam, M.; Renault, J.P.; Alba-Simionesco, Ch.

    2010-01-01

    Measurement of H 2 production from electron irradiation (10 MeV) on SBA-15 materials has shown that adsorbed water is attacked preferentially. Silanol groups are only attacked when they are in the majority with respect to adsorbed water, however they are much less efficient at producing H 2 . The comparison between water content before and after electron irradiation and the corresponding H 2 production indicates that water desorption is the main route to adsorbed water loss for SBA-15 materials. On the other hand, surface silanol groups are more susceptible to attack,leading to H 2 production when SBA-15 samples have undergone extensive thermal treatment. Electron irradiation of SBA-15-Cu materials has shown that the presence of Cu(II) on the surface reduces and inhibits the production of H 2 . This inhibiting power affects adsorbed water bonded to grafted copper but not surface silanol groups. (authors)

  11. Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

    Paul, Manidipa; Pal, Nabanita; Bhaumik, Asim

    2012-01-01

    Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces. - Graphical abstract: Highly ordered 2D-hexagonal mesoporous borosilicate materials have been synthesized by using Pluronic P123 as template. The materials show very good adsorption and release of organic cationic dye molecules under physiological conditions. Highlights: ► Highly ordered 2D-hexagonal mesoporous borosilicate. ► Nonionic Pluoronic P123 templated mesoporous material. ► Adsorption of organic dyes at the mesopore surface. ► Controlled release of dyes under physiological pH and temperature. ► Release of safranine T (ST) and malachite green (MG) dyes in simulated body fluids.

  12. MCM-41 ordered mesoporous molecular sieves synthesis and characterization

    Rogério A.A. Melo

    1999-07-01

    Full Text Available The aim of this work was to study the hydrothermal synthesis of Si and SiAlMCM-41 performed under both autogenic pressure and refluxing conditions. XRD data showed that the MCM-41 phase may be formed by both processes and that the synthesized material in the presence of Al and/or under reflux presents the hexagonally arrangement of less ordered mesopores. However, as verified by XRD and physisorption data, the order was improved with higher synthesis times. 29Si and 1H - 29Si C/P MAS NMR spectra showed that a great part of the Si atoms exists as silanol groups which originate resonance peaks at -110, -100 and -91 ppm. The presence of Al atoms may generate Si(3Si, Al and Si(2Si, 2Al environments which might be contributing to resonance peaks at -100 and -91 ppm. The 27Al MAS NMR spectrum of the as synthesized AlSiMCM-41 showed a resonance peak of tetrahedral framework aluminum close to 53 ppm and two others, one close to 14 ppm attributed to Al(H2O6+3 species and the other a weak signal close to 32 ppm attributed to pentacoordinated Al. 27Al MAS NMR spectra of the calcined sample showed a peak at 0 ppm corresponding to an hexacoordinated extra-framework aluminum formed during calcination.

  13. CTAB assisted microwave synthesis of ordered mesoporous carbon supported Pt nanoparticles for hydrogen electro-oxidation

    Zhou, Jian-Hua; He, Jian-Ping; Ji, Ya-Jun; Dang, Wang-Juan; Liu, Xiao-Lei; Zhao, Gui-Wang; Zhang, Chuan-Xiang; Zhao, Ji-Shuang; Fu, Qing-Bin; Hu, Huo-Ping

    2007-01-01

    Mesoporous carbon with ordered hexagonal structure derived from the co-assembly of triblock copolymer F127 and resol was employed as the carbon support of Pt catalysts for hydrogen electro-oxidation. Structural characterizations revealed that the mesoporous carbon exhibited large surface area and uniform mesopores. The Pt nanoparticles supported on the novel mesoporous carbon were fabricated by a facile CTAB assisted microwave synthesis process, wherein CTAB was expected to improve the wettability of carbon support as well as the dispersion of Pt nanoparticles. X-ray diffraction and transmission electron microscopy were applied to characterize the Pt catalysts. It was found that the Pt nanoparticles were uniform in size and highly dispersed on the mesoporous carbon supports. The cyclic voltammograms in sulfuric acid demonstrated that the electrochemical active surface area of Pt catalysts prepared with CTAB was two times than that without CTAB

  14. A rational repeating template method for synthesis of 2D hexagonally ordered mesoporous precious metals.

    Takai, Azusa; Doi, Yoji; Yamauchi, Yusuke; Kuroda, Kazuyuki

    2011-03-01

    A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor-infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen-adsorption-desorption isotherm, and small-angle X-ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft-templating methods, can be prepared. This study has overcome the composition variation limitations of the soft-templating method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Macrocyclic ligand decorated ordered mesoporous silica with large-pore and short-channel characteristics for effective separation of lithium isotopes: synthesis, adsorptive behavior study and DFT modeling.

    Liu, Yuekun; Liu, Fei; Ye, Gang; Pu, Ning; Wu, Fengcheng; Wang, Zhe; Huo, Xiaomei; Xu, Jian; Chen, Jing

    2016-10-18

    Effective separation of lithium isotopes is of strategic value which attracts growing attention worldwide. This study reports a new class of macrocyclic ligand decorated ordered mesoporous silica (OMS) with large-pore and short-channel characteristics, which holds the potential to effectively separate lithium isotopes in aqueous solutions. Initially, a series of benzo-15-crown-5 (B15C5) derivatives containing different electron-donating or -withdrawing substituents were synthesized. Extractive separation of lithium isotopes in a liquid-liquid system was comparatively studied, highlighting the effect of the substituent, solvent, counter anion and temperature. The optimal NH 2 -B15C5 ligands were then covalently anchored to a short-channel SBA-15 OMS precursor bearing alkyl halides via a post-modification protocol. Adsorptive separation of the lithium isotopes was fully investigated, combined with kinetics and thermodynamics analysis, and simulation by using classic adsorption isotherm models. The NH 2 -B15C5 ligand functionalized OMSs exhibited selectivity to lithium ions against other alkali metal ions including K(i). Additionally, a more efficient separation of lithium isotopes could be obtained at a lower temperature in systems with softer counter anions and solvents with a lower dielectric constant. The highest value separation factor (α = 1.049 ± 0.002) was obtained in CF 3 COOLi aqueous solution at 288.15 K. Moreover, theoretical computation based on the density functional theory (DFT) was performed to elucidate the complexation interactions between the macrocyclic ligands and lithium ions. A suggested mechanism involving an isotopic exchange equilibrium was proposed to describe the lithium isotope separation by the functionalized OMSs.

  16. Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

    Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

    2016-07-25

    Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pore ordering in mesoporous matrices induced by different directing agents

    Putz, A.-M.; Cecilia, S.; Ianasi, C.; Dudás, Z.; Székely, N. K.; Plocek, Jiří; Sfarloaga, P.; Sacarescu, L.; Almásy, L.

    2015-01-01

    Roč. 22, č. 2 (2015), s. 321-331 ISSN 1380-2224 Institutional support: RVO:61388980 Keywords : Mesoporous silica * MCM-41 * Dodecyl-trimethyl ammonium bromide * Hexadecyl-trimethylammonium bromide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.385, year: 2015

  18. Surface structural, morphological, and catalytic studies of homogeneously dispersed anisotropic Ag nanostructures within mesoporous silica

    Sareen, Shweta [Thapar University, School of Chemistry and Biochemistry (India); Mutreja, Vishal [Maharishi Markandeshwar University, Department of Chemistry (India); Pal, Bonamali; Singh, Satnam, E-mail: ssingh@thapar.edu [Thapar University, School of Chemistry and Biochemistry (India)

    2016-11-15

    Highly dispersed anisotropic Ag nanostructures were synthesized within the channels of 3-aminopropyltrimethoxysilane (APTMS)-modified mesoporous SBA-15 for catalyzing the reduction of p-dinitrobenzene, p-nitrophenol, and p-nitroacetophenone, respectively. A green templating process without involving any reducing agent, by varying the amount (1–10 wt.%) of Ag loading followed by calcination at 350 °C under H{sub 2} led to change in the morphology of Ag nanoparticles from nanospheres (~7–8 nm) to nanorods (aspect ratio ~12–30 nm) without any deformation in mesoporous sieves. In comparison to white bare SBA-15, gray-colored samples were formed with Ag impregnation exhibiting absorption bands at 484 and 840 nm indicating the formation of anisotropic Ag nanostructures within mesoporous matrix. TEM and FE-SEM micrographs confirmed the presence of evenly dispersed Ag nanostructures within as well as on the surface of mesoporous matrix. AFM studies indicated a small decrease in the average roughness of SBA-15 from 20.59 to 19.21 nm for 4 wt.% Ag/m-SBA-15, illustrating the encapsulation of majority of Ag nanoparticles in the siliceous matrix and presence of small amount of Ag nanoparticles on the mesoporous support. Moreover, due to plugging of mesopores with Ag, a significant decrease in surface area from 680 m{sup 2}/g of SBA-15 to 385 m{sup 2}/g was observed. The Ag-impregnated SBA-15 catalyst displayed superior catalytic activity than did bare SBA-15 with 4 wt.% Ag-loaded catalyst exhibiting optimum activity for selective reduction of p-nitrophenol to p-aminophenol (100 %), p-nitroacetophenone to p-aminoacetophenone (100 %), and p-dinitrobenzene to p-nitroaniline (87 %), with a small amount of p-phenylenediamine formation.

  19. Investigation into the Catalytic Activity of Microporous and Mesoporous Catalysts in the Pyrolysis of Waste Polyethylene and Polypropylene Mixture

    Kaixin Li

    2016-06-01

    Full Text Available Catalytic pyrolysis behavior of synthesized microporous catalysts (conventional Zeolite Socony Mobil–5 (C-ZSM-5, highly uniform nanocrystalline ZSM-5 (HUN-ZSM-5 and β-zeolite, Mesoporous catalysts (highly hydrothermally stable Al-MCM-41 with accessible void defects (Al-MCM-41(hhs, Kanemite-derived folded silica (KFS-16B and well-ordered Al-SBA-15 (Al-SBA-15(wo were studied with waste polyethylene (PE and polypropylene (PP mixture which are the main constituents in municipal solid waste. All the catalysts were characterized by Brunauer-Emmett-Teller (BET, X-ray powder diffraction (XRD, and NH3-temperature programmed desorption (TPD. The results demonstrated that microporous catalysts exhibited high yields of gas products and high selectivity for aromatics and alkene, whereas the mesoporous catalysts showed high yields of liquid products with considerable amounts of aliphatic compounds. The differences between the microporous and mesoporous catalysts could be attributed to their characteristic acidic and textural properties. A significant amount of C2–C4 gases were produced from both types of catalysts. The composition of the liquid and gas products from catalytic pyrolysis is similar to petroleum-derived fuels. In other words, products of catalytic pyrolysis of plastic waste can be potential alternatives to the petroleum-derived fuels.

  20. Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

    Liang Ma

    2017-02-01

    Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

  1. Low-temperature fabrication of mesoporous solid strong bases by using multifunction of a carbon interlayer.

    Liu, Xiao-Yan; Sun, Lin-Bing; Liu, Xiao-Dan; Li, Ai-Guo; Lu, Feng; Liu, Xiao-Qin

    2013-10-09

    Mesoporous solid strong bases are highly promising for applications as environmentally benign catalysts in various reactions. Their preparation attracts increasing attention for the demand of sustainable chemistry. In the present study, a new strategy was designed to fabricate strong basicity on mesoporous silica by using multifunction of a carbon interlayer. A typical mesoporous silica, SBA-15, was precoated with a layer of carbon prior to the introduction of base precursor LiNO3. The carbon interlayer performs two functions by promoting the conversion of LiNO3 at low temperatures and by improving the alkali-resistant ability of siliceous host. Only a tiny amount of LiNO3 was decomposed on pristine SBA-15 at 400 °C; for the samples containing >8 wt % of carbon, however, LiNO3 can be entirely converted to strongly basic sites Li2O under the same conditions. The guest-host redox reaction was proven to be the answer for the conversion of LiNO3, which breaks the tradition of thermally induced decomposition. More importantly, the residual carbon layer can prevent the siliceous frameworks from corroding by the newly formed strongly basic species, which is different from the complete destruction of mesostructure in the absence of carbon. Therefore, materials possessing both ordered mesostructure and strong basicity were successfully fabricated, which is extremely desirable for catalysis and impossible to realize by conventional methods. We also demonstrated that the resultant mesoporous basic materials are active in heterogeneous synthesis of dimethyl carbonate (DMC) and the yield of DMC can reach 32.4%, which is apparently higher than that over the catalysts without a carbon interlayer (<12.9%) despite the same lithium content. The strong basicity, in combination with the uniform mesopores, is believed to be responsible for such a high activity.

  2. Catalytic Activity and Photophysical Properties of Biomolecules Immobilized on Mesoporous Silica

    Ikemoto, Hideki

    Mesoporous silicas, based on Santa Barbara Amorphous-15 (SBA-15), with different morphology, structure, pore size and functional groups have been synthesized. Two metalloenzymes and a photosynthetic membrane protein were immobilized on or confined in the pores of the mesoporous silicas to prepare...

  3. Insights into the Hydrothermal Stability of Triamine-Functionalized SBA-15 Silica for CO2 Adsorption.

    Jahandar Lashaki, Masoud; Ziaei-Azad, Hessam; Sayari, Abdelhamid

    2017-10-23

    The hydrothermal stability of triamine-grafted, large-pore SBA-15 CO 2 adsorbents was studied by using steam stripping. Following two 3 h cycles of steam regeneration, lower CO 2 uptakes, lower CO 2 /N ratios, and slower adsorption kinetics were observed relative to fresh samples, particularly at the lowest adsorption temperature (25 °C). CO 2 adsorption measurements for a selected sample exposed to 48 h of steam stripping depicted that after the initial loss during the first exposure to steam (3-6 h), the adsorptive properties stabilized. For higher adsorption temperatures (i.e., 50 and 75 °C), however, all adsorptive properties remained almost unchanged after steaming, indicating the significance of diffusional limitations. Thermogravimetric analysis and FTIR spectroscopy on grafted samples before and after steam stripping showed no amine leaching and no change in the chemical nature of the amine groups, respectively. Also, a six-cycle CO 2 adsorption/desorption experiment under dry conditions showed no thermal degradation. However, N 2 adsorption measurement at 77 K showed significant reductions in the BET surface area of the grafted samples following steaming. Based on the pore size distribution of calcined, grafted samples before and after steaming, it is proposed that exposure to steam restructured the grafted materials, causing mass transfer resistance. It is inferred that triamine-grafted, large-pore SBA-15 adsorbents are potential candidates for CO 2 capture at relatively high temperatures (50-75 °C; for example, flue gas) combined with steam regeneration. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Immobilization of HRP in Mesoporous Silica and Its Application for the Construction of Polyaniline Modified Hydrogen Peroxide Biosensor

    Chien-Chung Chen

    2009-06-01

    Full Text Available Polyaniline (PANI, an attractive conductive polymer, has been successfully applied in fabricating various types of enzyme-based biosensors. In this study, we have employed mesoporous silica SBA-15 to stably entrap horseradish peroxidase (HRP, and then deposited the loaded SBA-15 on the PANI modified platinum electrode to construct a GA/SBA-15(HRP/PANI/Pt biosensor. The mesoporous structures and morphologies of SBA-15 with or without HRP were characterized. Enzymatic protein assays were employed to evaluate HRP immobilization efficiency. Our results demonstrated that the constructed biosensor displayed a fine linear correlation between cathodic response and H2O2 concentration in the range of 0.02 to 18.5 mM, with enhanced sensitivity. In particular, the current approach provided the PANI modified biosensor with improved stability for multiple measurements.

  5. Nanostructured nitrogen-doped mesoporous carbon derived from polyacrylonitrile for advanced lithium sulfur batteries

    Liu, Ying; Zhao, Xiaohui; Chauhan, Ghanshyam S. [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Ahn, Jou-Hyeon, E-mail: jhahn@gnu.ac.kr [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Department of Materials Engineering and Convergence Technology and RIGET, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of)

    2016-09-01

    Graphical abstract: Well-ordered nitrogen-doped mesoporous carbon materials were prepared by in-situ polymerization of polyacrylonitrile in SBA-15 template. The composite of sulfur and nitrogen-doped carbon was successfully used as a cathode material for lithium sulfur battery. - Highlights: • N-doped mesoporous carbons were prepared with PAN as carbon source. • Highly ordered pore system facilitates sulfur loading. • Ladder-type carbon matrix provides good structural stability for confining sulfur. • N-doping ensures an improved absorbability of soluble polysulfides. - Abstract: Nitrogen doping in carbon matrix can effectively improve the wettability of electrolyte and increase electric conductivity of carbon by ensuring fast transfer of ions. We synthesized a series of nitrogen-doped mesoporous carbons (CPANs) via in situ polymerization of polyacrylonitrile (PAN) in SBA-15 template followed by carbonization at different temperatures. Carbonization results in the formation of ladder structure which enhances the stability of the matrix. In this study, CPAN-800, carbon matrix synthesized by the carbonization at 800 °C, was found to possess many desirable properties such as high specific surface area and pore volume, moderate nitrogen content, and highly ordered mesoporous structure. Therefore, it was used to prepare S/CPAN-800 composite as cathode material in lithium sulfur (Li-S) batteries. The S/CPAN-800 composite was proved to be an excellent material for Li-S cells which delivered a high initial discharge capacity of 1585 mAh g{sup −1} and enhanced capacity retention of 862 mAh g{sup −1} at 0.1 C after 100 cycles.

  6. Pore Structure Control of Ordered Mesoporous Silica Film Using Mixed Surfactants

    Tae-Jung Ha

    2011-01-01

    Full Text Available Materials with nanosized and well-arranged pores have been researched actively in order to be applied to new technology fields. Especially, mesoporous material containing various pore structures is expected to have different pore structure. To form a mixed pore structure, ordered mesoporous silica films were prepared with a mixture of surfactant; Brij-76 and P-123 block copolymer. In mixed surfactant system, mixed pore structure was observed in the region of P-123/(Brij-76 + P-123 with about 50.0 wt.% while a single pore structure was observed in regions which have large difference in ratio between Brij-76 and P-123 through the X-ray diffraction analysis. Regardless of surfactant ratio, porosity was retained almost the same. It is expected that ordered mesoporous silica film with mixed pore structure can be one of the new materials which has distinctive properties.

  7. CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligand

    Pasha, Fahran Ahmad; Bendjeriou-Sedjerari, Anissa; Abou-Hamad, Edy; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    Density functional theory calculations and 2D 1H-13C HETCOR solid state NMR spectroscopy prove that CO2 can probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(≡Si-O-)(≡Si-N=)[Zr]H] and [(≡Si

  8. Understanding the effect of post-synthesis ammonium treatment on the catalytic activity of Au/Ti-SBA-15 catalysts for the oxidation of propene

    Sacaliuc-Parvulescu, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

    2008-01-01

    Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti- SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3

  9. Understanding the effect of postsynthesis ammonium treatment on the catalytic activity of Au/TI-SBA-15 catalysts for the oxidation of propene

    Sacaliuc, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

    2008-01-01

    Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti-SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3 mgPO

  10. A Dual-Functional [SBA-15/Fe3O4/P(N-iPAAm] Hybrid System as a Potential Nanoplatform for Biomedical Application

    Andreza de Sousa

    2014-01-01

    Full Text Available The synthesis strategy of a multifunctional system of [SBA-15/Fe3O4/P(N-iPAAm] hybrids of interest for bioapplications was explored. Magnetite nanoparticles coated by mesoporous silica were prepared by an alternative chemical route using neutral surfactant and without the application of any functionalization method. Monomer adsorption followed by in situ polymerization initiated by a radical was the adopted procedure to incorporate the hydrogel into the pore channels of silica nanocomposite. Characterization of the materials was carried out by using X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR, N2 adsorption, transmission electron microscopy (TEM, and Temperature programmed reduction studies (TPR. Their application as drug delivery system using atenolol as a model drug to assess the influence of the application of low frequency alternating magnetic fields on drug release was evaluated. The structural characteristics of the magnetic hybrid nanocomposite, including the effect of the swelling behavior on heating by the application of an alternating magnetic field, are presented and discussed.

  11. A mesoporous silica composite scaffold: Cell behaviors, biomineralization and mechanical properties

    Xu, Yong; Gao, Dan; Feng, Pei; Gao, Chengde; Peng, Shuping; Ma, HaoTian; Yang, Sheng; Shuai, Cijun

    2017-11-01

    Mesoporous structure is beneficial to cellular response due to the large specific surface area and high pore volume. In this study, mesoporous silica (SBA15) was incorporated into poly-L-lactic acid (PLLA) to construct composite scaffold by selective laser sintering. The results showed that SBA15 facilitated cells proliferation, which was mainly attributed to its unique intrinsic mesoporous structure and the released bioactive silicon. Moreover, the hydrolyzate of soluble mesoporous silica can adsorb ions to form nucleation sites that promote biomineralization, leading to improve biological activity of the composite scaffold. In addition, the compressive strength, compressive modulus and Vickers hardness of the scaffold were increased by 47.6%, 35.5% and 29.53% respectively with 1.5 wt.% SBA15. It was found that the particle enhancement of uniform distributed SBA15 accounted for the mechanic reinforcement of the composite scaffold. It indicated that the PLLA-SBA15 composite scaffold had potential applications in bone tissue engineering.

  12. Application of a hybrid ordered mesoporous silica as sorbent for solid-phase multi-residue extraction of veterinary drugs in meat by ultra-high-performance liquid chromatography coupled to ion-trap tandem mass spectrometry.

    Casado, Natalia; Morante-Zarcero, Sonia; Pérez-Quintanilla, Damián; Sierra, Isabel

    2016-08-12

    A quick, sensitive and selective analytical reversed-phase multi-residue method using ultra-high performance liquid chromatography coupled to an ion-trap mass spectrometry detector (UHPLC-IT-MS/MS) operating in both positive and negative ion mode was developed for the simultaneous determination of 23 veterinary drug residues (β-blockers, β-agonists and Non-Steroidal Anti-inflammatory Drugs (NSAIDs)) in meat samples. The sample treatment involved a liquid-solid extraction followed by a solid-phase extraction (SPE) procedure. SBA-15 type mesoporous silica was synthetized and modified with octadecylsilane, and the resulting hybrid material (denoted as SBA-15-C18) was applied and evaluated as SPE sorbent in the purification of samples. The materials were comprehensively characterized, and they showed a high surface area, high pore volume and a homogeneous distribution of the pores. Chromatographic conditions and extraction procedure were optimized, and the method was validated according to the Commission Decision 2002/657/EC. The method detection limits (MDLs) and the method quantification limits (MQLs) were determined for all the analytes in meat samples and found to range between 0.01-18.75μg/kg and 0.02-62.50μg/kg, respectively. Recoveries for 15 of the target analytes ranged from 71 to 98%. In addition, for comparative purpose SBA-15-C18 was evaluated towards commercial C18 amorphous silica. Results revealed that SBA-15-C18 was clearly more successful in the multi-residue extraction of the 23 mentioned analytes with higher recovery values. The method was successfully tested to analyze prepacked preparations of mince bovine meat. Traces of propranolol, ketoprofen and diclofenac were detected in some samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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

    2016-08-01

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

  14. Nature of capillary condensation and evaporation processes in ordered porous materials.

    Grosman, Annie; Ortega, Camille

    2005-11-08

    We report on a detailed experimental study of capillary condensation-evaporation processes of N(2) in ordered mesoporous SBA-15 silica. We have carried out measurements of boundary hysteresis loops, reversal curves, and subloops in order to test whether this material behaves as an assembly of independent cylindrical pores open at both ends. With these data, we come to the conclusion that, whereas the boundary hysteresis loop has the classical shape of type H1 associated with condensation-evaporation in cylindrical pores open at both ends, the capillary evaporation does not take place at equilibrium as it is generally assumed. Moreover, the pores do not desorb independently of one another.

  15. Recent progress of ordered mesoporous silica-supported chiral metallic catalysts

    LIU Rui

    2013-02-01

    Full Text Available Recently,ordered silica-based mesoporous chiral organometallics-functionalized heterogeneous catalysts have attracted extensive research interest due to their excellent properties,such as easy preparation,high activity and convenient recycle.This review mainly summarizesthe generally prepared strategy and the silica-based organometallics-functionalized heterogeneous catalysts reported in the literatures.

  16. The Epoxidation of Limonene over the TS-1 and Ti-SBA-15 Catalysts

    Agnieszka Wróblewska

    2014-11-01

    Full Text Available Limonene belongs to a group of very important intermediates used in the production of fine chemicals. This monoterpene compound can be obtained from peels of oranges or lemon which are a (biomass waste from the orange juice industry. Thus, limonene is a renewable, easy available and a relatively cheap compound. This work presents preliminary studies on the process of limonene epoxidation over zeolite type catalysts such as: TS-1 and Ti-SBA-15. In these studies methanol was used as a solvent and as an oxidizing agent a 60 wt % hydrogen peroxide solution was applied. The activity of each catalyst was investigated for four chosen temperatures (0 °C, 40 °C, 80 °C and 120 °C. The reaction time was changed from 0.5 to 24 h. For each catalyst the most beneficial conditions (the appropriate temperature and the reaction time have been established. The obtained results were compared and the most active catalyst was chosen. These studies have also shown different possible ways of limonene transformation, not only in the direction of 1,2-epoxylimonene and its corresponding diol, but also in direction of carveol, carvone and perillyl alcohol—compounds with a lot of applications. The possible mechanisms of formation of the allylic oxidation products were proposed.

  17. Preparation of ionic liquid-modified SBA-15 doped with molybdovanadophosphoric acid for oxidative desulfurization

    Zhuang, Jiang Zhou; Jin, Xiao Yin; Shen, Xian Lin; Tan, Jun Jun; Nie, Long Hui; Xiang, Jian; Hu, Bing

    2015-01-01

    A series of catalysts, ionic liquid-modified SBA-15 (denoted ILSBA) doped with H 5 PMo 10 V 2 O 40 (HPMoV 2 ) have been synthesized and characterized by XRD, FT-IR, 1 H NMR, TG-DTA, and TEM. The catalyst was used for the removal of dibenzothiophene (DBT) in model oil combined with hydrogen peroxide (the oxidant) and acetonitrile (the phase-transfer agent). It was observed that the sulfur content of DBT can be reduced from 500 to 2 ppm by adjusting the amount of catalyst, the reaction temperatures and the reaction time. Besides, the catalyst activity for different sulfur compounds showed a huge difference which may be mainly affected by the electron densities of sulfur atom. Moreover, the catalyst can be recycled seven times without a significant loss in activity, which could be ascribed to the strong electrostatic interaction between ILSBA and HPMoV 2 . In addition, a postulated mechanism was proposed to reveal the oxidative desulfurization process

  18. Preparation of ionic liquid-modified SBA-15 doped with molybdovanadophosphoric acid for oxidative desulfurization

    Zhuang, Jiang Zhou; Jin, Xiao Yin; Shen, Xian Lin; Tan, Jun Jun; Nie, Long Hui; Xiang, Jian; Hu, Bing [Dept. of chool of Chemistry and Chemical Engineering, Hubei University of Technology, Wuhan (China)

    2015-07-15

    A series of catalysts, ionic liquid-modified SBA-15 (denoted ILSBA) doped with H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} (HPMoV{sub 2}) have been synthesized and characterized by XRD, FT-IR, {sup 1}H NMR, TG-DTA, and TEM. The catalyst was used for the removal of dibenzothiophene (DBT) in model oil combined with hydrogen peroxide (the oxidant) and acetonitrile (the phase-transfer agent). It was observed that the sulfur content of DBT can be reduced from 500 to 2 ppm by adjusting the amount of catalyst, the reaction temperatures and the reaction time. Besides, the catalyst activity for different sulfur compounds showed a huge difference which may be mainly affected by the electron densities of sulfur atom. Moreover, the catalyst can be recycled seven times without a significant loss in activity, which could be ascribed to the strong electrostatic interaction between ILSBA and HPMoV{sub 2}. In addition, a postulated mechanism was proposed to reveal the oxidative desulfurization process.

  19. Ordered Mesoporous NiCeAl Containing Catalysts for Hydrogenolysis of Sorbitol to Glycols

    Zhou, Zhiwei; Zhang, Jiaqi; Qin, Juan; Li, Dong; Wu, Wenliang

    2018-03-01

    Cellulose-derived sorbitol is emerging as a feasible and renewable feedstock for the production of value-added chemicals. Highly active and stable catalyst is essential for sorbitol hydrogenolysis. Ordered mesoporous M- xNi yCeAl catalysts with different loadings of nickel and cerium species were successfully synthesized via one-pot evaporation-induced self-assembly strategy (EISA) and their catalytic performance were tested in the hydrogenolysis of sorbitol. The physical chemical properties for the catalysts were characterized by XRD, N2 physisorption, H2-TPR, H2 impulse chemisorption, ICP and TEM techniques. The results showed that the ordered mesopores with uniform pore sizes can be obtained and the Ni nanoparticles around 6 nm in size were homogeneously dispersed in the mesopore channels. A little amount of cerium species introduced would be beneficial to their textural properties resulting in higher Ni dispersion, metal area and smaller size of Ni nanoparticles. The M-10Ni2CeAl catalyst with Ni and Ce loading of 10.9 and 6.3 wt % shows better catalytic performance than other catalysts, and the yield of 1,2-PG and EG can reach 56.9% at 493 K and 6 MPa pressure for 8 h after repeating reactions for 12 times without obvious deterioration of physical and chemical properties. Ordered mesoporous M-NiCeAl catalysts are active and stable in sorbitol hydrogenolysis.

  20. Recent Advances in Catalysis Over Mesoporous Molecular Sieves

    Martín-Aranda, R. M.; Čejka, Jiří

    2010-01-01

    Roč. 53, 3-4 (2010), s. 141-153 ISSN 1022-5528 R&D Projects: GA AV ČR KAN100400701; GA AV ČR IAA400400805; GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : mesoporous molecular sieves * MCM-41 * SBA-15 * mesoporous alumina Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.359, year: 2010

  1. Mesoporous silica materials modified with alumina polycations as catalysts for the synthesis of dimethyl ether from methanol

    Macina, Daniel; Piwowarska, Zofia; Tarach, Karolina; Góra-Marek, Kinga [Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Kraków (Poland); Ryczkowski, Janusz [Maria Curie Skłodowska University, Faculty of Chemistry, Maria Curie-Skłodowska 2, 20-031 Lublin (Poland); Chmielarz, Lucjan, E-mail: chmielar@chemia.uj.edu.pl [Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Kraków (Poland)

    2016-02-15

    Highlights: • Deposition of alumina ologoctaions on mesoporous silicas modified with surface −SO{sub 3}H groups. • Alumina aggregates generated acid properties in the silica supports. • Alumina modified SBA-15 and MCF were active and selective catalysts in DME synthesis. - Abstract: Mesoporous silica materials (SBA-15 and MCF) were used as catalytic supports for the deposition of aggregated alumina species using the method consisting of the following steps: (i) anchoring 3-(mercaptopropyl)trimethoxysilane (MPTMS) on the silica surface followed by (ii) oxidation of −SH to−SO{sub 3}H groups and then (iii) deposition of aluminum Keggin oligocations by ion-exchange method and (iv) calcination. The obtained samples were tested as catalysts for synthesis of dimethyl ether from methanol. The modified silicas were characterized with respect to the ordering of their porous structure (XRD), textural properties (BET), chemical composition (EDS, CHNS), structure ({sup 27}Al NMR, FTIR) and location of alumina species (EDX-TEM), surface acidity (NH{sub 3}-TPD, Py-FTIR) and thermal stability (TGA). The obtained materials were found to be active and selective catalysts for methanol dehydration to dimethyl ether (DME) in the MTD process (methanol-to-dimethyl ether).

  2. Synthesis, characterization, and catalytic application of ordered mesoporous carbon–niobium oxide composites

    Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling; Liu, Zhao-Tie; Dong, Wen-Sheng, E-mail: wsdong@snnu.edu.cn

    2014-11-15

    Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride as precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.

  3. Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition.

    Lu, An-Hui; Nitz, Joerg-Joachim; Comotti, Massimiliano; Weidenthaler, Claudia; Schlichte, Klaus; Lehmann, Christian W; Terasaki, Osamu; Schüth, Ferdi

    2010-10-13

    Uniform and highly dispersed γ-Fe(2)O(3) nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe(2)O(3) nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe(2)O(3)/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60,000 cm(3) g(cat)(-1) h(-1). At a space velocity of 7500 cm(3) g(cat)(-1) h(-1), complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe(2)O(3) nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe(2)O(3) and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe(2)O(3)/CMK-5 catalyst is much more active than the benchmark NiO/Al(2)O(3) catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe(2)O(3) nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity.

  4. Iron-functionalized nanoporous silica type SBA-15: Synthesis, characterization and application in alkene epoxidation in presence of hydrogen peroxide

    Mahdieh Ghazizadeh

    2017-05-01

    Full Text Available Fe(IIIsalophen complex on a SBA-15 support functionalized with (3-aminopropyltriethoxysilane as a linker. It has been synthesized and characterized by XRD, adsorption–desorption of nitrogen, SEM, FT-IR and UV–Vis. The formation of metal-salophen complex with the amino groups as connectors to the SBA-15 surface was confirmed. This material was successfully used as a heterogeneous catalyst for the epoxidation of alkenes and the effects of reaction time, different solvents and amount of catalyst on catalytic activity were investigated. This catalyst gave suitable and comparable yield and percentage conversion values. It is also stable and can be recycled and reused in the epoxidation of alkenes.

  5. Comparison of the Acidity of Heteropolyacids Encapsulated in or Impregnated on SBA-15

    Pinto Teresa

    2016-03-01

    Full Text Available Heteropolyacids (HPA immobilized onto SBA-15 silica were prepared by two different ways using either impregnation or encapsulation methodologies. Two Keggin-type HPA, H3PW12O40 and H4SiW12O40 were considered in this study. The resulting hybrid materials were fully characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, Raman, diffuse reflectance UV-Vis spectroscopies and 31P MAS NMR. All characterization methods showed that at room temperature the catalysts contained well-dispersed and intact Keggin units throughout the solid. The catalytic activity of these solids was investigated in the isomerization of n-hexane. The impregnated and encapsulated phosphotungstic catalysts performed similarly in catalysis showing that the amount of active sites was nearly the same in both catalysts. On the contrary, the tungstosilicic encapsulated material was completely inactive while its impregnated counterpart was even more active than the phosphotungstic derived catalysts. The acidity of the solids was measured by various methods: microcalorimetry of ammonia adsorption, ammonia desorption followed by Temperature Programmed Desorption (TPD and DRIFT/GC-MS and pyridine adsorption followed by infrared spectroscopy. Only pyridine adsorption and ammonia desorption followed by DRIFT/GC-MS agreed with the catalytic data. Ammonia adsorption followed by microcalorimetry was not able to differentiate between the four catalysts while the TPD experiments led to unreliable results, as not only the evolved ammonia but also other molecules such as water were taken into account in the measurements. The behavior difference between the encapsulated silico- and phosphotungstic acids was explained by a more pronounced encapsulation in the case of silicon.

  6. Ordered mesoporous carbon coating on cordierite: Synthesis and application as an efficient adsorbent

    Wan, Ying, E-mail: ywan@shnu.edu.cn [Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234 (China); Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China); Cui, Xiangting; Wen, Zhentao [Department of Chemistry, Shanghai Normal University, Shanghai 200234 (China)

    2011-12-30

    Highlight: Black-Right-Pointing-Pointer Surfactant self-assembly of ordered mesoporous carbon coating on honeycomb cordierite. Black-Right-Pointing-Pointer Carbon coating with opened, hexagonally ordered pore arrays. Black-Right-Pointing-Pointer Honeycomb adsorbents for removal of p-chlorophenol. Black-Right-Pointing-Pointer The adsorbents exhibit large processing volume, and great advantages in reusability. - Abstract: Ordered mesoporous carbon coating on the honeycomb cordierite substrate has been prepared using low-polymerized phenolic resins as carbon sources and triblock copolymer F127 as the structure directing agent via the evaporation induced self-assembly route. The high-resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), and nitrogen sorption techniques prove the hexagonally ordered pore arrays of carbon coating on the cordierite. The honeycomb monolith adsorbents coated by ordered mesoporous carbons are directly used without any activation, and exhibit adsorption capacities for chlorinated organic pollutants in water with 200 mg/g for p-chlorophenol and 178 mg/g for p-chloroaniline (with respect to the net carbon coating), high adsorption ratio for low-concentration pollutants, large processing volumes and reusability. More than 200 repeated times can be achieved without obvious loss in both adsorption capacity and weight.

  7. Synthesis of Ordered Mesoporous Carbon Loaded Fe, Co, Ni Nanocrystals by the Soft Templating Route and Their Characterization%有序介孔碳负载Fe、Co、Ni纳米晶的软模板合成及其表征

    李健生; 顾娟; 凌晓凤; 孙秀云; 沈锦优; 韩卫清; 王连军

    2011-01-01

    报道了在有序介孔碳基体中一步合成负载Fe、Co、Ni纳米晶的方法.以间二苯酚和甲醛为碳源,F127为模板剂,Fe、Co、Ni的硝酸盐为前驱体,通过软模板组装路线在酸性条件下合成了负载型有序介孔碳复合材料.采用X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征.结果表明:合成的材料具有类似于SBA-15的有序介孔结构,有序介孔碳负载Fe、Co、Ni纳米晶复合材料的比表面积分别为586、626和698m2·g-1.XRD和TEM表征结果证实了金属物种以高分散纳米晶的形式分布在介孔碳基体中.%We report a one-step method for the synthesis of M(Fe, Co, Ni) nanocrystals supported by ordered mesoporous carbon (OMC) materials. M/OMC composites were obtained by the soft templating route under acidic conditions using resorcinol and formaldehyde as carbon precursors, tdblock copolymer Pluronic F127 as a template and Fe, Co, Ni nitrates as metal precursors. The as-synthesized materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and N2 adsorption.Characterization revealed that the as-synthesized materials possessed an ordered hexagonal mesoporous structure similar to SBA-15. The specific surface areas of the Fe/OMC, Co/OMC, and Ni/OMC composites were found to be 586, 626, and 698 m2· g-1, respectively. The fact that the metal species were present as highly dispersed nanocrystals in the OMC matrix was confirmed by XRD and high-resolution TEM.

  8. Adsorption removal of acid black 1 from aqueous solution using ordered mesoporous carbon

    Peng, Xiaoming, E-mail: pengxiaoming70@126.com [School of Civil Engineering, Southeast University, Nanjing 210096 (China); Hu, Xijun [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong,China (China); Fu, Dafang, E-mail: fdf@seu.edu.cn [School of Civil Engineering, Southeast University, Nanjing 210096 (China); Lam, Frank L.Y. [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong,China (China)

    2014-03-01

    Highlights: • Ordered mesoporous carbon was prepared using template. • Ordered mesoporous carbon was introduced of N-containing group by Chemical vapor deposition method. • Modified CMK-3 have better adsorption capacity and efficiency than virgin CMK-3 to removal AB1 dye. - Abstract: A novel ordered mesoporous carbon CMK-3 and synthetic CMK-3 containing nitrogen functional groups by ammonia-treated were applied for acid black 1(AB1) dye adsorption. The ammonia-treated(chemical vapor deposition method) before and after CMK-3 were characterized by using a Micrometitics ASAP 2020 surface area analyzer (ASAP 2020), Fourier transform infrared spectrophotometer (FT–IR), X-ray Photoelectron Spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM) and equilibrium studies. This result indicates that the prepared CMK-3 and modified CMK-3 were almost uniform, as rope-like domains and their uniform mesopore with diameter centered at 3.2 nm and 3.7 nm. The FIIR analysis depicted that the presence of a variety of new basic functional groups on the modified CMK-3 surface. Several effect variables of pH, dye concentration and temperature were studied. The pseudo second-order model showed the fitter well to agree with the kinetic data. The experimental data were analyzed by the Langmuir and Freundlich models, with the latter found to closely the isotherm model. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The results show that CMK-3 using ammonia gas modified by thermal treatment system is an effective method to improvement capacity as it shows the highest adsorption capacity of AB1, as compared to the unmodified CMK-3 and the bamboo-based carbon, respectively.

  9. Nanocomposite of cobalt oxide and ordered mesoporous carbon as the electrode materials for supercapacitor

    Xu, J.; Liu, P.; Zhao, J.; Feng, J.; Tang, B. [Shanghai Univ. of Engineering Science (China). College of Chemistry and Chemical Engineering

    2010-07-01

    An incipient wetness impregnation method was used to prepare a cobalt oxide ordered mesoporous carbon composite for use as an electrode in supercapacitor applications. The composite was then incorporated inside periodic nanoholes in the ordered mesoporous carbon (OMC). X-ray diffraction (XRD), transmission electron microscopy (TEM) and N{sub 2} adsorption-desorption isotherm analyses were used to characterize the structures of the samples. The specific capacitance of the synthesized materials was estimated using cyclic voltammetric (CV) analyses. The study showed that composites prepared using the new method exhibited a higher reversible specific capacitance of 594.8 F per g at a scan rate of 5 mV per second. The composite also showed good cyclic stability. Results suggested that the composite can be used as an electrode material in supercapacitors.

  10. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnO{sub x}/SBA-15

    Sun, Qiangqiang; Wang, Yu [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Li, Laisheng, E-mail: llsh@scnu.edu.cn [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Bing, Jishuai [Key Laboratory of Aquatic Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Wang, Yingxin; Yan, Huihua [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China)

    2015-04-09

    Highlights: • Clofibric acid (CA) is efficiently mineralized by O{sub 3}/MnO{sub x}/SBA-15. • Adsorption of CA and its intermediates on MnO{sub x}/SBA-15 is proved unimportant. • Initiation of hydroxyl radicals (·OH) is enhanced in O{sub 3}/MnO{sub x}/SBA-15. • Uniformly distributed MnO{sub x} accounts for the high activity of MnO{sub x}/SBA-15. • Degradation routes of CA in ozonation alone and catalytic ozonation are proposed. - Abstract: Comparative experiments were conducted to investigate the catalytic ability of MnO{sub x}/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O{sub 3}/MnO{sub x}/SBA-15). Adsorption of CA and its intermediates by MnO{sub x}/SBA-15 was proved unimportant in O{sub 3}/MnO{sub x}/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO{sub 3}) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO{sub x}/SBA-15 facilitated the generation of hydroxyl radicals (·OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO{sub x} on SBA-15 were believed to be the main active component in MnO{sub x}/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more ·OH.

  11. Comparative Study of Molecular Basket Sorbents Consisting of Polyallylamine and Polyethylenimine Functionalized SBA-15 for CO2 Capture from Flue Gas.

    Wang, Dongxiang; Wang, Xiaoxing; Song, Chunshan

    2017-11-17

    Polyallylamine (PAA)-based molecular basket sorbents (MBS) have been studied for CO 2 capture in comparison with polyethylenimine (PEI)-based MBS. The characterizations including N 2 physisorption, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and thermogravimetric analysis (TGA) showed that PAA (M n =15 000) is more rigid and has more steric hindrance inside SBA-15 pores than PEI owing mainly to its different polymer structure. The effects of temperature and PAA loading on the CO 2 sorption capacity of PAA-based MBS have been examined by TGA by using 100 % CO 2 gas stream and compared with PEI/SBA-15. It was found that the capacity of the PAA/SBA-15 sorbent increased with increasing temperature. The optimum capacity of 88 mg CO2  g sorb -1 was obtained at 140 °C for PAA(50)/SBA-15 whereas the optimum sorption temperature was 75 and 90 °C for PEI-I(50)/SBA-15 (PEI-I, M n =423) and PEI-II(50)/SBA-15 (PEI-II, M n =25 000), respectively. The capacity initially increased with the increase of PAA loading and then dropped at high amine contents, owing to the increased diffusion barrier. The highest CO 2 capacity of 109 mg CO2  g sorb -1 was obtained at a PAA loading of 65 wt %, whereas the PAA(50)/SBA-15 sorbent gave the best amine efficiency of 0.23 mol CO2  mol N -1 . The effect of moisture was examined in a fixed-bed flow system with simulated flue gas containing 15 % CO 2 and 4.5 % O 2 in N 2 . It was found that the presence of moisture significantly enhanced CO 2 sorption over PAA(50)/SBA-15 and greatly improved its cyclic stability and regenerability. Compared with PEI/SBA-15, PAA/SBA-15 possesses a better thermal stability and higher resistance to oxidative degradation. However, the CO 2 sorption rate over the PAA(50)/SBA-15 sorbent was much slower. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors.

    Nam, Inho; Kim, Nam Dong; Kim, Gil-Pyo; Park, Junsu; Yi, Jongheop

    2012-07-01

    A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.

  13. Ordered mesoporous polyaniline film as a new matrix for enzyme immobilization and biosensor construction

    Xu Qin; Zhu Junjie; Hu Xiaoya

    2007-01-01

    Ordered mesoporous polyaniline film has been fabricated by electrodepositing from the hexagonal lyotropic liquid crystalline (LCC). Horseradish peroxidase (HRP), as a symbol biomolecule, was successfully immobilized on the film to construct a new kind of hydrogen peroxide biosensor. The biosensor combined the advantages of the good conductivity of polyaniline and the higher surface area of the ordered mesoporous film. Polyaniline could be served as a wire to relay electron between HRP and the electrode. The high surface area of the film supplied more sites for HRP immobilization, therefore increased the catalytic activity of the biosensor. The ordered mesoporous character of the film increased the rate of mass transport, which resulted in the improvement of sensor response and linearity. The biosensor displayed excellent electrocatalytic response to the detection of H 2 O 2 in a concentration range from 1.0 μM to 2.0 mM with a detection limit of 0.63 μM. Good reproducibility, stability, high precision, wide linearity and low detection limit were assessed for the biosensor

  14. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  15. Production of Ethylene through Ethanol Dehydration on SBA-15 Catalysts Synthesized by Sol-gel and One-step Hydrothermal Methods.

    Autthanit, Chaowat; Jongsomjit, Bunjerd

    2018-02-01

    The present work deals with the catalytic performance of SBA-15 supported catalysts in the gas phase catalytic dehydration of ethanol in the temperature range of 200 to 400°C. The SBA-15 support was incorporated on a zirconium (Zr) and bimetal of zirconium and lanthanum (Zr-La) prepared by sol-gel (SG) and hydrothermal (HT) methods. The catalysts were characterized by means of N 2 physisorption, SEM/EDX, and NH 3 -TPD. The experimental results demonstrated that the Zr-La/SBA-15-HT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. The best catalytic results were achieved for Zr-La/SBA-15-HT indicating values of ethanol conversion and ethylene yield of ca. 84% and 80%, respectively at 400°C. The most important parameter influencing their catalytic properties appears to be the interaction between metal and support depending on different methods. The metal dispersion inside the siliceous matrix of SBA-15 has a direct influence on their surface acidity. Meanwhile, the performance of these SBA-15 supported catalysts in ethanol dehydration is also related with the alteration of surface acidity caused by the introduction of Zr and Zr-La.

  16. Surface PEGylation of mesoporous silica materials via surface-initiated chain transfer free radical polymerization: Characterization and controlled drug release.

    Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2017-12-01

    As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Amine bridges grafted mesoporous silica, as a prolonged/controlled drug release system for the enhanced therapeutic effect of short life drugs

    Rehman, Fozia; Ahmed, Khalid; Airoldi, Claudio; Gaisford, Simon; Buanz, Asma; Rahim, Abdur; Muhammad, Nawshad; Volpe, Pedro L.O.

    2017-01-01

    Hybrid mesoporous silica SBA-15, with surface incorporated cross-linked long hydrophobic organic bridges was synthesized using stepwise synthesis. The synthesized materials were characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, nitrogen adsorption, X-rays diffraction, thermogravimetry and scanning and transmission electron microscopy. The functionalized material showed highly ordered mesoporous network with a surface area of 629.0 m 2 g −1 . The incorporation of long hydrophobic amine chains on silica surface resulted in high drug loading capacity (21% Mass/Mass) and prolonged release of ibuprofen up till 75.5 h. The preliminary investigations suggests that the synthesized materials could be proposed as controlled release devices to prolong the therapeutic effect of short life drugs such as ibuprofen to increase its efficacy and to reduce frequent dosage. - Highlights: • Silica SBA-15 was synthesized and modified with long hydrophobic amine linkers. • These materials were characterized using different techniques. • The modified material showed high drug loading capacity and control ibuprofen release in biological fluids.

  18. Amine bridges grafted mesoporous silica, as a prolonged/controlled drug release system for the enhanced therapeutic effect of short life drugs

    Rehman, Fozia, E-mail: foziaics@yahoo.com [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084–971 Campinas, SP (Brazil); Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS Institute of Information Technology, Lahore (Pakistan); Ahmed, Khalid; Airoldi, Claudio [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084–971 Campinas, SP (Brazil); Gaisford, Simon; Buanz, Asma [UCL School of Pharmacy, University College London, 29-39 Brunswick Square, London WC1N 1AX (United Kingdom); Rahim, Abdur; Muhammad, Nawshad [Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS Institute of Information Technology, Lahore (Pakistan); Volpe, Pedro L.O. [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084–971 Campinas, SP (Brazil)

    2017-03-01

    Hybrid mesoporous silica SBA-15, with surface incorporated cross-linked long hydrophobic organic bridges was synthesized using stepwise synthesis. The synthesized materials were characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, nitrogen adsorption, X-rays diffraction, thermogravimetry and scanning and transmission electron microscopy. The functionalized material showed highly ordered mesoporous network with a surface area of 629.0 m{sup 2} g{sup −1}. The incorporation of long hydrophobic amine chains on silica surface resulted in high drug loading capacity (21% Mass/Mass) and prolonged release of ibuprofen up till 75.5 h. The preliminary investigations suggests that the synthesized materials could be proposed as controlled release devices to prolong the therapeutic effect of short life drugs such as ibuprofen to increase its efficacy and to reduce frequent dosage. - Highlights: • Silica SBA-15 was synthesized and modified with long hydrophobic amine linkers. • These materials were characterized using different techniques. • The modified material showed high drug loading capacity and control ibuprofen release in biological fluids.

  19. Immobilization induced molecular compression of ionic liquid in ordered mesoporous matrix

    Tripathi, Alok Kumar; Singh, Rajendra Kumar

    2018-02-01

    In this work, ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([EMIM][FSI]) has been immobilized into ordered mesoporous silica MCM-41 by a physical imbibition process. Transmission electron microscopy confirms the filling of mesopores of MCM-41. The effect of IL content in MCM-41 was probed in terms of thermal stability, chemical interactions, and dielectric properties. N2-sorption results indicate the compression of the IL in the nanopores of MCM-41, which contributes to an increase of the melting point probed by differential scanning calorimetry. The quantum chemical calculations confirmed that the ion-ion interaction in ion-pairs of IL were preferred over the hydrogen bonding interaction in the presence of SiO2 molecules, and these interactions probably compress the molecular size in the nanopores of MCM-41. Strong interactions between IL and porous MCM-41 were suggested as the mechanism of this immobilization, which was characterized by FTIR and dielectric spectroscopy.

  20. Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry

    2013-01-01

    Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed. PMID:24237719

  1. Efficient capture of CO2 over ordered micro-mesoporous hybrid carbon nanosphere

    Chen, Changwei; Yu, Yanke; He, Chi; Wang, Li; Huang, Huang; Albilali, Reem; Cheng, Jie; Hao, Zhengping

    2018-05-01

    Four kinds of carbon-based adsorbents (micro-mesoporous hybrid carbon nanosphere and N-doped hollow carbon sphere with single-, double- or ruga-shell morphology) with different structural and textural properties were prepared and systematically studied in CO2 capture. All synthesized samples possess high specific surface area (828-910 m2 g-1), large pore volume (0.71-1.81 cm3 g-1), and different micropore contents varied from 2.1% to 46.4%. Amongst, the ordered micro-mesoporous carbon nanosphere (OM-CNS) exhibits the best adsorption performance with CO2 uptake as high as 3.01 mmol g-1 under conditions of 298 K and 1.0 bar, better than most of the reported CO2 adsorbents. The excellent CO2 adsorption capacity of OM-CNS can be reasonably attributed to the synergistic effect of ordered mesopore channels and abundant structural micropores which are beneficial for the diffusion and trapping of CO2 adsorbate. Moreover, the OM-CNS shows excellent CO2 trapping selectivity and superior stability and recyclability, which endow the OM-CNS as a promising and environmental-friendly adsorbent for CO2 capture and separation under practical conditions.

  2. Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis

    Li, Keyan; Zhao, Yongqin; Song, Chunshan; Guo, Xinwen

    2017-12-01

    Magnetic Fe3O4/CeO2 composites with highly ordered mesoporous structure and large surface area were synthesized by impregnation-calcination method, and the mesoporous CeO2 as support was synthesized via the hard template approach. The composition, morphology and physicochemical properties of the materials were characterized by XRD, SEM, TEM, XPS, Raman spectra and N2 adsorption/desorption analysis. The mesoporous Fe3O4/CeO2 composite played a dual-function role as both adsorbent and Fenton-like catalyst for removal of organic dye. The methylene blue (MB) removal efficiency of mesoporous Fe3O4/CeO2 was much higher than that of irregular porous Fe3O4/CeO2. The superior adsorption ability of mesoporous materials was attributed to the abundant oxygen vacancies on the surface of CeO2, high surface area and ordered mesoporous channels. The good oxidative degradation resulted from high Ce3+ content and the synergistic effect between Fe and Ce. The mesoporous Fe3O4/CeO2 composite presented low metal leaching (iron 0.22 mg L-1 and cerium 0.63 mg L-1), which could be ascribed to the strong metal-support interactions for dispersion and stabilization of Fe species. In addition, the composite can be easily separated from reaction solution with an external magnetic field due to its magnetic property, which is important to its practical applications.

  3. Facile fabrication of ordered mesoporous graphitic carbon nitride for RhB photocatalytic degradation

    Luo, Lei; Zhang, Anfeng [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Janik, Michael J. [EMS Energy Institute, PSU-DUT Joint Center for Energy Research and Department of Energy & Mineral Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Li, Keyan [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Song, Chunshan [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); EMS Energy Institute, PSU-DUT Joint Center for Energy Research and Department of Energy & Mineral Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Guo, Xinwen, E-mail: guoxw@dlut.edu.cn [State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China)

    2017-02-28

    Highlights: • Ordered mesoporous graphitic carbon nitrides with S{sub BET} = 279.3 m{sup 2}/g were prepared. • Enhanced photocatalytic activity and reusability were presented. • Improved S{sub BET} and charge carrier separation efficiency contribute to the activity. - Abstract: Ordered mesoporous graphitic carbon nitrides were prepared by directly condensing the uniform mixtures of melamine and KIT-6. After removal of the KIT-6 sacrificial template, the carbon nitrides were characterized with TEM, N{sub 2} physical adsorption, XRD, FT-IR, XPS, UV–vis and PL spectrometries, and tested for their RhB photocatalytic degradation activity. Together, these characterizations confirmed the as-prepared tunable mesoporous materials with enhanced charge separation efficiency and superior photocatalytic performance. Compared with a conventional bulk g-C{sub 3}N{sub 4}, ordered mesoporous g-C{sub 3}N{sub 4} exhibits a larger specific surface area of 279.3 m{sup 2}/g and a pore size distribution about 4.0 nm and 13.0 nm. Meanwhile, the reduced bandgap energy of 2.77 eV and lower photogenerated electron-hole pair recombination frequency were evidenced by UV–Vis and PL spectra. The RhB photocatalytic degradation activity maximizes with a mass ratio of KIT-6/melamine of 80% (KCN80), and the kinetic constant reaches 0.0760 min{sup −1} which is 16 times higher than that of the bulk sample. Reusability of KCN80 was demonstrated by a lack of evident deactivation after three consecutive reaction periods. The direct condensation of the KIT-6 and melamine mixture does not require pre-casting of the precursor into the pore system of the templates. Owing to its high product yield, improved S{sub BET}, reduced bandgap energy and limited charge recombination, the facile-prepared ordered mesoporous g-C{sub 3}N{sub 4} is a practical candidate for further modification.

  4. Orientation specific deposition of mesoporous particles

    Tomas Kjellman

    2014-11-01

    Full Text Available 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.

  5. CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligand

    Pasha, Fahran Ahmad

    2016-01-04

    Density functional theory calculations and 2D 1H-13C HETCOR solid state NMR spectroscopy prove that CO2 can probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(≡Si-O-)(≡Si-N=)[Zr]H] and [(≡Si-NH-)(≡Si-X-)[Zr]H2] (X = O or NH). Moreover, [(≡Si-O-)(≡Si-N=)[Zr]H] activates CO2 more efficiently than the other complexes and leads to a carbimato Zr formate.

  6. Construction of order mesoporous (Eu–La)/ZnO composite material and its luminescent characters

    Bao, Na; Liu, Yu; Li, Zi-Wei [School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun 130022 (China); Yu, Hui, E-mail: yh2001101@163.com [School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun 130022 (China); Bai, Hao-tian [School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun 130022 (China); Xia, Long, E-mail: xialong_aron@163.com [School of Materials Science and Engineering, Harbin Institute of Technology at Weihai, Weihai 264209 (China); Feng, Da-wei [Changchun University of Science and Technology Science Park, Changchun 130022 (China); Guangdong College of Business and Technology, Zhaoqing 526020 (China); Zhang, Hong-bo; Dong, Xiang-ting; Wang, Tian-yang; Han, Ji; Wu, Rong-yi; Zhang, Qi [School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun 130022 (China)

    2016-09-15

    For the first time, the order mesoporous zinc oxide was synthesized by a soft template synthesis method. The Eu and La phosphate were introduced into the prepared mesoporous zinc oxide by the high temperature solid phase method, and got the mesoporous rare earth/zinc oxide composite materials. The luminescence characters of the materials were studied. The influences of La to Eu luminescent properties had been studied, and the optimum proportion of Eu and La was discussed. The influences of La and Eu to ZnO luminescence properties were also been studied. La phosphate had the large influence to Eu luminescent. ZnO had a strong emission peak at 469 nm, which overlapped with the {sup 7}F{sub 0}–{sup 5}D{sub 2} transition excitation peak of Eu at 465 nm. It indicated that the effective energy transfer happened between ZnO and Eu, which strongly enhanced the luminescence intensity of Eu. At the same time, the Eu and La phosphates could regulate the defect density of ZnO, which could regulate the luminescent intensity of ZnO, and realized the adjustment of luminescent color between green and red light.

  7. Ordered mesoporous crystalline gamma-Al2O3 with variable architecture and porosity from a single hard template.

    Wu, Zhangxiong; Li, Qiang; Feng, Dan; Webley, Paul A; Zhao, Dongyuan

    2010-09-01

    In this paper, an efficient route is developed for controllable synthesis of ordered mesoporous alumina (OMA) materials with variable pore architectures and high mesoporosity, as well as crystalline framework. The route is based on the nanocasting pathway with bimodal mesoporous carbon as the hard template. In contrast to conventional reports, we first realize the possibility of creating two ordered mesopore architectures by using a single carbon hard template obtained from organic-organic self-assembly, which is also the first time such carbon materials are adopted to replicate ordered mesoporous materials. The mesopore architecture and surface property of the carbon template are rationally designed in order to obtain ordered alumina mesostructures. We found that the key factors rely on the unique bimodal mesopore architecture and surface functionalization of the carbon hard template. Namely, the bimodal mesopores (2.3 and 5.9 nm) and the surface functionalities make it possible to selectively load alumina into the small mesopores dominantly and/or with a layer of alumina coated on the inner surface of the large primary mesopores with different thicknesses until full loading is achieved. Thus, OMA materials with variable pore architectures (similar and reverse mesostructures relative to the carbon template) and controllable mesoporosity in a wide range are achieved. Meanwhile, in situ ammonia hydrolysis for conversion of the metal precursor to its hydroxide is helpful for easy crystallization (as low as approximately 500 degrees C). Well-crystallized alumina frameworks composed of gamma-Al(2)O(3) nanocrystals with sizes of 6-7 nm are obtained after burning out the carbon template at 600 degrees C, which is advantageous over soft-templated aluminas. The effects of synthesis factors are demonstrated and discussed relative to control experiments. Furthermore, our method is versatile enough to be used for general synthesis of other important but difficult

  8. Phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure as high-performance electrode materials for supercapacitors

    Cai, Tingwei; Zhou, Min; Han, Guangshuai; Guan, Shiyou

    2013-11-01

    A novel phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure is synthesized by the facile evaporation induced self-assembly strategy under a basic aqueous condition with SiO2 particles as template. The prepared bimodal mesoporous carbons (BMCs) are composed of ordered mesoporous and disordered mesoporous with diameter of about 3.5 nm and 7.0 nm, respectively. They can be employed as supercapacitor electrodes in H2SO4 aqueous electrolyte after the simple acid-treatment. BMC exhibits an exceptional specific capacitance of 344 F g-1 at the current density of 0.1 A g-1, although it has a relatively low surface area of 722 m2 g-1. And the BMC electrode displays an excellent cycling stability over 10,000 cycles.

  9. A novel, efficient and facile method for the template removal from mesoporous materials

    Chen, Lu; Jiang, Shang; Wang, Runwei; Zhang, Zongtao; Qiu, Shilun

    2014-01-01

    © 2014, Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH. A new catalytic-oxidation method was adopted to remove the templates from SBA-15 and MCM-41 mesoporous materials via Fenton

  10. Microspectroscopic analysis of green fluorescent proteins infiltrated into mesoporous silica nanochannels

    Ma, Yujie; Rajendran, Prayanka; Blum, Christian; Cesa, Yanina; Gartmann, Nando; Brühwiler, Dominik; Subramaniam, Vinod

    2011-01-01

    The infiltration of enhanced green fluorescent protein (EGFP) into nanochannels of different diameters in mesoporous silica particles was studied in detail by fluorescence microspectroscopy at room temperature. Silica particles from the MCM-41, ASNCs and SBA-15 families possessing nanometer-sized

  11. MgO-modified mesoporous silicas impregnated by potassium carbonate for carbon dioxide adsorption

    Zukal, Arnošt; Pastva, Jakub; Čejka, Jiří

    2013-01-01

    Roč. 167, FEB 2013 (2013), s. 44-50 ISSN 1387-1811 R&D Projects: GA ČR GA203/08/0604 Institutional support: RVO:61388955 Keywords : mesoporous adsorbents * SBA-15 silica * introducing of MgO and K2CO3 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.209, year: 2013

  12. Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr Catalysts Supported on SBA-15 Silica

    Alicia Carrero

    2017-02-01

    Full Text Available Glycerol steam reforming (GSR is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES, N2-physisorption, X-ray powder diffraction (XRD, hydrogen temperature programmed reduction (H2-TPR, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and thermogravimetric analyses (TGA, and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material.

  13. Synthesis of partially graphitic ordered mesoporous carbons with high surface areas

    Gao, Wenjun; Wan, Ying [Department of Chemistry, Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234 (China); Dou, Yuqian; Zhao, Dongyuan [Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China)

    2011-01-01

    Graphitic carbons with ordered mesostructure and high surface areas (of great interest in applications such as energy storage) have been synthesized by a direct triblock-copolymer-templating method. Pluronic F127 is used as a structure-directing agent, with a low-molecular-weight phenolic resol as a carbon source, ferric oxide as a catalyst, and silica as an additive. Inorganic oxides can be completely eliminated from the carbon. Small-angle XRD and N{sub 2} sorption analysis show that the resultant carbon materials possess an ordered 2D hexagonal mesostructure, uniform bimodal mesopores (about 1.5 and 6 nm), high surface area ({proportional_to}1300 m{sup 2}/g), and large pore volumes ({proportional_to}1.50 cm{sup 3}/g) after low-temperature pyrolysis (900 C). All surface areas come from mesopores. Wide-angle XRD patterns demonstrate that the presence of the ferric oxide catalyst and the silica additive lead to a marked enhancement of graphitic ordering in the framework. Raman spectra provide evidence of the increased content of graphitic sp{sup 2} carbon structures. Transmission electron microscopy images confirm that numerous domains in the ordered mesostructures are composed of characteristic graphitic carbon nanostructures. The evolution of the graphitic structure is dependent on the temperature and the concentrations of the silica additive, and ferric oxide catalyst. Electrochemical measurements performed on this graphitic mesoporous carbon when used as an electrode material for an electrochemical double layer capacitor shows rectangular-shaped cyclic voltammetry curves over a wide range of scan rates, even up to 200 mV/s, with a large capacitance of 155 F/g in KOH electrolyte. This method can be widely applied to the synthesis of graphitized carbon nanostructures. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

    Saha, Dipendu; Barakat, Soukaina; Van Bramer, Scott E; Nelson, Karl A; Hensley, Dale K; Chen, Jihua

    2016-12-14

    In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SO x . SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m 2 /g with total pore volume of 0.71-2.3 cm 3 /g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl 2 ), lead (as Pb(NO 3 ) 2 ), cadmium (as CdCl 2 ), and nickel (as NiCl 2 ) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO 4 , 14% and 2% of Pb was converted to PbSO 4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO 4 . Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

  15. Synthesis of Nitrogen-Doped Mesoporous Carbon for the Catalytic Oxidation of Ethylbenzene

    Wang, Ruicong; Yu, Yifeng; Zhang, Yue; Lv, Haijun; Chen, Aibing

    2017-06-01

    Nitrogen-doped ordered mesoporous carbon (NOMC) was fabricated via a simple hard-template method by functionalized ionic liquids as carbon and nitrogen source, SBA-15 as a hard-template. The obtained NOMC materials have a high nitrogen content of 5.55 %, a high surface area of 446.2 m2 g-1, and an excellent performance in catalysing oxidation of ethylbenzene. The conversion rate of ethylbenzene can be up to 84.5% and the yield of acetophenone can be up to 69.9%, the results indicated that the NOMC materials have a faster catalytic rate and a higher production of acetophenone than catalyst-free and CMK-3, due to their uniform pore size, high surface area and rich active sites in the carbon pore walls.

  16. A novel visible light-driven Ag{sub 3}PO{sub 4}/SBA-15 nanocomposite: Preparation and application in the photo-degradation of pollutants

    Chai, Yuanyuan; Wang, Li; Ren, Jia; Dai, Wei-Lin, E-mail: wldai@fudan.edu.cn

    2015-01-01

    Graphical abstract: - Highlights: • Highly efficient visible-light-driven Ag{sub 3}PO{sub 4}/SBA-15 nanocomposite. • Application in the photo-degradation of RhB. • Synthesis from a facile and simple colloidal method. • 20%-Ag{sub 3}PO{sub 4}/SBA-15 shows 8 times faster degradation rate than Ag{sub 3}PO{sub 4}. • Super stability and recycling ability. - Abstract: A novel visible light-driven environmental-benign Ag{sub 3}PO{sub 4}/SBA-15 nanocomposite photo-catalyst was synthesized for the photo-degradation of pollutants. The exploration on adsorption and photo-catalysis of dye or organic pollution for the nanocomposite was carried out. The adsorption capability for Ag{sub 3}PO{sub 4}/SBA-15 nanocomposite increases by 3 times compared with that of the Ag{sub 3}PO{sub 4} particles. The photo-catalytic activity of nanocomposite is higher than pristine Ag{sub 3}PO{sub 4} nanoparticle for the degradation of RhB or MO under visible light irradiation (λ > 420 nm). The effect of Ag{sub 3}PO{sub 4} loading on the catalytic performance was also studied. The results show that the optimum degradation is achieved over 20% Ag{sub 3}PO{sub 4}/SBA-15. Compared to pure Ag{sub 3}PO{sub 4} nanoparticle, the most efficient catalyst showed 8 times higher photo-catalytic activity for the degradation of RhB. The Ag{sub 3}PO{sub 4}/SBA-15 catalysts were systematically characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–Vis diffuse reflectance spectroscopy (DRS), and N{sub 2}-adsorption–desorption isotherms (BET). A possible mechanism scheme regarding photo-degradation enhancement induced by dye enrichments has been proposed on the Ag{sub 3}PO{sub 4}/SBA-15 nanocomposite. Additionally, the SBA-15 support can enhance the efficiency of separation of catalyst from the reaction mixture, implying that the Ag{sub 3}PO{sub 4} loading on the SBA-15 catalyst will not result in the extra environment and health

  17. A novel visible light-driven Ag3PO4/SBA-15 nanocomposite: Preparation and application in the photo-degradation of pollutants

    Chai, Yuanyuan; Wang, Li; Ren, Jia; Dai, Wei-Lin

    2015-01-01

    Graphical abstract: - Highlights: • Highly efficient visible-light-driven Ag 3 PO 4 /SBA-15 nanocomposite. • Application in the photo-degradation of RhB. • Synthesis from a facile and simple colloidal method. • 20%-Ag 3 PO 4 /SBA-15 shows 8 times faster degradation rate than Ag 3 PO 4 . • Super stability and recycling ability. - Abstract: A novel visible light-driven environmental-benign Ag 3 PO 4 /SBA-15 nanocomposite photo-catalyst was synthesized for the photo-degradation of pollutants. The exploration on adsorption and photo-catalysis of dye or organic pollution for the nanocomposite was carried out. The adsorption capability for Ag 3 PO 4 /SBA-15 nanocomposite increases by 3 times compared with that of the Ag 3 PO 4 particles. The photo-catalytic activity of nanocomposite is higher than pristine Ag 3 PO 4 nanoparticle for the degradation of RhB or MO under visible light irradiation (λ > 420 nm). The effect of Ag 3 PO 4 loading on the catalytic performance was also studied. The results show that the optimum degradation is achieved over 20% Ag 3 PO 4 /SBA-15. Compared to pure Ag 3 PO 4 nanoparticle, the most efficient catalyst showed 8 times higher photo-catalytic activity for the degradation of RhB. The Ag 3 PO 4 /SBA-15 catalysts were systematically characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–Vis diffuse reflectance spectroscopy (DRS), and N 2 -adsorption–desorption isotherms (BET). A possible mechanism scheme regarding photo-degradation enhancement induced by dye enrichments has been proposed on the Ag 3 PO 4 /SBA-15 nanocomposite. Additionally, the SBA-15 support can enhance the efficiency of separation of catalyst from the reaction mixture, implying that the Ag 3 PO 4 loading on the SBA-15 catalyst will not result in the extra environment and health problems and reduce the cost of wastewater treatment

  18. A highly sensitive electrochemical sensor for the determination of methanol based on PdNPs@SBA-15-PrEn modified electrode.

    Karimi, Ziba; Shamsipur, Mojtaba; Tabrizi, Mahmoud Amouzadeh; Rostamnia, Sadegh

    2018-05-01

    In this study, a novel electrochemical sensor for the determination of methanol based on palladium nanoparticles supported on Santa barbara amorphous-15- PrNHEtNH 2 (PdNPs@SBA-15-PrEn) as nanocatalysis platform is presented. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical methods are employed to characterize the PdNPs@SBA-15-PrEn nanocomposite. The Nafion-Pd@SBA-15-PrEn modified glassy carbon electrode (Nafion-PdNPs@SBA-15-PrEn/GCE) displayed the high electrochemical activity and excellent catalytic characteristic for electro-oxidation of methanol in an alkaline solution. The electro-oxidation performance of the proposed sensor was investigated using cyclic voltammetry (CV) and amperometry. The sensor exhibits a good sensitivity of 0.0905 Amol -1 Lcm -2 , linear range of 20-1000 μM and the corresponding detection limit of 12 μM (3σ). The results demonstrate that the Nafion-PdNPs@SBA-15-PrEn/GCE has potential as an efficient and integrated sensor for methanol detection. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. Catalytic Steam Reforming of Toluene as a Model Compound of Biomass Gasification Tar Using Ni-CeO2/SBA-15 Catalysts

    Erik Dahlquist

    2013-07-01

    Full Text Available Nickel supported on SBA-15 doped with CeO2 catalysts (Ni-CeO2/SBA-15 was prepared, and used for steam reforming of toluene which was selected as a model compound of biomass gasification tar. A fixed-bed lab-scale set was designed and employed to evaluate the catalytic performances of the Ni-CeO2/SBA-15 catalysts. Experiments were performed to reveal the effects of several factors on the toluene conversion and product gas composition, including the reaction temperature, steam/carbon (S/C ratio, and CeO2 loading content. Moreover, the catalysts were subjected to analysis of their carbon contents after the steam reforming experiments, as well as to test the catalytic stability over a long experimental period. The results indicated that the Ni-CeO2/SBA-15 catalysts exhibited promising capabilities on the toluene conversion, anti-coke deposition and catalytic stability. The toluene conversion reached as high as 98.9% at steam reforming temperature of 850 °C and S/C ratio of 3 using the Ni-CeO2(3wt%/SBA-15 catalyst. Negligible coke formation was detected on the used catalyst. The gaseous products mainly consisted of H2 and CO, together with a little CO2 and CH4.

  20. Covalent immobilization of lipase onto chitosan-mesoporous silica hybrid nanomaterials by carboxyl functionalized ionic liquids as the coupling agent.

    Xiang, Xinran; Suo, Hongbo; Xu, Chao; Hu, Yi

    2018-05-01

    Chitosan-mesoporous silica SBA-15 hybrid nanomaterials (CTS-SBA-15) were synthesized by means of carboxyl functionalized ionic liquids as the coupling agent. The as-prepared CTS-SBA-15 support was characterized by TEM, FTIR, TG and nitrogen adsorption-desorption techniques. Porcine pancreas lipase (PPL) was then bound to the hybrid nanomaterials by using the cross-linking reagent glutaraldehyde (GA). Further, the parameters like cross-linking concentration, time and ratio of supports to enzyme were optimized. The property of immobilized lipase were tested in detail by enzyme activity assays. The results indicated that the hybrid nanomaterials could form three-dimensional (3D) structure with homogeneous mesoporous structures and immobilized PPL revealed excellent enzymatic performance. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

    Farzin Nejad, N., E-mail: Farzinnejadn@ripi.ir [Petroleum Refining Technology Development Division, Research Institute of Petroleum Industry, Tehran 14857-33111 (Iran, Islamic Republic of); Shams, E.; Amini, M.K. [Department of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

    2015-09-15

    In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm and transmission electron microscopy. Nitrogen adsorption–desorption measurement revealed the high surface area (810 m{sup 2} g{sup −1}), maxima pore size of 3.3 nm and large pore volume (1.01 cm{sup 3} g{sup −1}) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g{sup −1} of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles. - Highlights: • Adsorptive desulfurization of model oil with magnetic ordered mesoporous carbon adsorbent, Fe-OMC, was studied. • Maximum adsorption capacity (q{sub max}) of Fe-OMC for DBT was found to be 111.1 mg g{sup −1}. • Freundlich isotherm best represents the equilibrium adsorption data. • Rate of DBT adsorption process onto Fe-OMC is controlled by at least two steps.

  2. Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

    Farzin Nejad, N.; Shams, E.; Amini, M.K.

    2015-01-01

    In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm and transmission electron microscopy. Nitrogen adsorption–desorption measurement revealed the high surface area (810 m 2 g −1 ), maxima pore size of 3.3 nm and large pore volume (1.01 cm 3 g −1 ) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g −1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles. - Highlights: • Adsorptive desulfurization of model oil with magnetic ordered mesoporous carbon adsorbent, Fe-OMC, was studied. • Maximum adsorption capacity (q max ) of Fe-OMC for DBT was found to be 111.1 mg g −1 . • Freundlich isotherm best represents the equilibrium adsorption data. • Rate of DBT adsorption process onto Fe-OMC is controlled by at least two steps

  3. Thermal and mechanical properties of novel nanocomposites from modified ordered mesoporous carbon FDU-15 and poly(methyl methacrylate)

    Mohammadnezhad, Gholamhossein, E-mail: mohammadnezhad@cc.iut.ac.ir; Dinari, Mohammad, E-mail: dinari@cc.iut.ac.ir; Soltani, Roozbeh; Bozorgmehr, Zahra

    2015-08-15

    Graphical abstract: - Highlights: • The surface of mesoporous carbon, FDU-15, was modified by 3-mercaptopropyl-trimethoxysilane. • Nanocomposites of PMMA and modified FDU-15 were prepared by solution polymerization. • XRD shows that modified mesoporous FDU-15 has an ordered hexagonal mesostructure. • TEM and SEM images confirm the presence of large pores and ordered mesostructure. • Mechanical data indicated improvement in the tensile strength and modulus. - Abstract: With its well-ordered pore structure, high specific surface area and tunable pore diameters, ordered mesoporous carbons are suitable for applications in many areas of modern science and technology. In the present investigation, an ultrasonic irradiation was used for the modification of the mesoporous carbon FDU-15. Three nanocomposite films of the poly(methyl methacrylate) (PMMA) and modified FDU-15 were prepared by solution polymerization technique. The surface morphology and thermal and mechanical properties of the hybrid materials were evaluated by different methods. X-ray diffraction patterns showed that modified mesoporous FDU-15 had an ordered hexagonal mesostructure. Transmission electron microscopy (TEM) and field emission-scanning electron microscopy images confirmed the presence of large pores and a relatively ordered mesostructure for the functionalized materials. Thermogravimetric analysis data also revealed that the onset of decomposition temperature of the nanocomposites was higher than that of pristine PMMA, shifting toward higher temperatures as the amount of modified-FDU was increased. TEM images showed the well-ordered hexagonal arrays of mesopores FDU-15. Mechanical data indicated the improvement in the tensile strength and modulus with the modified FDU-15 loading. The film containing 1 wt.% of modified FDU-15 had a tensile strength of the order of 42 MPa, relative to the 28 MPa of the pristine PMMA.

  4. Thermal and mechanical properties of novel nanocomposites from modified ordered mesoporous carbon FDU-15 and poly(methyl methacrylate)

    Mohammadnezhad, Gholamhossein; Dinari, Mohammad; Soltani, Roozbeh; Bozorgmehr, Zahra

    2015-01-01

    Graphical abstract: - Highlights: • The surface of mesoporous carbon, FDU-15, was modified by 3-mercaptopropyl-trimethoxysilane. • Nanocomposites of PMMA and modified FDU-15 were prepared by solution polymerization. • XRD shows that modified mesoporous FDU-15 has an ordered hexagonal mesostructure. • TEM and SEM images confirm the presence of large pores and ordered mesostructure. • Mechanical data indicated improvement in the tensile strength and modulus. - Abstract: With its well-ordered pore structure, high specific surface area and tunable pore diameters, ordered mesoporous carbons are suitable for applications in many areas of modern science and technology. In the present investigation, an ultrasonic irradiation was used for the modification of the mesoporous carbon FDU-15. Three nanocomposite films of the poly(methyl methacrylate) (PMMA) and modified FDU-15 were prepared by solution polymerization technique. The surface morphology and thermal and mechanical properties of the hybrid materials were evaluated by different methods. X-ray diffraction patterns showed that modified mesoporous FDU-15 had an ordered hexagonal mesostructure. Transmission electron microscopy (TEM) and field emission-scanning electron microscopy images confirmed the presence of large pores and a relatively ordered mesostructure for the functionalized materials. Thermogravimetric analysis data also revealed that the onset of decomposition temperature of the nanocomposites was higher than that of pristine PMMA, shifting toward higher temperatures as the amount of modified-FDU was increased. TEM images showed the well-ordered hexagonal arrays of mesopores FDU-15. Mechanical data indicated the improvement in the tensile strength and modulus with the modified FDU-15 loading. The film containing 1 wt.% of modified FDU-15 had a tensile strength of the order of 42 MPa, relative to the 28 MPa of the pristine PMMA

  5. Mesoporous Silica-Supported Sulfonyldiamine Ligand for Microwave-Assisted Transfer Hydrogenation

    Shaheen M. Sarkar

    2015-01-01

    Full Text Available N-Sulfonyl-1,2-diamine ligands, derived from 1,2-diaminocyclohexane and 1,2-diaminopropane, were immobilized onto mesoporous SBA-15 silica. The SBA-15-supported sulfonyldiamine-Ru complex was prepared in situ under microwave heating at 60 W for 3 min. The prepared sulfonyldiamine-Ru complex was used as an efficient catalyst for the transfer hydrogenation of ketones to the corresponding secondary alcohols. The heterogeneous complex showed extremely high catalytic activity with 99% conversion rate under microwave heating condition. The complexes were regenerated by simple filtration and reused two times without significant loss of activity.

  6. Enhanced microwave absorption properties of Ni-doped ordered mesoporous carbon/polyaniline nanocomposites

    Wang, Liuding; Wu, Hongjing; Shen, Zhongyuan; Guo, Shaoli; Wang, Yiming

    2012-01-01

    Highlights: ► OMC-Ni/PANI nanocomposites were prepared by in situ polymerization method. ► The effective absorption bandwidth was 4.7 GHz for OMC-Ni0.15/PANI. ► OMC-Ni/PANI showed excellent microwave absorption with respect to OMC-Ni. ► This effect could be mainly attributed to the improvement of impendence matching. - Abstract: We propose and demonstrate a new scheme to improve microwave absorption property through polyaniline (PANI)-functionalized Ni-doped ordered mesoporous carbon (OMC) by in situ polymerization method. The polymer-functionalized nanocomposites, embedding polyaniline within ordered mesoporous carbon, exhibit strong and broadband microwave absorption due to its better dielectric loss characteristic. OMC-Ni0.15/PANI exhibits an effective absorption bandwidth (i.e., reflection loss (RL) ≤ −10 dB) of 4.7 GHz and an absorption peak of −51 dB at 9.0 GHz. The absorption peak intensity and position can be tuned by controlling the thickness of the coating.

  7. Morphology control of ordered mesoporous carbons for high capacity lithium sulfur batteries

    Schuster, Joerg David

    2011-06-07

    The focus of this thesis concerns the morphology control of ordered mesoporous carbon (OMC) materials. Ordered mesoporous carbons with diverse morphologies, that are thin films, fibers - embedded in anodic alumina membranes and free-standing - or spherical nanoparticles, have been successfully prepared by soft-templating procedures. The mechanisms of structure formation and processing were investigated with in-situ SAXS measurements and their application in high capacity lithium-sulfur batteries was successfully tested in cooperation with Guang He and Linda Nazar from the University of Waterloo in Canada. The Li-S batteries receive increasing attention due to their high theoretical energy density which is 3 to 5 times higher than from lithium-ion batteries. For this type of battery the specific pore volume is crucial for the content of the active component (sulfur) in the cathode and therefore correlates with the capacity and gravimetric energy density of the battery. At first, mesoporous thin films with 2D-hexagonal structure were obtained through organic-organic self-assembly of a preformed oligomeric resol precursor and the triblock copolymer template Pluronic P123. The formation of a condensed-wall material through thermopolymerization of the precursor oligomers resulted in mesostructured phenolic resin films. Subsequent decomposition of the surfactant and partial carbonization were achieved through thermal treatment in inert atmosphere. The films were crack-free with tunable homogenous thicknesses, and showed either 2D-hexagonal or lamellar mesostructure. An additional, yet unknown 3D-mesostructure was also found. In the second part, cubic and circular hexagonal mesoporous carbon phases in the confined environment of tubular anodic alumina membrane (AAM) pores were obtained by self-assembly of the mentioned resol precursor and the triblock copolymer templates Pluronic F127 or P123, respectively. Casting and solvent-evaporation were also followed by

  8. Large third-order optical nonlinearity in vertically oriented mesoporous silica thin films embedded with Ag nanoparticles

    Tan, Min; Liu, Qiming, E-mail: qmliu@whu.edu.cn [Wuhan University, Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education, School of Physics and Technology (China)

    2016-12-15

    Taking advantage of the channel confinement of mesoporous films to prevent the agglomeration of Ag nanoparticles to achieve large third-order optical nonlinearity in amorphous materials, Ag-loaded composite mesoporous silica film was prepared by the electrochemical deposition method on ITO substrate. Ag ions were firstly transported into the channels of mesoporous film by the diffusion and binding force of channels, which were reduced to nanoparticles by applying suitable voltage. The existence and uniform distribution of Ag nanoparticles ranging in 1–10 nm in the mesoporous silica thin films were exhibited by UV spectrophotometer, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements. The third-order optical nonlinearity induced by Ag nanoparticles was studied by the Z-scan technique. Due to the local field surface plasmon resonance, the maximum third-order nonlinear optical susceptibility of Ag-loaded composite mesoporous silica film is 1.53×10{sup −10} esu, which is 1000 times larger than that of the Ag-contained chalcogenide glasses which showed large nonlinearity in amorphous materials.

  9. Thiol-Functionalized Mesoporous Silica for Effective Trap of Mercury in Rats

    Wei Zhao

    2016-01-01

    Full Text Available The chance of exposure to heavy metal for human being rises severely today due to the increasing water contamination and air pollution. Here, we prepared a series of thiol-functionalized mesoporous silica as oral formulation for the prevention and treatment of heavy metal poisoning. The successful incorporation of thiol was verified by the FTIR spectra. SBA15-SH-10 was used for the study as it is of uniform mesopores and fine water dispersibility. In simulated gastrointestinal fluid, the thiol-functionalized mesoporous silica can selectively capture heavy metal, showing a very high affinity for inorganic mercury (II. The blood and urine mercury levels of rats fed with a diet containing Hg (II and material were significantly lower than those of rats fed with the metal-rich diet only. On the contrary, the mercury content in fecal excretion of the treatment group increased more than twice as much as that of the control group. This result indicated that SBA15-SH-10 could effectively remove mercury (II in vivo and the mercury loaded on SBA15-SH-10 would be excreted out. Hence, SBA15-SH-10 has potential application in preventing and treating heavy metal poisoning via digestive system.

  10. Size Effect of Ordered Mesoporous Carbon Nanospheres for Anodes in Li-Ion Battery

    Pei-Yi Chang

    2015-12-01

    Full Text Available The present work demonstrates the application of various sizes of ordered mesoporous carbon nanospheres (OMCS with diameters of 46–130 nm as an active anode material for Li-ion batteries (LIB. The physical and chemical properties of OMCS have been evaluated by performing scanning electron microscopy (SEM, transmission electron microscopy (TEM, N2 adsorption-desorption analysis; small-angle scattering system (SAXS and X-ray diffraction (XRD. The electrochemical analysis of using various sizes of OMCS as anode materials showed high capacity and rate capability with the specific capacity up to 560 mA·h·g−1 at 0.1 C after 85 cycles. In terms of performance at high current rate compared to other amorphous carbonaceous materials; a stable and extremely high specific capacity of 240 mA·h·g−1 at 5 C after 15 cycles was achieved. Such excellent performance is mainly attributed to the suitable particle size distribution of OMCS and intimate contact between OMCS and conductive additives; which can be supported from the TEM images. Results obtained from this study clearly indicate the excellence of size distribution of highly integrated mesoporous structure of carbon nanospheres for LIB application.

  11. Tuning the Pore Geometry of Ordered Mesoporous Carbons for Enhanced Adsorption of Bisphenol-A

    Wannes Libbrecht

    2015-04-01

    Full Text Available Mesoporous carbons were synthesized via both soft and hard template methods and compared to a commercial powder activated carbon (PAC for the adsorption ability of bisphenol-A (BPA from an aqueous solution. The commercial PAC had a BET-surface of 1027 m2/g with fine pores of 3 nm and less. The hard templated carbon (CMK-3 material had an even higher BET-surface of 1420 m2/g with an average pore size of 4 nm. The soft templated carbon (SMC reached a BET-surface of 476 m2/g and a pore size of 7 nm. The maximum observed adsorption capacity (qmax of CMK-3 was the highest with 474 mg/g, compared to 290 mg/g for PAC and 154 mg/g for SMC. The difference in adsorption capacities was attributed to the specific surface area and hydrophobicity of the adsorbent. The microporous PAC showed the slowest adsorption, while the ordered mesopores of SMC and CMK-3 enhanced the BPA diffusion into the adsorbent. This difference in adsorption kinetics is caused by the increase in pore diameter. However, CMK-3 with an open geometry consisting of interlinked nanorods allows for even faster intraparticle diffusion.

  12. Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC.

    Huang, Lili; Lu, Juan; Di, Bin; Feng, Fang; Su, Mengxiang; Yan, Fang

    2011-09-01

    Monodisperse spherical periodic mesoporous organosilicas (PMOs) with ethane integrated in the framework were synthesized and their application as stationary phase for chromatographic separation is demonstrated. The ethane-PMOs were prepared by condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) in basic condition using octadecyltrimethylammonium chloride (C(18)TMACl) as template and ethanol as co-solvent. The morphology and mesoporous structure of ethane-PMOs were controlled under different concentrations of sodium hydroxide (NaOH) and EtOH. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis showed that ethane-PMOs have spherical morphology, uniform particle distribution, highly ordered pore structure, high surface area and narrow pore-size distribution. The column packed with these materials exhibits good permeability, high chemical stability and good selectivity of mixtures of aromatic hydrocarbons in normal phase high-performance liquid chromatography (HPLC). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Tuning the Pore Geometry of Ordered Mesoporous Carbons for Enhanced Adsorption of Bisphenol-A

    Libbrecht, Wannes; Vandaele, Koen; De Buysser, Klaartje; Verberckmoes, An; Thybaut, Joris W.; Poelman, Hilde; De Clercq, Jeriffa; Van Der Voort, Pascal

    2015-01-01

    Mesoporous carbons were synthesized via both soft and hard template methods and compared to a commercial powder activated carbon (PAC) for the adsorption ability of bisphenol-A (BPA) from an aqueous solution. The commercial PAC had a BET-surface of 1027 m2/g with fine pores of 3 nm and less. The hard templated carbon (CMK-3) material had an even higher BET-surface of 1420 m2/g with an average pore size of 4 nm. The soft templated carbon (SMC) reached a BET-surface of 476 m2/g and a pore size of 7 nm. The maximum observed adsorption capacity (qmax) of CMK-3 was the highest with 474 mg/g, compared to 290 mg/g for PAC and 154 mg/g for SMC. The difference in adsorption capacities was attributed to the specific surface area and hydrophobicity of the adsorbent. The microporous PAC showed the slowest adsorption, while the ordered mesopores of SMC and CMK-3 enhanced the BPA diffusion into the adsorbent. This difference in adsorption kinetics is caused by the increase in pore diameter. However, CMK-3 with an open geometry consisting of interlinked nanorods allows for even faster intraparticle diffusion. PMID:28788023

  14. 3D visualization of TiO2 nanocrystals in mesoporous nanocomposite using energy filtered transmission electron microscopy tomography

    Gondo, Takashi; Kasama, Takeshi; Kaneko, Kenji

    2014-01-01

    Mesoporous silica, SBA-15, is one of the best candidate for the supporting material of catalytic nanoparticles because of its relative large and controllable pore size and large specific surface area [1]. So far, various nanoparticles, such as Au, Pt and Pd, have been introduced into the pore for...

  15. Ordered mesoporous carbon/FeO(OH) composites for supercapacitors with high capacitive performance

    Liao, H.; Zhao, J.; Tang, B.; Xu, J. [Shanghai Univ. of Engineering Science (China). College of Chemistry and Chemical Engineering

    2010-07-01

    In this study, ordered mesoporous carbon/FeO(OH) composites were synthesized using an incipient wetness impregnation method. X-ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen gas (N{sub 2}) adsorption/desorption analyses were used to characterize the morphology and microstructure of the composite samples. The analyses indicated that a new hydrate iron oxide was obtained for use as a low-cost composite electrode. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses were conducted in 2 M KOH aqueous solutions in order to characterize the capacitor properties of the composite materials. The study showed that the highest special capacitance obtained by the composites was 486.27 F/g measured at 5 mV/s for an OMCL composite material containing 9.6 per cent FeO(OH). The capacitor properties of various amounts of FeO(OH) were also investigated.

  16. Oriented Decoration in Metal-Functionalized Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds

    Shijian Zhou

    2018-02-01

    Full Text Available Ordered mesoporous silicas (OMSs attract considerable attention due to their advanced structural properties. However, for the pristine silica materials, the inert property greatly inhibits their catalytic applications. Thus, to contribute to the versatile surface of OMSs, different metal active sites, including acidic/basic sites and redox sites, have been introduced into specific locations (mesoporous channels and framework of OMSs and the metal-functionalized ordered mesoporous silicas (MOMSs show great potential in the catalytic applications. In this review, we first present the categories of metal active sites. Then, the synthesized processes of MOMSs are thoroughly discussed, in which the metal active sites would be introduced with the assistance of organic groups into the specific locations of OMSs. In addition, the structural morphologies of OMSs are elaborated and the catalytic applications of MOMSs in the oxidation of aromatic compounds are illustrated in detail. Finally, the prospects for the future development in this field are proposed.

  17. Thermal and mechanical properties of novel nanocomposites from modified ordered mesoporous carbon FDU-15 and poly(methyl methacrylate)

    Mohammadnezhad, Gholamhossein; Dinari, Mohammad; Soltani, Roozbeh; Bozorgmehr, Zahra

    2015-08-01

    With its well-ordered pore structure, high specific surface area and tunable pore diameters, ordered mesoporous carbons are suitable for applications in many areas of modern science and technology. In the present investigation, an ultrasonic irradiation was used for the modification of the mesoporous carbon FDU-15. Three nanocomposite films of the poly(methyl methacrylate) (PMMA) and modified FDU-15 were prepared by solution polymerization technique. The surface morphology and thermal and mechanical properties of the hybrid materials were evaluated by different methods. X-ray diffraction patterns showed that modified mesoporous FDU-15 had an ordered hexagonal mesostructure. Transmission electron microscopy (TEM) and field emission-scanning electron microscopy images confirmed the presence of large pores and a relatively ordered mesostructure for the functionalized materials. Thermogravimetric analysis data also revealed that the onset of decomposition temperature of the nanocomposites was higher than that of pristine PMMA, shifting toward higher temperatures as the amount of modified-FDU was increased. TEM images showed the well-ordered hexagonal arrays of mesopores FDU-15. Mechanical data indicated the improvement in the tensile strength and modulus with the modified FDU-15 loading. The film containing 1 wt.% of modified FDU-15 had a tensile strength of the order of 42 MPa, relative to the 28 MPa of the pristine PMMA.

  18. Assessment of the adjuvant activity of mesoporous silica nanoparticles in recombinant Mycoplasma hyopneumoniae antigen vaccines

    Veridiana Gomes Virginio

    2017-01-01

    Full Text Available The adjuvant potential of two mesoporous silica nanoparticles (MSNs, SBa-15 and SBa-16, was assessed in combination with a recombinant HSP70 surface polypeptide domain from Mycoplasma hyopneumoniae, the etiological agent of porcine enzootic pneumonia (PEP. The recombinant antigen (HSP70212-600, previously shown as immunogenic in formulation with classic adjuvants, was used to immunize BALB/c mice in combination with SBa-15 or SBa-16 MSNs, and the effects obtained with these formulations were compared to those obtained with alum, the adjuvant traditionally used in anti-PEP bacterins. The HSP70212-600 + SBa-15 vaccine elicited a strong humoral immune response, with high serum total IgG levels, comparable to those obtained using HSP70212-600 + alum. The HSP70212-600 + SBa-16 vaccine elicited a moderate humoral immune response, with lower levels of total IgG. The cellular immune response was assessed by the detection of IFN-γ, IL-4 and IL-10 in splenocyte culture supernatants. The HSP70212-600 + SBa-15 vaccine increased IFN-γ, IL-4 and IL-10 levels, while no stimulation was detected with the HSP70212-600 + SBa-16 vaccine. The HSP70212-600 + SBa-15 vaccine induced a mixed Th1/Th2-type response, with an additional IL-10 mediated anti-inflammatory effect, both of relevance for an anti-PEP vaccine. Alum adjuvant controls stimulated an unspecific cellular immune response, with similar levels of cytokines detected in mice immunized either with HSP70212-600 + alum or with the adjuvant alone. The better humoral and cellular immune responses elicited in mice indicated that SBa-15 has adjuvant potential, and can be considered as an alternative to the use of alum in veterinary vaccines. The use of SBa-15 with HSP70212-600 is also promising as a potential anti-PEP subunit vaccine formulation.

  19. Hierarchically ordered mesoporous carbon/graphene composites as supercapacitor electrode materials.

    Song, Yanjie; Li, Zhu; Guo, Kunkun; Shao, Ting

    2016-08-25

    Hierarchically ordered mesoporous carbon/graphene (OMC/G) composites have been fabricated by means of a solvent-evaporation-induced self-assembly (EISA) method. The structures of these composites are characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and nitrogen adsorption-desorption at 77 K. These results indicate that OMC/G composites possess the hierarchically ordered hexagonal p6mm mesostructure with the lattice unit parameter and pore diameter close to 10 nm and 3 nm, respectively. The specific surface area of OMC/G composites after KOH activation is high up to 2109.2 m(2) g(-1), which is significantly greater than OMC after activation (1474.6 m(2) g(-1)). Subsequently, the resulting OMC/G composites as supercapacitor electrode materials exhibit an outstanding capacitance as high as 329.5 F g(-1) in 6 M KOH electrolyte at a current density of 0.5 A g(-1), which is much higher than both OMC (234.2 F g(-1)) and a sample made by mechanical mixing of OMC with graphene (217.7 F g(-1)). In addition, the obtained OMC/G composites display good cyclic stability, and the final capacitance retention is approximately 96% after 5000 cycles. These ordered mesopores in the OMC/G composites are beneficial to the accessibility and rapid diffusion of the electrolyte, while graphene in OMC/G composites can also facilitate the transport of electrons during the processes of charging and discharging owing to its high conductivity, thereby leading to an excellent energy storage performance. The method demonstrated in this work would open up a new route to design and develop graphene-based architectures for supercapacitor applications.

  20. Gold and palladium adsorption from leached electronic scrap using ordered mesoporous carbon nanoscaffolds

    McDowell, Rocklan; Dutech, Guy

    2014-09-01

    Ordered mesoporous carbon (OMC) nanoscaffolds are engineered agglomerates of carbon nanotubes held together by small carbon nanofibers with uniform pore sizes, high pore volume, and high channel permeability. These materials exhibit very high affinity for the adsorption of gold from aqueous acidic mixtures. The efficiency of gold recovery is comparable to those typically accomplished using biopolymer-based adsorbents. The adsorption efficiency for other precious metals such as palladium and platinum is lower. Studies on the precious metal (Au, Pd) adsorption on OMC materials from actual liquors of leached electronics will be presented. Adsorption properties will be compared for several different sorbents used for the recovery of precious metals. The leach liquor compositions for three different types of electronic scrap materials (personal computer board, cell phone and tv input/output board) will be presented. The sorption efficiencies for Au, Pd, together with a spectrum of competing and non-competing metals, from such leach mixtures will be compared.

  1. Comparative study on the electrocatalytic activities of ordered mesoporous carbons and graphene

    Wang Huan; Qi Bin; Lu Baoping; Bo Xiangjie; Guo Liping

    2011-01-01

    In this work, a comparative study on the electrocatalytic activities of ordered mesoporous carbons (OMCs) and graphene (GR) is presented. Using voltammetry and amperometry as detection methods, four DNA bases, double-stranded DNA (dsDNA), six important electroactive compounds and various biomolecules were employed to investigate their electrochemical responses on OMC and GR modified glassy carbon electrodes (OMC/GCE and GR/GCE). The results show that OMC/GCE enhances the electron transfer kinetics of these compounds compared to GR/GCE. The discrepancy in electrochemical activities can be attributed to the different microstructures of OMC and GR, which were examined by transmission electron microscopy, X-ray photoelectron spectra, X-ray diffraction, Raman spectra and nitrogen adsorption-desorption.

  2. Gold and palladium adsorption from leached electronic scrap using ordered mesoporous carbon nanoscaffolds

    McDowell, Rocklan; Dutech, Guy

    2014-01-01

    Ordered mesoporous carbon (OMC) nanoscaffolds are engineered agglomerates of carbon nanotubes held together by small carbon nanofibers with uniform pore sizes, high pore volume, and high channel permeability. These materials exhibit very high affinity for the adsorption of gold from aqueous acidic mixtures. The efficiency of gold recovery is comparable to those typically accomplished using biopolymer-based adsorbents. The adsorption efficiency for other precious metals such as palladium and platinum is lower. Studies on the precious metal (Au, Pd) adsorption on OMC materials from actual liquors of leached electronics will be presented. Adsorption properties will be compared for several different sorbents used for the recovery of precious metals. The leach liquor compositions for three different types of electronic scrap materials (personal computer board, cell phone and tv input/output board) will be presented. The sorption efficiencies for Au, Pd, together with a spectrum of competing and non-competing metals, from such leach mixtures will be compared.

  3. A novel method to prepare binary Ni-Fe compounds and ordered mesoporous carbon composite as a supercapacitor electrode

    Feng, J.; Tang, B.; Zhao, J.; Liu, P.; Xu, J. [Shanghai Univ. of Engineering Science (China). College of Chemistry and Chemical Engineering

    2010-07-01

    Superapacitor electrodes with nickel/iron compounds and ordered mesoporous carbon (OMC) nanocomposites were fabricated using a incipient wetness impregnation and hydrothermal methods. The use of the nickel-iron compounds within the OMC framework resulted in a synergistic effect. Resistance was also improved. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses demonstrated that the host structure was preserved during the impregnation and hydrothermal procedures. Nano-sized metal compounds were formed within the mesopore system. Nitrogen adsorption and desorption isotherm measurements demonstrated mesoporosity for the host/guest composites.

  4. Generation of Well-Defined Pairs of Silylamine on Highly Dehydroxylated SBA-15: Application to the Surface Organometallic Chemistry of Zirconium

    Azzi, Joachim

    2012-01-01

    achieved by an ammonia treatment of a highly dehydroxylated SBA-15 at 1000°C (SBA-151000). This support is known to contain mainly strained reactive siloxane bridges (≡Si-O-Si≡)[1] along with a small amount of isolated plus germinal silanols =Si(OH)2

  5. Facile synthesis of gold nanoparticles on propylamine functionalized SBA-15 and effect of surface functionality of its enhanced bactericidal activity against gram positive bacteria

    Bhuyan, Diganta; Saikia, Mrinal; Saikia, Lakshi; Gogoi, Animesh; Saikia, Ratul

    2015-01-01

    The facile synthesis of an SBA-15-pr- + NH 3 .Au 0 nano-hybrid material by spontaneous autoreduction of aqueous chloroaurate anions on propylamine functionalized SBA-15 was successfully demonstrated. The as-synthesized SBA-15-pr- + NH 3 .Au 0 nano-hybrid material was well characterized using low and wide angle x-ray diffraction (XRD), N 2 adsorption–desorption isotherms, Fourier transform infrared (FTIR), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX), x-ray photoelectron spectroscopy (XPS), UV-Visible spectroscopy and atomic absorption spectroscopy (AAS). The activity of the nano-hybrid material as a potent bactericidal agent was successfully tested against Gram positive/negative bacteria viz. Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The colony killing percentage of Gram positive bacteria was found to be higher than Gram negative bacteria due to the stronger electrostatic interaction between the positively-charged amine functionality of SBA-15 and the negatively charged functionality of the bacterial cell wall. (paper)

  6. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Albayati, Talib M.; Doyle, Aidan M.

    2015-02-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  7. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Albayati, Talib M., E-mail: talib-albyati@yahoo.com [University of Technology, Department of Chemical Engineering (Iraq); Doyle, Aidan M., E-mail: a.m.doyle@mmu.ac.uk [Manchester Metropolitan University, Division of Chemistry and Environmental Science (United Kingdom)

    2015-02-15

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  8. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    Albayati, Talib M.; Doyle, Aidan M.

    2015-01-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption–desorption porosimetry (Brunauer–Emmett–Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96–99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction

  9. The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

    Yu, Xiaofang; Yu, Xiaobo; Wu, Shujie; Liu, Bo; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-02-01

    Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N 2 adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization.

  10. Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

    Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

    2014-01-01

    Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

  11. An enzyme-assisted electrochemiluminescent biosensor developed on order mesoporous carbons substrate for ultrasensitive glyphosate sensing

    Zhang, Qingrong; Xu, Guifang; Gong, Lingshan; Dai, Hong; Zhang, Shupei; Li, Yilin; Lin, Yanyu

    2015-01-01

    In this paper, a strategy of developing a late-model and sensitive electrochemiluminescence (ECL) biosensor for glyphosate detection based on enzyme-assisted in situ generation of ZnS quantum dots (QDs) on ordered mesoporous carbons (OMC) substrate was proposed. OMC, as a typically ordered mesoporous carbon material, not only provides a protective microenvironment for enzyme to retain its structure and activity but also has a synergistic effect with chitosan for the absorption of Zn 2+ ions by virtue of its high surface area and high pore volume and thus employed as the matrix of proposed biosensor. Then horseradish peroxidase (HRP) was introduced to expedite the generation of ZnS QDs via accelerating the reduction of Na 2 S 2 O 3 with H 2 O 2 to yield H 2 S that reacted with Zn 2+ ions. Glyphosate, as a kind of organic pesticide with amine, carboxyl and phosphonate group which would coordinate strongly to metal ions, possessed the potential to inhibited the activity of HRP, because HRP contain iron (III) protoporphyrin IX (ferriprotoporphyrin IX) as the prosthetic group which would react with the amine, carboxyl and phosphonate group of glyphosate. Accordingly, the proposed ECL QDs biosensor was employed to determine the Gly and shown a wide linear range from 0.1 nM to 10 mM with excellent sensitivity, reproducibility and selectivity. Further, the half maximal inhibitory concentration (IC 50 ) and the Michaelis–Menten constant were studied, and all the results indicated that the proposed strategy is practicable and provide a new opportunity to develop novel ECL sensing platforms in various applications.

  12. Direct esterification of olive-pomace oil using mesoporous silica supported sulfonic acids

    F. Alrouh

    2017-02-01

    Full Text Available Mesoporous silica MCM-41 and SBA-15 containing propyl sulfonic acid groups were synthesized according to the literature and were characterized by X-ray diffraction, N2 adsorption and the H+ exchange capacities of the sulfonic acid groups were titrated. The esterification reaction of glycerol with olive-pomace oil has been carried out by using prepared functionalized mesoporous silica (MCM-41 and SBA-15 as catalysts. It has been monitored by GC two fatty acids (palmitic and oleic acids as reactants in olive-pomace oil and their related monoacylglycerols (Glycerol monopalmitate GMP and monooleate GMO as reaction product. The catalytic activities of the functionalized mesoporous silica were compared with commercial catalysts, these included homogeneous catalysts (p-toluenesulfonic acid and heterogeneous catalysts (Amberlyst-15. The total yield of monoacylglycerols (GMO + GMP was nearly 40%. Remarkably, we found that MCM-41-SO3H was recycled at least 3 times without any loss of activity.

  13. Polymeric carbon nitride/mesoporous silica composites as catalyst support for Au and Pt nanoparticles.

    Xiao, Ping; Zhao, Yanxi; Wang, Tao; Zhan, Yingying; Wang, Huihu; Li, Jinlin; Thomas, Arne; Zhu, Junjiang

    2014-03-03

    Small and homogeneously dispersed Au and Pt nanoparticles (NPs) were prepared on polymeric carbon nitride (CNx )/mesoporous silica (SBA-15) composites, which were synthesized by thermal polycondensation of dicyandiamide-impregnated preformed SBA-15. By changing the condensation temperature, the degree of condensation and the loading of CNx can be controlled to give adjustable particle sizes of the Pt and Au NPs subsequently formed on the composites. In contrast to the pure SBA-15 support, coating of SBA-15 with polymeric CNx resulted in much smaller and better-dispersed metal NPs. Furthermore, under catalytic conditions the CNx coating helps to stabilize the metal NPs. However, metal NPs on CNx /SBA-15 can show very different catalytic behaviors in, for example, the CO oxidation reaction. Whereas the Pt NPs already show full CO conversion at 160 °C, the catalytic activity of Au NPs seems to be inhibited by the CNx support. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Catalytic Activity of Cobalt Grafted on Ordered Mesoporous Silica Materials in N2O Decomposition and CO Oxidation.

    Kuboňová, L.; Peikertová, P.; Mamulová Kutláková, K.; Jirátová, Květa; Słowik, G.; Obalová, L.; Cool, P.

    2017-01-01

    Roč. 437, AUG 2017 (2017), s. 57-72 ISSN 2468-8231 R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : mesoporous ordered silica * cobalt * N2O decomposition Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering

  15. The Multi-Template Molecularly Imprinted Polymer Based on SBA-15 for Selective Separation and Determination of Panax notoginseng Saponins Simultaneously in Biological Samples

    Chenghong Sun

    2017-11-01

    Full Text Available The feasible, reliable and selective multi-template molecularly imprinted polymers (MT-MIPs based on SBA-15 (SBA-15@MT-MIPs for the selective separation and determination of the trace level of ginsenoside Rb1 (Rb1, ginsenoside Rg1 (Rg1 and notoginsenoside R1 (R1 simultaneously from biological samples were developed. The polymers were constructed by SBA-15 as support, Rb1, Rg1, R1 as multi-template, acrylamide (AM as functional monomer and ethylene glycol dimethacrylate (EGDMA as cross-linker. The new synthetic SBA-15@MT-MIPs were satisfactorily applied to solid-phase extraction (SPE coupled with high performance liquid chromatography (HPLC for the separation and determination of trace Rb1, Rg1 and R1 in plasma samples. Under the optimized conditions, the limits of detection (LODs and quantitation (LOQs of the proposed method for Rb1, Rg1 and R1 were in the range of 0.63–0.75 ng·mL−1 and 2.1–2.5 ng·mL−1, respectively. The recoveries of R1, Rb1 and Rg1 were obtained between 93.4% and 104.3% with relative standard deviations (RSDs in the range of 3.3–4.2%. All results show that the obtained SBA-15@MT-MIPs could be a promising prospect for the practical application in the selective separation and enrichment of trace Panax notoginseng saponins (PNS in the biological samples.

  16. Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

    Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

    2015-01-15

    Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.

  17. Structural and surface properties of highly ordered mesoporous magnesium-aluminium composite oxides derived from facile synthesis

    Pan, Dahai, E-mail: pandahai@foxmail.com; Dong, Zhaoyang; He, Min; Chen, Wei; Chen, Shuwei; Yu, Feng; Fan, Binbin; Cui, Xingyu; Li, Ruifeng, E-mail: rfli@tyut.edu.cn

    2017-01-15

    Highly ordered mesoporous magnesium-aluminium composite oxides (denoted as OMMA-x) with a variety of n{sub Al}/n{sub Mg} ratios have been successfully synthesized via a facile strategy, and a salt effect was proposed to explain the formation mechanism. The incorporation of Mg can significantly improve the structural and surface properties of ordered mesoporous alumina (OMA) material. The resultant OMMA-x exhibited a much more ordered 2-D hexagonal mesostructure, a narrower pore size distribution, a higher specific surface area and pore volume, and a stronger basicity than those of OMA. More importantly, the highly homogeneous incorporation of Mg at the atomic level and the formation of framework Mg−O−Al bonds could effectively suppress the formation of crystalline alumina during the calcination process. As a result, OMMA-x demonstrated a superior thermal stability. For example, the ordered mesostructure of OMMA-8 could be well maintained with a high surface area of 182 m{sup 2}/g even after thermal treatment at 1000 °C. - Graphical abstract: A schematic procedure to illustrate the preparation of highly ordered mesoporous Mg-Al composite oxides (OMMA-x) with highly homogeneously dispersed Mg species and enhanced structural stability. - Highlights: • Mesoporous Mg-Al composite oxides with excellent structural and surface properties. • A highly homogeneous incorporation of Mg into the mesoporous framework of alumina. • A superior structural stability up to 1000 °C coupled with a large surface area. • A salt effect from the addition of Mg(NO{sub 3}){sub 2}·6H{sub 2}O to explain the formation mechanism.

  18. 有序介孔炭的研究进展%Research development of ordered mesoporous carbon

    刘攀博; 焦剑; 黄英

    2012-01-01

    综述了以硬模板法、软模板法和混合模板法合成有序介孔炭的研究进展.对上述三种制备有序介孔炭的方法和原理进行了的简单介绍,指出各种方法在制备有序介孔炭时存在的长处与不足.讨论了采用不同模板剂和炭前躯体对所制备的有序介孔炭的结构、孔径大小、孔径分布及物理化学性能的影响,指出在制备有序介孔炭的过程中,主要问题是选择一种与模板剂可产生较强相互作用的炭前躯体并控制炭前躯体与模板之间的摩尔比率.最后对有序介孔炭的潜在应用和发展方向进行了展望.%The research development of ordered mesoporous carbon synthesized by hard template method, soft template method and mixed template method was summarized. The above three synthesis methods and principles of ordered mesoporous carbon were introdued briefly, and the advantages and disadvantages of each method were also pointed out. Structure, pore size, pore size distribution and physical and chemical properties of ordered mesoporous carbon synthesized by different template types and carbon precursors were discussed. The main problems in the preparation of ordered mesoporous carbon are choosing a suitable carbon precursor which can strongly interact with template and controlling the molar ratio between the carbon precursor and template. Finally, the potential applications and developing direction of ordered mesoporous carbon were prospected.

  19. Ordered nanoporous silica as carriers for improved delivery of water insoluble drugs: a comparative study between three dimensional and two dimensional macroporous silica

    Wang Y

    2013-10-01

    Full Text Available Ying Wang, Qinfu Zhao, Yanchen Hu, Lizhang Sun, Ling Bai, Tongying Jiang, Siling WangDepartment of Pharmaceutics, Shenyang Pharmaceutical University, Liaoning Province, People’s Republic of ChinaAbstract: The goal of the present study was to compare the drug release properties and stability of the nanoporous silica with different pore architectures as a matrix for improved delivery of poorly soluble drugs. For this purpose, three dimensional ordered macroporous (3DOM silica with 3D continuous and interconnected macropores of different sizes (200 nm and 500 nm and classic mesoporous silica (ie, Mobil Composition of Matter [MCM]-41 and Santa Barbara Amorphous [SBA]-15 with well-ordered two dimensional (2D cylindrical mesopores were successfully fabricated and then loaded with the model drug indomethacin (IMC via the solvent deposition method. Scanning electron microscopy (SEM, N2 adsorption, differential scanning calorimetry (DSC, and X-ray diffraction (XRD were applied to systematically characterize all IMC-loaded nanoporous silica formulations, evidencing the successful inclusion of IMC into nanopores, the reduced crystallinity, and finally accelerated dissolution of IMC. It was worth mentioning that, in comparison to 2D mesoporous silica, 3DOM silica displayed a more rapid release profile, which may be ascribed to the 3D interconnected pore networks and the highly accessible surface areas. The results obtained from the stability test indicated that the amorphous state of IMC entrapped in the 2D mesoporous silica (SBA-15 and MCM-41 has a better physical stability than in that of 3DOM silica. Moreover, the dissolution rate and stability of IMC loaded in 3DOM silica was closely related to the pore size of macroporous silica. The colorimetric 3-(4,5-Dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and Cell Counting Kit (CCK-8 assays in combination with direct morphology observations demonstrated the good biocompatibility of nanoporous

  20. Modeling of boldine alkaloid adsorption onto pure and propyl-sulfonic acid-modified mesoporous silicas. A comparative study

    Geszke-Moritz, Małgorzata, E-mail: Malgorzata.Geszke-Moritz@amu.edu.pl [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Moritz, Michał, E-mail: michal.moritz@put.poznan.pl [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemistry and Technical Electrochemistry, Berdychowo 4, 60-965 Poznań (Poland)

    2016-12-01

    The present study deals with the adsorption of boldine onto pure and propyl-sulfonic acid-functionalized SBA-15, SBA-16 and mesocellular foam (MCF) materials. Siliceous adsorbents were characterized by nitrogen sorption analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy and thermogravimetric analysis. The equilibrium adsorption data were analyzed using the Langmuir, Freundlich, Redlich-Peterson, and Temkin isotherms. Moreover, the Dubinin-Radushkevich and Dubinin-Astakhov isotherm models based on the Polanyi adsorption potential were employed. The latter was calculated using two alternative formulas including solubility-normalized (S-model) and empirical C-model. In order to find the best-fit isotherm, both linear regression and nonlinear fitting analysis were carried out. The Dubinin-Astakhov (S-model) isotherm revealed the best fit to the experimental points for adsorption of boldine onto pure mesoporous materials using both linear and nonlinear fitting analysis. Meanwhile, the process of boldine sorption onto modified silicas was described the best by the Langmuir and Temkin isotherms using linear regression and nonlinear fitting analysis, respectively. The values of adsorption energy (below 8 kJ/mol) indicate the physical nature of boldine adsorption onto unmodified silicas whereas the ionic interactions seem to be the main force of alkaloid adsorption onto functionalized sorbents (energy of adsorption above 8 kJ/mol). - Graphical abstract: Modeling of boldine adsorption onto unmodified and propyl-sulfonic acid-modified mesoporous adsorbents. - Highlights: • The process of boldine adsorption onto SBA-15, SBA-16 and MCF silicas was examined. • Siliceous adsorbents were functionalized with propyl-sulfonic acid groups. • The equilibrium adsorption data were analyzed using several isotherm models. • Both linear regression and nonlinear fitting analysis were carried out.

  1. Silicon oxynitrides of KCC-1, SBA-15 and MCM-41 for CO 2 capture with excellent stability and regenerability

    Patil, Umesh; Fihri, Aziz; Emwas, Abdul-Hamid M.; Polshettiwar, Vivek

    2012-01-01

    ammonia gas, and they demonstrated excellent CO 2 capture capabilities. These materials overcome several limitations of conventional amine-grafted mesoporous silica. They offer good CO 2 capture capacity, faster adsorption-desorption kinetics, efficient

  2. Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

    Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François

    2015-06-08

    The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite

    Xuan Hoan Vu

    2015-10-01

    Full Text Available The catalytic cracking of triglyceride-rich biomass toward C2–C4 olefins was evaluated over a hierarchically textured nano-ZSM-5/SBA-15 analog composite (ZSC-24 under fluid catalytic cracking (FCC conditions. The experiments were performed on a fully automated Single-Receiver Short-Contact-Time Microactivity Test unit (SR-SCT-MAT, Grace Davison at 550 °C and different catalyst-to-oil mass ratios (0–1.2 g∙g−1. The ZSC-24 catalyst is very effective for transformation of triglycerides to valuable hydrocarbons, particularly lower olefins. The selectivity to C2–C4 olefins is remarkably high (>90% throughout the investigated catalyst-to-oil ratio range. The superior catalytic performance of the ZSC-24 catalyst can be attributed to the combination of its medium acid site amount and improved molecular transport provided by the bimodal pore system, which effectively suppresses the secondary reactions of primarily formed lower olefins.

  4. Mesoporous silica particles modified with graphitic carbon: interaction with human red blood cells and plasma proteins

    Martinez, Diego Stefani Teodoro; Franqui, Lidiane Silva; Bettini, Jefferson; Strauss, Mathias, E-mail: diego.martinez@lnnano.cnpem.br [Centro Nacional de Pesquisa em Energia e Materiais (CNPEM), Campinas, SP (Brazil); Damasceno, Joao Paulo Vita; Mazali, Italo Odone [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)

    2016-07-01

    Full text: In this work the interaction of the mesoporous silica particles (SBA-15, ∼700 nm) modified with graphitic carbon (SBA-15/C) on human red blood cells (hemolysis) and plasma proteins (protein corona formation) is studied. XPS and CHN analysis showed that the carbon content on the SBA-15/C samples varied from 2 to 10% and was tuned by the functionalization step. The formed carbon structures where associated to graphitic nanodomains coating the pores surface as verified by Raman spectroscopy and {sup 13}C NMR. Advanced TEM/EELS analysis showed that the carbon structures are distributed along the SBA-15 mesopores. SAXS and textural analyses were used to confirm that the porous structure of the silica support is kept after the modification procedure and to calculate the number of graphitic carbon stacked layers coating the mesopores. After incubation of SBA-15 with human red blood cells (RBCs), it was observed a dose-dependent hemolytic effect, probably, due to binding of the material silanol-rich surface to the phosphatidylcholine molecules from the RBC membrane. The graphitic carbon modifications have mitigated this effect, indicating that the graphitic carbon coating protected the silanol groups of the particle surface hindering the hemolysis. Considering the protein corona formation, selective biomolecular interaction of proteins was observed for the different materials using gel electrophoresis (SDS-PAGE) analysis. Besides, graphitic carbon modification decreased the amount of proteins on the corona. Together, the in vitro hemolysis and protein corona assays are promising biological models to understand the influence of silica surface functionalization on their bionano-interactions. Finally, our work contributes to the development of fundamental research on such nanomaterials chemistry in the emerging field of nanobioscience and nanotoxicology. (author)

  5. Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

    Farzin Nejad, N.; Shams, E.; Amini, M. K.

    2015-09-01

    In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption-desorption isotherm and transmission electron microscopy. Nitrogen adsorption-desorption measurement revealed the high surface area (810 m2 g-1), maxima pore size of 3.3 nm and large pore volume (1.01 cm3 g-1) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g-1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles.

  6. Electrochemistry and electrocatalysis of polyoxometalate-ordered mesoporous carbon modified electrode

    Zhou Ming; Guo Liping; Lin Fanyun; Liu Haixia

    2007-01-01

    In this work, we have developed a convenient and efficient method for the functionalization of ordered mesoporous carbon (OMC) using polyoxometalate H 6 P 2 Mo 18 O 62 .xH 2 O (P 2 Mo 18 ). By the method, glassy carbon (GC) electrode modified with P 2 Mo 18 which was immobilized on the channel surface of OMC was prepared and characterized for the first time. The large specific surface area and porous structure of the modified OMC particles result in high heteropolyacid loading, and the P 2 Mo 18 entrapped in this order matrix is stable. Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption-desorption isotherm and X-ray diffraction (XRD) were employed to give insight into the intermolecular interaction between OMC and P 2 Mo 18 . The electrochemical behavior of the modified electrode was studied in detail, including pH-dependence, stability and so on. The cyclic voltammetry (CV) and amperometry studies demonstrated that P 2 Mo 18 /OMC/GC electrode has high stability, fast response and good electrocatalytic activity for the reduction of nitrite, bromate, idonate, and hydrogen peroxide. The mechanism of catalysis on P 2 Mo 18 /OMC/GC electrode was discussed. Moreover, the development of our approach for OMC functionalization suggests the potential applications in catalysis, molecular electronics and sensors

  7. Equilibrium, kinetic and thermodynamic studies for adsorption of BTEX onto Ordered Mesoporous Carbon (OMC).

    Konggidinata, Mas Iwan; Chao, Bing; Lian, Qiyu; Subramaniam, Ramalingam; Zappi, Mark; Gang, Daniel Dianchen

    2017-08-15

    Chemical and petrochemical industries produce substantial amounts of wastewater everyday. This wastewater contains organic pollutants such as benzene, toluene, ethylbenzene and xylenes (BTEX) that are toxic to human and aquatic life. Ordered Mesoporous Carbon (OMC), the adsorbent that possesses the characteristics of an ideal adsorbent was investigated to understand its properties and suitability for BTEX removal. Adsorption isotherms, adsorption kinetics, the effects of initial BTEX concentrations and temperatures on the adsorption process were studied. The OMCs were characterized using surface area and pore size analyzer, transmission electron microscopy (TEM), elemental analysis, thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). The results suggested that the Langmuir Isotherm and Pseudo-Second-Order Models described the experimental data well. The thermodynamic parameters, Gibbs free energy (ΔG°), the enthalpy change (ΔH°) and the entropy change (ΔS°) of adsorption indicated that the adsorption processes were physical, endothermic, and spontaneous. In addition, OMC had 27% higher overall adsorption capacities compared to granular activated carbon (GAC). Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Chung, Po-Wen [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    The dissertation begins with Chapter 1, which is a general introduction of the fundamental synthesis of mesoporous silica materials, the selective functionlization of mesoporous silica materials, and the synthesis of nanostructured porous materials via nanocasting. In Chapter 2, the thermo-responsive polymer coated mesoporous silica nanoparticles (MSN) was synthesized via surface-initated polymerization and exhibited unique partition activities in a biphasic solution with the thermally induced change. In Chapter 3, the monodispersed spherical MSN with different mesoporous structure (MCM-48) was developed and employed as a template for the synthesis of mesoporous carbon nanoparticles (MCN) via nanocasting. MCN was demonstrated for the delivery of membrane impermeable chemical agents inside the cells. The cellular uptake efficiency and biocompabtibility of MCN with human cervical cancer cells were also investigated. In addition to the biocompabtibility of MCN, MCN was demonstrated to support Rh-Mn nanoparticles for catalytic reaction in Chapter 4. Owing to the unique mesoporosity, Rh-Mn nanoparticles can be well distributed inside the mesoporous structure and exhibited interesting catalytic performance on CO hydrogenation. In Chapter 5, the synthesis route of the aforementioned MCM-48 MSN was discussed and investigated in details and other metal oxide nanoparticles were also developed via nanocasting by using MCM-48 MSN as a template. At last, there is a general conclusion summarized in Chapter 6.

  9. Mesoporous silica as carrier of antioxidant for food packaging materials

    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.

  10. Synthesis of Ordered Mesoporous CuO/CeO2 Composite Frameworks as Anode Catalysts for Water Oxidation

    Vassiliki Markoulaki Ι

    2015-11-01

    Full Text Available Cerium-rich metal oxide materials have recently emerged as promising candidates for the photocatalytic oxygen evolution reaction (OER. In this article, we report the synthesis of ordered mesoporous CuO/CeO2 composite frameworks with different contents of copper(II oxide and demonstrate their activity for photocatalytic O2 production via UV-Vis light-driven oxidation of water. Mesoporous CuO/CeO2 materials have been successfully prepared by a nanocasting route, using mesoporous silica as a rigid template. X-ray diffraction, electron transmission microscopy and N2 porosimetry characterization of the as-prepared products reveal a mesoporous structure composed of parallel arranged nanorods, with a large surface area and a narrow pore size distribution. The molecular structure and optical properties of the composite materials were investigated with Raman and UV-Vis/NIR diffuse reflectance spectroscopy. Catalytic results indicated that incorporation of CuO clusters in the CeO2 lattice improved the photochemical properties. As a result, the CuO/CeO2 composite catalyst containing ~38 wt % CuO reaches a high O2 evolution rate of ~19.6 µmol·h−1 (or 392 µmol·h−1·g−1 with an apparent quantum efficiency of 17.6% at λ = 365 ± 10 nm. This OER activity compares favorably with that obtained from the non-porous CuO/CeO2 counterpart (~1.3 µmol·h−1 and pure mesoporous CeO2 (~1 µmol·h−1.

  11. Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics.

    Wang, Guang-Hui; Cao, Zhengwen; Gu, Dong; Pfänder, Norbert; Swertz, Ann-Christin; Spliethoff, Bernd; Bongard, Hans-Josef; Weidenthaler, Claudia; Schmidt, Wolfgang; Rinaldi, Roberto; Schüth, Ferdi

    2016-07-25

    Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Optimization of the Adsorption of Malachite Green on the NH2-SBA-15 Nano-adsorbent Using the Taguchi Method by Qualitek-4 Software An Isotherm, Kinetic, and Thermodynamic Study

    Arghavan Mirahsani

    2015-01-01

    Full Text Available SBA-15 nanoporous silica was prepared and functionalized with propylamine groups via post-synthesis grafting to develop efficient adsorbents of dyes in wastewater. The materials thus prepared were then characterized by XRD, N2 adsorption-desorption, and FTIR. Adsorption of a cationic dye, malachite green, on functionalized SBA-15 was investigated under various conditions of pH (5, 6, and 7, temperature (10, 20, and 30 °C, adsorbent dosage (0.1, 0.3, and 0.5 g/L, and dye concentration (50, 100, 150, 200, 250, 300 mg/L. Maximum equilibrium adsorption capacity to achieve maximum removal percentage (R%=100% in optimum conditions (dye concentration=100 mg/L, pH=7, adsorbent dosage= 0.3 g/L was estimated at 333 mg/g. The Taguchi method was used to optimize the adsorption performances of the materials , and then the isotherm, kinetic, and thermodynamic properties were analyzed under the optimum conditions. The results showed that the overall process was fast and its kinetics was well-fitted by pseudo-second-order kinetic model. The experimental data agreed well with Freundlich model. Therefore, the maximum amount of multilayer dye adsorbed was estimated as 500 mg/g. Based on the results obtained, this process may be regarded as an endothermic one with a negative ∆G, which shows the process is also spontaneous. Finally, the results indicate that the silica‐based nanoporous organic–inorganic hybrid material can be a promising sorbent for the removal of malachite green from aquatic solutions

  13. Alizarin red S functionalized mesoporous silica modified glassy carbon electrode for electrochemical determination of anthracene

    Liu, Shan; Wei, Maochao; Zheng, Xiangli; Xu, Shuai; Xia, Fangquan; Zhou, Changli

    2015-01-01

    Highlights: • Alizarin red S-SBA15 composite was prepared and characterized. • A novel sensing platform was constructed for anthracene determination. • The proposed sensor exhibited high sensitivity and low detection limit for detecting anthracene. • This method can be applied to the practical detection of anthracene in waste water. - Abstract: In the paper, a novel and sensitive electrochemical sensor based on modification of electroactive alizarin red S functionalized mesoporous silica material SBA15 onto glassy carbon electrode (ARS-SBA15/GCE) was developed. Alizarin red S, called electrochemical probe that can selectively recognize polycyclic aromatic hydrocarbons (PAHs), as tools for the detection of tricyclic aromatic hydrocarbon anthracene. The morphology and interface property of ARS modified SBA15 (ARS-SBA15) were examined by transmission electron microscopy (TEM) and fourier transform infrared spectroscopy (FTIR). Taking advantage of the π-π stacking force between alizarin red S and anthracene, the ARS-SBA15/GCE sensor could detect anthracene quantitatively in a wide range of 1.0 pM–10.0 nM and a low detection limit of 0.5 pM (S/N = 3). Other PAHs, such as naphthalene, phenanthrene, pyrene, and benzo[a]pyrene show little interference on the detection. Consequently, a simple and sensitive electrochemical method was proposed for the determination of anthracene, which can be used to determine anthracene in waste water samples. The electrochemical method provides a general tool that complements the commonly used spectroscopic methods and immune method for the detection of PAHs

  14. Synthesis and characterization of mesoporous materials for CO_2 capture: influence of nickel oxide

    Nascimento, Alexsandra Rodrigues do

    2014-01-01

    Several materials are currently under study for the CO_2 capture process, like the metal oxides and mixed metal oxides, zeolites, carbonaceous materials, metal-organic frameworks (MOF's) organosilica and modified silica surfaces. In this work, evaluated the adsorption capacity of CO_2 in mesoporous materials of different structures, such as MCM-48 and SBA-15 without impregnating and impregnated with nickel in the proportions 5 %, 10 % and 20 % (m/m), known as 5Ni-MCM-48, 10Ni-MCM-48, 20Ni-MCM-48 and 5Ni-SBA-15, 10Ni-SBA-15, 20Ni-SBA-15. The materials were characterized by means of X-ray diffraction (XRD), thermal analysis (TG and DTG), Fourier transform infrared spectroscopy (FT-IR), N_2 adsorption and desorption (BET) and scanning electron microscopy (SEM) with EDS. The adsorption process was performed varying the pressure of 100 - 4000 kPa and keeping the temperature constant and equal to 298 K. At a pressure of 100 kPa, higher concentrations of adsorption occurred for the materials 5Ni-MCM-48 (0.795 mmol g"-"1) and SBA-15 (0.914 mmol g"-"1) is not impregnated, and at a pressure of 4000 kPa for MCM-48 materials (14.89 mmol g"-"1) and SBA-15 (9.97 mmol g"-"1) not impregnated. The results showed that the adsorption capacity varies positively with the specific area, however, has a direct dependency on the type and geometry of the porous structure of channels. The data were fitted using the Langmuir and Freundlich models and were evaluated thermodynamic parameters Gibbs free energy and entropy of the adsorption system. (author)

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

    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.

  16. Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

    Lee, In-Gu; Lee, Heejin; Kang, Bo Sung; Kim, Young-Min; Kim, Sang Chai; Jung, Sang-Chul; Ko, Chang Hyun; Park, Young-Kwon

    2018-02-01

    The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

  17. Controlling morphology, mesoporosity, crystallinity, and photocatalytic activity of ordered mesoporous TiO{sub 2} films prepared at low temperature

    Elgh, Björn; Yuan, Ning; Palmqvist, Anders E. C. [Applied Surface Chemistry, Department of Chemical and Biological Engineering, Chalmers University of Technology, SE 412 96 Göteborg (Sweden); Cho, Hae Sung; Terasaki, Osamu [Graduate School of EEWS (WCU), KAIST, Daejeon 305-701 (Korea, Republic of); Magerl, David; Philipp, Martine; Müller-Buschbaum, Peter [Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, 85748 Garching (Germany); Roth, Stephan V. [DESY, Notkestrasse 85, 22603 Hamburg (Germany); Yoon, Kyung Byung [Department of Chemistry, Sogang University, Seoul 121-742 (Korea, Republic of)

    2014-11-01

    Partly ordered mesoporous titania films with anatase crystallites incorporated into the pore walls were prepared at low temperature by spin-coating a microemulsion-based reaction solution. The effect of relative humidity employed during aging of the prepared films was studied using SEM, TEM, and grazing incidence small angle X-ray scattering to evaluate the mesoscopic order, porosity, and crystallinity of the films. The study shows unambiguously that crystal growth occurs mainly during storage of the films and proceeds at room temperature largely depending on relative humidity. Porosity, pore size, mesoscopic order, crystallinity, and photocatalytic activity of the films increased with relative humidity up to an optimum around 75%.

  18. New inorganic-organic hybrid materials based on SBA-15 molecular sieves involved in the quinolines synthesis

    López-Sanz, J.; Pérez-Mayoral, E.; Soriano, E.; Sturm, M.; Martín-Aranda, R. M.; López-Peinado, A. J.; Čejka, Jiří

    2012-01-01

    Roč. 187, č. 1 (2012), s. 97-103 ISSN 0920-5861 R&D Projects: GA AV ČR KAN100400701 Institutional support: RVO:61388955 Keywords : mesoporous molecular sieves * heterogeneous catalysis * quinolines Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.980, year: 2012

  19. Systematically controlled pore system of ordered mesoporous carbons using phosphoric acid as the in situ generated catalysts for carbonization and activation

    Jin, Xing; Lee, Chang Hyun; Kim, Jin Hoe; You, Dae Jong; Shon, Jeong Kuk; Kim, Ji Man [Dept. of Chemistry, Sungkyunkwan University, Suwon (Korea, Republic of); Pak, Chan Ho [Fuel Cell Group, Corporate R and D Center, Samsung SDI Co. Ltd., Yongin (Korea, Republic of)

    2015-08-15

    We report on a facile synthesis of the ordered mesoporous carbon (OMC) materials with systematically controlled microporosity and mesoporosity simultaneously through the nano-replication route using phosphoric acid as the acid catalyst and activation agent. The use of phosphoric acid affects the pore structures of OMC materials, such as the formation of numerous micropores by activation of the carbon framework and the enlargement of mesopores by spontaneous phase separation during the carbonization. The mesopore sizes, surface areas, total pore volumes, and micropore volumes of the OMC materials are highly dependent on the phosphoric acid content and can be systematically controlled in the range 3.7–7.5 nm, 1027–2782 m{sup 2} g{sup -1}, 1.12–3.53 cm{sup 3} g{sup -1} and 0.34–0.95 cm{sup 3} g{sup -1}, respectively. OMC materials with systematically controlled pore structures were successfully synthesized using phosphoric acid as the carbonization catalyst and mesoporous silica materials with cubic Ia3d and 2-D hexagonal mesostructures as the templates. The phosphoric acid in the synthesis of ordered mesoporous carbon materials acts as the chemical activating agent for micropore generation of the carbon framework and pore-expanding agent for controlling of mesopore size, in addition to functioning as the acid catalyst. The present synthesis pathway is very useful for preparing OMC materials with tunable mesopore sizes and well-developed microporosities at the same time.

  20. Microwave-induced synthesis of highly dispersed gold nanoparticles within the pore channels of mesoporous silica

    Gu Jinlou; Fan Wei; Shimojima, Atsushi; Okubo, Tatsuya

    2008-01-01

    Highly dispersed gold nanoparticles have been incorporated into the pore channels of SBA-15 mesoporous silica through a newly developed strategy assisted by microwave radiation (MR). The sizes of gold are effectively controlled attributed to the rapid and homogeneous nucleation, simultaneous propagation and termination of gold precursor by MR. Diol moieties with high dielectric and dielectric loss constants, and hence a high microwave activation, were firstly introduced to the pore channels of SBA-15 by a simple addition reaction between amino group and glycidiol and subsequently served as the reduction centers for gold nanoparticles. Extraction of the entrapped gold from the nanocomposite resulted in milligram quantities of gold nanoparticles with low dispersity. The successful assembly process of diol groups and formation of gold nanoparticles were monitored and tracked by solid-state NMR and UV-vis measurements. Characterization by small angle X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the incorporation of gold nanoparticles would not breakup the structural integrity and long-range periodicity of SBA-15. The gold nanoparticles had a narrow size distribution with diameters in the size range of 5-10 nm through TEM observation. The average particles size is 7.9 nm via calculation by the Scherrer formula and TEM measurements. Nitrogen adsorption and desorption isotherms gave further evidence that the employed method was efficient and gold nanoparticles were successfully incorporated into the pore channels of SBA-15. - Graphical abstract: A facile and novel strategy has been developed to incorporate gold nanoparticles into the pore channels of mesoporous SBA-15 assisted by microwave radiation (MR) with mild reaction condition and rapid reaction speed. Due to the rapid and homogeneous nucleation, simultaneous propagation and termination by MR, the size of gold nanoparticles are effectively controlled

  1. Amine-modified ordered mesoporous silica: Effect of pore size on carbon dioxide capture

    Zeleňák, V.; Badaničová, M.; Halamová, D.; Čejka, Jiří; Zukal, Arnošt; Murafa, Nataliya; Goerigk, G.

    2008-01-01

    Roč. 144, č. 2 (2008), s. 336-342 ISSN 1385-8947 R&D Projects: GA ČR GA203/08/0604 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : mesoporous silica * hexagonal * amine * carbon dioxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.813, year: 2008

  2. Highly-ordered mesoporous titania thin films prepared via surfactant assembly on conductive indium-tin-oxide/glass substrate and its optical properties

    Uchida, Hiroshi; Patel, Mehul N.; May, R. Alan; Gupta, Gaurav; Stevenson, Keith J.; Johnston, Keith P.

    2010-01-01

    Highly ordered mesoporous titanium dioxide (titania, TiO 2 ) thin films on indium-tin-oxide (ITO) coated glass were prepared via a Pluronic (P123) block copolymer template and a hydrophilic TiO 2 buffer layer. The contraction of the 3D hexagonal array of P123 micelles upon calcination merges the titania domains on the TiO 2 buffer layer to form mesoporous films with a mesochannel diameter of approximately 10 nm and a pore-to-pore distance of 10 nm. The mesoporous titania films on TiO 2 -buffered ITO/glass featured an inverse mesospace with a hexagonally-ordered structure, whereas the films formed without a TiO 2 buffer layer had a disordered microstructure with submicron cracks because of non-uniform water condensation on the hydrophobic ITO/glass surface. The density of the mesoporous film was 83% that of a bulk TiO 2 film. The optical band gap of the mesoporous titania thin film was approximately 3.4 eV, larger than that for nonporous anatase TiO 2 (∼ 3.2 eV), suggesting that the nanoscopic grain size leads to an increase in the band gap due to weak quantum confinement effects. The ability to form highly-ordered mesoporous titania films on electrically conductive and transparent substrates offers the potential for facile fabrication of high surface area semiconductive films with small diffusion lengths for optoelectronics applications.

  3. Template-mediated, Hierarchical Engineering of Ordered Mesoporous Films and Powders

    Tian, Zheng

    Hierarchical control over pore size, pore topology, and meso/mictrostructure as well as material morphology (e.g., powders, monoliths, thin films) is crucial for meeting diverse materials needs among applications spanning next generation catalysts, sensors, batteries, sorbents, etc. The overarching goal of this thesis is to establish fundamental mechanistic insight enabling new strategies for realizing such hierarchical textural control for carbon materials that is not currently achievable with sacrificial pore formation by 'one-pot' surfactant-based 'soft'-templating or multi-step inorganic 'hard-templating. While 'hard'-templating is often tacitly discounted based upon its perceived complexity, it offers potential for overcoming key 'soft'-templating challenges, including bolstering pore stability, accommodating a more versatile palette of replica precursors, realizing ordered/spanning porosity in the case of porous thin films, simplifying formation of bi-continuous pore topologies, and inducing microstructure control within porous replica materials. In this thesis, we establish strategies for hard-templating of hierarchically porous and structured carbon powders and tunable thin films by both multi-step hard-templating and a new 'one-pot' template-replica precursor co-assembly process. We first develop a nominal hard-templating technique to successfully prepare three-dimensionally ordered mesoporous (3DOm) and 3DOm-supported microporous carbon thin films by exploiting our ability to synthesize and assemble size-tunable silica nanoparticles into scalable, colloidal crystalline thin film templates of tunable mono- to multi-layer thickness. This robust thin film template accommodates liquid and/or vapor-phase infiltration, polymerization, and pyrolysis of various carbon sources without pore contraction and/or collapse upon template sacrifice. The result is robust, flexible 3DOm or 3DOm-supported ultra-thin microporous films that can be transferred by stamp

  4. Magnetic solid-phase extraction based on mesoporous silica-coated magnetic nanoparticles for analysis of oral antidiabetic drugs in human plasma

    Souza, Karynne Cristina de; Andrade, Gracielle Ferreira [Centro de Desenvolvimento da Tecnologia Nuclear, CDTN/CNEN, Rua Professor Mário Werneck, s/n. Campus Universitário, Belo Horizonte, MG CEP 30.123-970 (Brazil); Vasconcelos, Ingrid; Oliveira Viana, Iara Maíra de; Fernandes, Christian [Departamento de Produtos Farmacêuticos, Faculdade de Farmácia, Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil); Martins Barros de Sousa, Edésia, E-mail: sousaem@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear, CDTN/CNEN, Rua Professor Mário Werneck, s/n. Campus Universitário, Belo Horizonte, MG CEP 30.123-970 (Brazil)

    2014-07-01

    In the present work, magnetic nanoparticles embedded into mesoporous silica were prepared in two steps: first, magnetite was synthesized by oxidation–precipitation method, and next, the magnetic nanoparticles were coated with mesoporous silica by using nonionic block copolymer surfactants as structure-directing agents. The mesoporous SiO{sub 2}-coated Fe{sub 3}O{sub 4} samples were functionalized using octadecyltrimethoxysilane as silanizing agent. The pure and functionalized silica nanoparticles were physicochemically and morphologically characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N{sub 2} adsorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The resultant magnetic silica nanoparticles were applied as sorbents for magnetic solid-phase extraction (MSPE) of oral antidiabetic drugs in human plasma. Our results revealed that the magnetite nanoparticles were completely coated by well-ordered mesoporous silica with free pores and stable pore walls, and that the structural and magnetic properties of the Fe{sub 3}O{sub 4} nanoparticles were preserved in the applied synthesis route. Indeed, the sorbent material was capable of extracting the antidiabetic drugs from human plasma, being useful for the sample preparation in biological matrices. - Highlights: • SBA-15/Fe{sub 3}O{sub 4} was synthesized and functionalized with octadecyltrimethoxysilane. • Magnetite nanoparticles were completely coated by well-ordered mesoporous silica. • The samples were used as sorbent for magnetic solid-phase extraction (MSPE). • The sorbent material was capable of extracting drugs from human plasma. • The extraction ability makes the material a candidate to be employed as MSPE.

  5. Thiols make for better catalysts: Au nanoparticles supported on functional SBA-15 for catalysis of Ullmann-type homocouplings

    Chen, Tianyou

    2017-09-21

    A strategy for arraying small gold nanoparticles on a mesoporous support modified with single-component or mixed self-assembled monolayers is described. The use of mixed surface modifiers allows easy access to a range of surface chemistries and modalities of interaction between nanoparticles and supports. A combination of thiol groups and linear semifluorinated chains effectively stabilized the nanoparticles against aggregation, while preserving their catalytic activity. The thiol-fluorous-supported catalyst was found active in Ullmann-type homocoupling of aryl halides and showed exceptional selectivity in this reaction.

  6. Thiols make for better catalysts: Au nanoparticles supported on functional SBA-15 for catalysis of Ullmann-type homocouplings

    Chen, Tianyou; Chen, Batian; Bukhriakov, Konstantin; Rodionov, Valentin

    2017-01-01

    A strategy for arraying small gold nanoparticles on a mesoporous support modified with single-component or mixed self-assembled monolayers is described. The use of mixed surface modifiers allows easy access to a range of surface chemistries and modalities of interaction between nanoparticles and supports. A combination of thiol groups and linear semifluorinated chains effectively stabilized the nanoparticles against aggregation, while preserving their catalytic activity. The thiol-fluorous-supported catalyst was found active in Ullmann-type homocoupling of aryl halides and showed exceptional selectivity in this reaction.

  7. Hydrophilic and mesoporous SiO{sub 2}-TiO{sub 2}-SO{sub 3}H system for fuel cell membrane applications

    Hong, Lan-Young [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, 220 Kung-dong, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Oh, Song-Yul [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Matsuda, Atsunori, E-mail: matsuda@ee.tut.ac.j [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Lee, Chang-Soo [Department of Chemical Engineering, Chungnam National University, 220 Kung-dong, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Kim, Dong-Pyo, E-mail: dpkim@cnu.ac.k [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, 220 Kung-dong, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Graduate School of Analytical Science and Technology, Chungnam National University, 220 Kung-dong, Yuseong-gu, Daejeon 305-764 (Korea, Republic of)

    2011-03-30

    Graphical abstract: The composite films containing SiO{sub 2}-TiO{sub 2}-SO{sub 3}H resin additives, with strong water retention capabilities, showed superior proton conductivity, even at 120 {sup o}C and 25% RH, as well as a slightly improved current density at 30% RH and 70 {sup o}C, when compared to costly Nafion film. Display Omitted Research highlights: The hydrophilic and mesoporous SiO{sub 2}-TiO{sub 2}-SO{sub 3}H resins have a potential to be used as alternative membrane source materials in PEFCs. The sulfonation for hydrophilicity is conducted via simple chelating chemistry between catecholic groups and surface Ti ions. The proton conductivity of SiO{sub 2}-TiO{sub 2}-SO{sub 3}H composite films is superior to the commercial Nafion film. - Abstract: Hydrophilic and mesoporous sulfonated SiO{sub 2}-TiO{sub 2}-SO{sub 3}H systems as new additives for fuel cell electrolyte membranes are directly synthesized by the binary sol-gel reaction of TEOS-TiCl{sub 4} and consecutive sulfonation with a hydrophilic generator, dihydroxy-m-benzenedisulfonic acid disodium salt. The sulfonation approach makes use of the simple chelating chemistry between the catecholic groups (dihydroxy benzene) and surface Ti ions of the inorganic ordered mesoporous SBA-15 structure. The system is successfully employed in fuel cell membrane applications with a composite Nafion membrane mixed with a mesoporous hydrophilic resin additive, and reveals an obvious enhancement of the proton conductivity at low humidity and elevated temperatures. This improvement was attributed to the excellent water retention capability of the hydrophilic mesoporous resin.

  8. Space-confined preparation of high surface area tungsten oxide and tungsten nitride inside the pores of mesoporous silica SBA-15

    Meyer, Simon; Beyer, Hans; Köhler, Klaus

    2015-01-01

    For the direct preparation of high surface area nitride materials, a lack of suitable precursors exists. Indirect preparation by gas phase nitridation (e.g. by ammonia) requires high temperatures and often results in sintering. The present work demonstrates that the space-confined preparation of ...

  9. Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

    Basset, Jean-Marie; Hamzaoui, Bilel; Bendjeriou-Sedjerari, Anissa; Pump, Eva; Abou-Hamad, Edy; Sougrat, Rachid; Gurinov, Andrei; Huang, Kuo-Wei; Gajan, David; Lesage, Anne; Emsley, Lyndon

    2016-01-01

    by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear

  10. Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

    Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

    2017-07-12

    The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N 2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO 2 -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO 2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO 2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO 2 adsorption indicated the stronger interactions between the surfaces and CO 2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO 2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO 2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

  11. Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas.

    Liu, Ruili; Shi, Yifeng; Wan, Ying; Meng, Yan; Zhang, Fuqiang; Gu, Dong; Chen, Zhenxia; Tu, Bo; Zhao, Dongyuan

    2006-09-06

    Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.

  12. Crosslinked Enzyme Aggregates in Hierarchically-Ordered Mesoporous Silica: A Simple and Effective Method for Enzyme Stabilization

    Kim, Moon Il; Kim, Jungbae; Lee, Jinwoo; Jia, Hongfei; Na, Hyon Bin; Youn, Jongkyu; Kwak, Ja Hun; Dohnalkova, Alice; Grate, Jay W.; Wang, Ping; Hyeon, Taeghwan; Park, Hyun-Gyu; Chang, Ho Nam

    2007-02-01

    alpha-chymotrypsin (CT) and lipase (LP) were immobilized in hierarchically-ordered mesocellular mesoporous silica (HMMS) in a simple but effective way for the enzyme stabilization, which was achieved by the enzyme adsorption followed by glutaraldehyde (GA) crosslinking. This resulted in the formation of nanometer scale crosslinked enzyme aggregates (CLEAs) entrapped in the mesocellular pores of HMMS (37 nm), which did not leach out of HMMS through narrow mesoporous channels (13 nm). CLEA of alpha-chymotrypsin (CLEA-CT) in HMMS showed a high enzyme loading capacity and significantly increased enzyme stability. No activity decrease of CLEA-CT was observed for two weeks under even rigorously shaking condition, while adsorbed CT in HMMS and free CT showed a rapid inactivation due to the enzyme leaching and presumably autolysis, respectively. With the CLEA-CT in HMMS, however, there was no tryptic digestion observed suggesting that the CLEA-CT is not susceptible to autolysis. Moreover, CLEA of lipase (CLEA-LP) in HMMS retained 30% specific activity of free lipase with greatly enhanced stability. This work demonstrates that HMMS can be efficiently employed as host materials for enzyme immobilization leading to highly enhanced stability of the immobilized enzymes with high enzyme loading and activity.

  13. Nitrogen Doped Ordered Mesoporous Carbon as Support of PtRu Nanoparticles for Methanol Electro-Oxidation

    David Sebastián

    2018-04-01

    Full Text Available The low oxidation kinetics of alcohols and the need for expensive platinum group metals are still some of the main drawbacks for the commercialization of energy efficient direct alcohol fuel cells. In this work, we investigate the influence of nitrogen doping of ordered mesoporous carbon (CMK as support on the electrochemical activity of PtRu nanoparticles. Nitrogen doping procedures involve the utilization of pyrrole as both nitrogen and carbon precursor by means of a templating method using mesoporous silica. This method allows obtaining carbon supports with up to 14 wt. % nitrogen, with an effective introduction of pyridinic, pyrrolic and quaternary nitrogen. PtRu nanoparticles were deposited by sodium formate reduction method. The presence of nitrogen mainly influences the Pt:Ru atomic ratio at the near surface, passing from 50:50 on the bare (un-doped CMK to 70:30 for the N-doped CMK catalyst. The electroactivity towards the methanol oxidation reaction (MOR was evaluated in acid and alkaline electrolytes. The presence of nitrogen in the support favors a faster oxidation of methanol due to the enrichment of Pt at the near surface together with an increase of the intrinsic activity of PtRu nanoparticles.

  14. MoO2-ordered mesoporous carbon nanocomposite as an anode material for lithium-ion batteries.

    Zeng, Lingxing; Zheng, Cheng; Deng, Cuilin; Ding, Xiaokun; Wei, Mingdeng

    2013-03-01

    In the present work, the nanocomposite of MoO2-ordered mesoporous carbon (MoO2-OMC) was synthesized for the first time using a carbon thermal reduction route and the mesoporous carbon as the nanoreactor. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements. Furthermore, this nanocomposite was used as an anode material for Li-ion intercalation and exhibited large reversible capacity, high rate performance, and good cycling stability. For instance, a high reversible capacity of 689 mAh g(-1) can remain after 50 cycles at a current density of 50 mA g(-1). It is worth mentioning that the MoO2-OMC nanocomposite electrode can attain a high reversible capacity of 401 mAh g(-1) at a current density as high as 2 A g(-1). These results might be due to the intrinsic characteristics of nanocomposite, which offered a better accommodation of the strain and volume changes and a shorter path for Li-ion and electron transport, leading to the improved capacity and enhanced rate capability.

  15. Adsorption of CO₂, CH₄, and N₂ on ordered mesoporous carbon: approach for greenhouse gases capture and biogas upgrading.

    Yuan, Bin; Wu, Xiaofei; Chen, Yingxi; Huang, Jianhan; Luo, Hongmei; Deng, Shuguang

    2013-05-21

    Separation of CO₂ and N₂ from CH₄ is significantly important in natural gas upgrading, and capture/removal of CO₂, CH₄ from air (N₂) is essential to greenhouse gas emission control. Adsorption equilibrium and kinetics of CO₂, CH₄, and N₂ on an ordered mesoporous carbon (OMC) sample were systematically investigated to evaluate its capability in the above two applications. The OMC was synthesized and characterized with TEM, TGA, small-angle XRD, and nitrogen adsorption/desorption measurements. Pure component adsorption isotherms of CO₂, CH₄, and N₂ were measured at 278, 298, and 318 K and pressures up to 100 kPa, and correlated with the Langmuir model. These data were used to estimate the separation selectivities for CO₂/CH₄, CH₄/N₂, and CO₂/N₂ binary mixtures at different compositions and pressures according to the ideal adsorbed solution theory (IAST) model. At 278 K and 100 kPa, the predicted selectivities for equimolar CO₂/CH₄, CH4/N₂, and CO₂/N₂ are 3.4, 3.7, and 12.8, respectively; and the adsorption capacities for CH₄ and CO₂ are 1.3 and 3.0 mmol/g, respectively. This is the first report of a versatile mesoporous material that displays both high selectivities and large adsorption capacities for separating CO₂/CH₄, CH₄/N₂, and CO₂/N₂ mixtures.

  16. Aminopropyl-modified mesoporous molecular sieves as efficient adsorbents for removal of auxins

    Moritz, Michał; Geszke-Moritz, Małgorzata

    2015-01-01

    Graphical abstract: Adsorption of indole-3-acetic acid (IAA) on aminopropyl-modified mesoporous sieves. - Highlights: • Four types of mesoporous molecular sieves were used as sorbents for removal of auxins. • SBA-15, MCF, PHTS and SBA-16 were grafted with (3-aminopropyl)triethoxysilane. • The adsorption capacity of modified materials was higher as compared to pure silicas. • Surface modification and pore volume play important role in adsorption process. - Abstract: In the present study, mesoporous siliceous materials grafted with 3-aminopropyltriethoxysilane (APTES) were examined as sorbents for removal of chosen plant growth factors (auxins) such as 1-naphthaleneacetic acid (NAA), indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA). Four different types of mesoporous molecular sieves including SBA-15, PHTS, SBA-16 and MCF have been prepared via non-ionic surfactant-assisted soft templating method. Silica molecular sieves were thoroughly characterized by nitrogen adsorption–desorption analysis, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FT-IR). The maximum adsorption capacity (Q max ) for NAA, IAA and IBA was in the range from 51.0 to 140.8 mg/g and from 4.3 to 7.3 mg/g for aminopropyl-modified adsorbents and pure silicas, respectively. The best adsorption performance was observed for IAA entrapment using both APTES-functionalized SBA-15 and MCF matrices (Q max of 140.8 and 137.0 mg/g, respectively) which can be ascribed to their larger pore volumes and pore diameters. Moreover, these silicas were characterized by the highest adsorption efficiency exceeding 90% at low pollutant concentration. The experimental points for adsorption of plant growth factors onto aminopropyl-modified mesoporous molecular sieves fitted well to the Langmuir equation

  17. Aminopropyl-modified mesoporous molecular sieves as efficient adsorbents for removal of auxins

    Moritz, Michał, E-mail: michal.moritz@put.poznan.pl [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemistry and Technical Electrochemistry, Berdychowo 4, 60-965 Poznań (Poland); Geszke-Moritz, Małgorzata, E-mail: Malgorzata.Geszke-Moritz@amu.edu.pl [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)

    2015-03-15

    Graphical abstract: Adsorption of indole-3-acetic acid (IAA) on aminopropyl-modified mesoporous sieves. - Highlights: • Four types of mesoporous molecular sieves were used as sorbents for removal of auxins. • SBA-15, MCF, PHTS and SBA-16 were grafted with (3-aminopropyl)triethoxysilane. • The adsorption capacity of modified materials was higher as compared to pure silicas. • Surface modification and pore volume play important role in adsorption process. - Abstract: In the present study, mesoporous siliceous materials grafted with 3-aminopropyltriethoxysilane (APTES) were examined as sorbents for removal of chosen plant growth factors (auxins) such as 1-naphthaleneacetic acid (NAA), indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA). Four different types of mesoporous molecular sieves including SBA-15, PHTS, SBA-16 and MCF have been prepared via non-ionic surfactant-assisted soft templating method. Silica molecular sieves were thoroughly characterized by nitrogen adsorption–desorption analysis, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FT-IR). The maximum adsorption capacity (Q{sub max}) for NAA, IAA and IBA was in the range from 51.0 to 140.8 mg/g and from 4.3 to 7.3 mg/g for aminopropyl-modified adsorbents and pure silicas, respectively. The best adsorption performance was observed for IAA entrapment using both APTES-functionalized SBA-15 and MCF matrices (Q{sub max} of 140.8 and 137.0 mg/g, respectively) which can be ascribed to their larger pore volumes and pore diameters. Moreover, these silicas were characterized by the highest adsorption efficiency exceeding 90% at low pollutant concentration. The experimental points for adsorption of plant growth factors onto aminopropyl-modified mesoporous molecular sieves fitted well to the Langmuir equation.

  18. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  19. Control of ordered mesoporous titanium dioxide nanostructures formed using plasma enhanced glancing angle deposition

    Gibson, Des [Institute of Thin Films, Sensors & Imaging, Scottish Universities Physics Alliance, University of West of Scotland, Paisley, PA1 2BE (United Kingdom); Child, David, E-mail: david.child@uws.ac.uk [Institute of Thin Films, Sensors & Imaging, Scottish Universities Physics Alliance, University of West of Scotland, Paisley, PA1 2BE (United Kingdom); Song, Shigeng; Zhao, Chao [Institute of Thin Films, Sensors & Imaging, Scottish Universities Physics Alliance, University of West of Scotland, Paisley, PA1 2BE (United Kingdom); Alajiani, Yahya [Institute of Thin Films, Sensors & Imaging, Scottish Universities Physics Alliance, University of West of Scotland, Paisley, PA1 2BE (United Kingdom); Department of Physics, Faculty of Science, Jazan University, Jazan (Saudi Arabia); Waddell, Ewan [Thin Film Solutions Ltd, West of Scotland Science Park, Glasgow, G20 0TH (United Kingdom)

    2015-10-01

    Three dimensional nanostructures of mesoporous (pore diameter between 2-50 nm) nanocrystalline titania (TiO{sub 2}) were produced using glancing angle deposition combined with plasma ion assisted deposition, providing plasma enhanced glancing angle deposition eliminating the need for post-annealing to achieve film crystallinity. Electron beam evaporation was chosen to deposit nanostructures at various azimuthal angles, achieving designed variation in three dimensional nanostructure. A thermionic broad beam hollow cathode plasma source was used to enhance electron beam deposition, with ability to vary in real time ion fluxes and energies providing a means to modify and control TiO{sub 2} nanostructure real time with controlled density and porosity along and lateral to film growth direction. Plasma ion assisted deposition was carried out at room temperature using a hollow cathode plasma source, ensuring low heat loading to the substrate during deposition. Plasma enhanced glancing angle TiO{sub 2} structures were deposited onto borosilicate microscope slides and used to characterise the effects of glancing angle and plasma ion energy distribution function on the optical and nanostructural properties. Variation in TiO{sub 2} refractive index from 1.40 to 2.45 (@ 550 nm) using PEGLAD is demonstrated. Results and analysis of the influence of plasma enhanced glancing angle deposition on evaporant path and resultant glancing angle deviation from standard GLAD are described. Control of mesoporous morphology is described, providing a means of optimising light trapping features and film porosity, relevant to applications such as fabrication of dye sensitised solar cells. - Highlights: • Plasma assistance during glancing angle deposition enables control of morphology. • Ion energy variation during glancing angle deposition varies columnar angle • Column thickness of glancing angle deposition dependant on ion current density • Ion current density variation during

  20. The effect of Co-doping on the humidity sensing properties of ordered mesoporous TiO2

    Li, Zhong; Haidry, Azhar Ali; Gao, Bin; Wang, Tao; Yao, ZhengJun

    2017-08-01

    Monitoring of humidity is of utmost importance as it is essential part of almost every process in our life. Many commercial humidity sensors based on metal oxide semiconductors are available in the market, but there is still need to synthesize low-cost, fast and highly sensitive humidity sensors with no interference from background environment. The aim of this work was to fabricate the ordered mesoporous un-doped and Co-doped TiO2 (0.1-5 mol% Co) and to analyze its humidity sensing properties at room temperatures. The ordered mesoporous powders with high specific surface area (SSA) were prepared by multicomponent self-assembly procedure and then spray-coated onto the sensor substrates with interdigitated gold electrodes. The sensors exhibited excellent stability and reproducible resistance change under various relative humidity percentages (9-90% RH) with negligible effect of background environment. For instance, the response to 90% RH at room temperature was about five orders of magnitude (∼1.39 × 105) and the response time (Tres) was ∼24 s. The reaction/recovery times of the sensors were compared with commercial humidity sensor to show that the reaction times in this work are not given by the surface reaction of water vapor on the sensor surfaces, rather these are mainly influenced by the experimental setup. The sensor response increased up to 3 mol% Co-contents and then decreased for 5 mol% Co-contents. Based on the experimental results, the surface reaction of humidity is discussed related to specific surface area, average grain size and cobalt contents to understand the humidity sensing mechanism.

  1. Optimization of fuel cell membrane electrode assemblies for transition metal ion-chelating ordered mesoporous carbon cathode catalysts

    Johanna K. Dombrovskis

    2014-12-01

    Full Text Available Transition metal ion-chelating ordered mesoporous carbon (TM-OMC materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

  2. Fine-tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

    Han, Dandan; Yan, Yancui; Wei, Jishi; Wang, Biwei; Li, Tongtao; Guo, Guannan; Yang, Dong; Xie, Songhai; Dong, Angang

    2017-12-01

    Because of their unique physical properties, three-dimensional (3D) graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG). By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene by tailoring the hydrocarbon ligands attached to the nanocrystal surface. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with its 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites resulting from its ultrathin wall thickness and high surface area.

  3. Highly stable and active Ni-doped ordered mesoporous carbon catalyst on the steam reforming of ethanol application

    Josh Y.Z. Chiou

    2017-02-01

    Full Text Available A novel one-step direct synthesis of nickel embedded in an ordered mesoporous carbon catalyst (NiOMC is done in a basic medium of nonaqueous solution by a solvent evaporation-induced self-assembly process. The NiOMC sample is characterized by a variety of analytical and spectroscopy techniques, e.g., N2 adsorption/desorption isotherm measurement, X-ray diffraction (XRD, transmission electron microscopy (TEM and temperature-programed reduction (TPR. In this study, the NiOMC catalyst is found to exhibit superior catalytic activity for the steam reforming of ethanol (SRE, showing high hydrogen selectivity and durability. Ethanol can be completely converted at 350 °C over the NiOMC catalyst. Also, the durability of the NiOMC catalyst on the SRE reaction exceeds 100 h at 450 °C, with SH2 approaching 65% and SCO of less than 1%.

  4. Fine-Tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

    Dandan Han

    2017-12-01

    Full Text Available Because of their unique physical properties, three-dimensional (3D graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG. By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with their 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites arising from the thin wall thickness and high surface area.

  5. Ordered molecular arrays as templates: A new approach to synthesis of mesoporous materials

    Behrens, P.; Stucky, G.

    There has been a growing interest in the extension of the microporous molecular sieve synthesis and applications to mesoscopic dimensions. Typical areas for the application of mesoscopic zeolite-type structures are in separation (e.g., protein separation and selective adsorption of large organic molecules from waste waters) and catalysis (e.g., processing of tar sand and of the high distillates of crude oils to valuable low-boiling products). Another is in the supramolecular assembly of molecular array and polymers for electronic and optical applications. In a new concept in the synthesis of porous material the templating agent is no longer a single, solvated, organic molecule or metal ion, but rather a self-assembled molecular array. This template leads to mesoporous materials with adjustable pore sizes between 16 and greater than 100 Angstrom, covering well the mesophorous range of greatest interest. The periodic arrangement of pores is very regular, and the pore size distribution measured by absorption is nearly as sharp as that of conventional zeolites.

  6. Gyroidal mesoporous carbon materials and methods thereof

    Wiesner, Ulrich B.; Werner, Joerg G.

    2017-07-25

    The present invention relates to, inter alia, gyroidal mesoporous carbon materials and methods of use and manufacture thereof. In one embodiment, the present invention relates to a mesoporous carbon composition comprising a gyroidal mesoporous carbon having an ordered gyroidal structure and mesopores having a pore size of greater than 2 nanometers (nm) in diameter, and more particularly greater than 11 nm in diameter.

  7. Amine-modified ordered mesoporous silica: The effect of pore size on CO{sub 2} capture performance

    Wang, Lin; Yao, Manli [Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004 (China); Hu, Xin [College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004 (China); Hu, Gengshen, E-mail: gshu@zjnu.edu.cn [Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004 (China); Lu, Jiqing; Luo, Mengfei [Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004 (China); Fan, Maohong, E-mail: mfan@uwyo.edu [Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071 (United States)

    2015-01-01

    Highlights: • Larger pore size could decrease the mass transfer resistance and increase the interaction between CO{sub 2} and TEPA. • The CO{sub 2} uptakes of sorbents were enhanced in the presence of moisture. • The sorbents are stable and regenerable under test conditions. - Abstract: The objective of current research is to investigate the effect of pore size of mesoporous silica supports on the CO{sub 2} capture performance of solid amine sorbents. Two ordered mesoporous silicas (OMS) with different pore sizes (5.6 nm and 7.6 nm) were synthesized as tetraethylenepentamine (TEPA) supports. A serious of techniques, such as physical adsorption, infrared spectroscopy and thermal gravimetric analysis were used to characterize the solid amine sorbents. The CO{sub 2} capture performances of the sorbents were evaluated using breakthrough method with a fixed-bed reactor equipped with an online mass spectrometer. The experimental results indicate that the pore size has significant influence on CO{sub 2} capture performance. Larger pore size could decrease the mass transfer resistance and increase the interaction between CO{sub 2} and TEPA. Therefore, OMS-7.6 is better than OMS-5.6 as amine support. The highest CO{sub 2} sorption capacities achieved with OMS-7.6 with 50 wt% TEPA loading (OMS-7.6-50) in the absence and presence of moisture are 3.45 mmol/g and 4.28 mmol/g, respectively, under the conditions of 10.0% CO{sub 2}/N{sub 2} mixture at 75 °C. Cyclic CO{sub 2} adsorption–desorption experiments indicate that the solid amine sorbents are fairly stable and regenerable.

  8. Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

    Yang, Ying; Gao, Guang; Zhang, Xin; Li, Fuwei [ChinaU - Petroleum; (Chinese Aca. Sci.)

    2016-02-04

    Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (RuxNi1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophase before pyrolysis and silica removal. The resulting RuxNi1–x–OMC materials are in-depth characterized with X-ray diffraction, N2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru0.9Ni0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h–1) was obtained, and the Ru0.9Ni0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.

  9. Highly efficient synthesis of ordered nitrogen-doped mesoporous carbons with tunable properties and its application in high performance supercapacitors

    Liu, Dan; Zeng, Chao; Qu, Deyu; Tang, Haolin; Li, Yu; Su, Bao-Lian; Qu, Deyang

    2016-07-01

    Nitrogen-doped ordered mesoporous carbons (OMCs) have been synthesized via aqueous cooperative assembly route in the presence of basic amino acids as either polymerization catalysts or nitrogen dopants. This method allows the large-scale production of nitrogen-doped OMCs with tunable composition, structure and morphology while maintaining highly ordered mesostructures. For instances, the nitrogen content can be varied from ∼1 wt% to ∼6.3 wt% and the mesophase can be either 3-D body-centered cubic or 2-D hexagonal. The specific surface area for typical OMCs is around 600 m2 g-1, and further KOH activation can significantly enhance the surface area to 1866 m2 g-1 without destroying the ordered mesostructures. Benefiting from hierarchically ordered porous structure, nitrogen-doping effect and large-scale production availability, the synthesized OMCs show a great potential towards supercapacitor application. When measured in a symmetrical two-electrode configuration with an areal mass loading of ∼3 mg cm-2, the activated OMC exhibits high capacitance (186 F g-1 at 0.25 A g-1) and good rate capability (75% capacity retention at 20 A g-1) in ionic liquid electrolyte. Even as the mass loading is up to ∼12 mg cm-2, the OMC electrode still yields a specific capacitance of 126 F g-1 at 20 A g-1.

  10. Nitrogen-doped mesoporous carbons for high performance supercapacitors

    Wu, Kai; Liu, Qiming

    2016-08-01

    The mesoporous carbons have been synthesized by using α-D(+)-Glucose, D-Glucosamine hydrochloride or their mixture as carbon precursors and mesoporous silicas (SBA-15 or MCF) as hard templates. The as-prepared products show a large pore volume (0.59-0.97 cm3 g-1), high surface areas (352.72-1152.67 m2 g-1) and rational nitrogen content (ca. 2.5-3.9 wt.%). The results of electrochemical tests demonstrate that both heteroatom doping and suitable pore structure play a decisive role in the performance of supercapacitors. The representative sample of SBA-15 replica obtained using D-Glucosamine hydrochloride only exhibits high specific capacitance (212.8 F g-1 at 0.5 A g-1) and good cycle durability (86.1% of the initial capacitance after 2000 cycles) in 6 M KOH aqueous electrolyte, which is attributed to the contribution of double layer capacitance and pseudo-capacitance. The excellent electrochemical performance makes it a promising electrode material for supercapacitors.

  11. Quantitative analysis of flavanones from citrus fruits by using mesoporous molecular sieve-based miniaturized solid phase extraction coupled to ultrahigh-performance liquid chromatography and quadrupole time-of-flight mass spectrometry.

    Cao, Wan; Ye, Li-Hong; Cao, Jun; Xu, Jing-Jing; Peng, Li-Qing; Zhu, Qiong-Yao; Zhang, Qian-Yun; Hu, Shuai-Shuai

    2015-08-07

    An analytical procedure based on miniaturized solid phase extraction (SPE) and ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry was developed and validated for determination of six flavanones in Citrus fruits. The mesoporous molecular sieve SBA-15 as a solid sorbent was characterised by Fourier transform-infrared spectroscopy and scanning electron microscopy. Additionally, compared with reported extraction techniques, the mesoporous SBA-15 based SPE method possessed the advantages of shorter analysis time and higher sensitivity. Furthermore, considering the different nature of the tested compounds, all of the parameters, including the SBA-15 amount, solution pH, elution solvent, and the sorbent type, were investigated in detail. Under the optimum condition, the instrumental detection and quantitation limits calculated were less than 4.26 and 14.29ngmL(-1), respectively. The recoveries obtained for all the analytes were ranging from 89.22% to 103.46%. The experimental results suggested that SBA-15 was a promising material for the purification and enrichment of target flavanones from complex citrus fruit samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC

    Mojca Rangus

    2014-05-01

    Full Text Available Iron-functionalized disordered mesoporous silica (FeKIL-2 is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM. We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05. From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1 the optimal concentration of stable isolated Fe3+ in the silica support; and (2 accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2 when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41.

  13. Enhancement of visible-light photocatalytic activity of silver and mesoporous carbon co-modified Bi2WO6

    Zhao, Qian; Gong, Ming; Liu, Wangping; Mao, Yulin; Le, Shukun; Ju, Shang; Long, Fei; Liu, Xiufang; Liu, Kai; Jiang, Tingshun

    2015-01-01

    Graphical abstract: - Highlights: • Silver and mesoporous carbon co-modified Bi 2 WO 6 (Ag/Bi 2 WO 6 /CMK-3) composite was prepared. • Photocatalytic activity of Bi 2 WO 6 was remarkably enhanced by co-modification of silver and mesoporous carbon. • The degradation rate of MB can reach ca. 95.1% under visible light irradiation. • The Ag/Bi 2 WO 6 /CMK-3 composite has good stability and potential application prospects. - Abstract: Ordered mesoporous carbon CMK-3 was prepared by hard template method using SBA-15 as template, sucrose as carbon source. Flower/sphere-like Bi 2 WO 6 and CMK-3/Bi 2 WO 6 photocatalysts were synthesized by hydrothermal method, and then Ag/Bi 2 WO 6 and Ag/Bi 2 WO 6 /CMK-3 composite photocatalysts were prepared via a photoreduction process. The samples were characterized by XRD, UV–vis, TEM (HR-TEM), SEM, N 2 physical adsorption and PL and their photocatalytic activities were evaluated by the photocatalytic degradation of methylene blue (MB) under visible light irradiation. The results show that both incorporating of CMK-3 and Ag loading greatly improved the photocatalytic activity of Bi 2 WO 6 , and the content of CMK-3 and silver have an impact on the photocatalytic activity of Bi 2 WO 6 . The photocatalytic activity of Ag/Bi 2 WO 6 /CMK-3 photocatalyst is superior to the activities of CMK-3/Bi 2 WO 6 and Ag/Bi 2 WO 6 under comparable conditions, and Ag/Bi 2 WO 6 /CMK-3 photocatalyst has high stability and is easy to be recycled. Also, the mechanism for the enhancement of the photocatalytic activity of CMK-3 and Ag co-modified Bi 2 WO 6 was also investigated

  14. Ordered mesoporous carbon film as an effective solid-phase microextraction coating for determination of benzene series from aqueous media

    Jiang, Hui [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); School of Geography Science, Nantong University, Nantong 226001 (China); Li, Jiansheng, E-mail: lijsh@mail.njust.edu.cn [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Jiang, Mingyue; Lu, Rui; Shen, Jinyou; Sun, Xiuyun; Han, Weiqing [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Wang, Lianjun, E-mail: wanglj@mail.njust.edu.cn [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China)

    2015-08-12

    The present work reports preparation of ordered mesoporous carbon (OMC) film supported on a graphite fiber as a new type of solid-phase microextraction (SPME) fiber for determination of benzene series from aqueous media. The strategy for the supported OMC film preparation was combined dip-coating technology with solvent evaporation-induced self-assembly (EISA) approach. A graphite fiber was immersed in an ethanol solution containing phenolic resin and Pluronic triblock copolymer. Upon solvent evaporation and subsequent pyrolysis under 700 °C, the phenolic resin and the surfactant self-assembled on the surface of the graphite fiber to form smooth OMC film. X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen isothermal adsorption results indicate that the resultant OMC film possesses well-ordered two dimensional hexagonal mesostructure with pore diameters of 4.5 nm and BET surfaces of 630 m{sup 2}/g. Scanning electron microscopy (SEM) studies show the supported OMC film with thickness at 8.5 μm is continuous and defect-free. The SPME efficiency of the OMC fiber was evaluated by analysis of five benzene series (benzene, toluene, ethylbenzene, p-xylene and m-xylene) from water samples by gas chromatography-flame ionization detection (GC-FID). The analysis results indicate that the prepared OMC fiber has wide linear ranges (0.5–500 μg/L), low detection limits (0.01–0.05 μg/L) and good repeatabilities (4.0–5.8% for one fiber, 2.9–8.7% for fiber-to-fiber). Compared with commercial counterparts, the OMC fiber exhibits improved extraction efficiency for benzene series and PAHs. - Highlights: • Ordered mesoporous carbon film supported on graphite fiber was first reported as solid-phase microextraction coating. • The strategy for the film preparation was combined dip-coating technology with evaporation-induced self-assembly approach. • The obtained fiber showed enhanced thermal stability and organic solvents resistance. • The

  15. Bioactive SrO-SiO2 glass with well-ordered mesopores: characterization, physiochemistry and biological properties.

    Wu, Chengtie; Fan, Wei; Gelinsky, Michael; Xiao, Yin; Simon, Paul; Schulze, Renate; Doert, Thomas; Luo, Yongxiang; Cuniberti, Gianaurelio

    2011-04-01

    For a biomaterial to be considered suitable for bone repair it should ideally be both bioactive and have a capacity for controllable drug delivery; as such, mesoporous SiO(2) glass has been proposed as a new class of bone regeneration material by virtue of its high drug-loading ability and generally good biocompatibility. It does, however, have less than optimum bioactivity and controllable drug delivery properties. In this study, we incorporated strontium (Sr) into mesoporous SiO(2) in an effort to develop a bioactive mesoporous SrO-SiO(2) (Sr-Si) glass with the capacity to deliver Sr(2+) ions, as well as a drug, at a controlled rate, thereby producing a material better suited for bone repair. The effects of Sr(2+) on the structure, physiochemistry, drug delivery and biological properties of mesoporous Sr-Si glass were investigated. The prepared mesoporous Sr-Si glass was found to have an excellent release profile of bioactive Sr(2+) ions and dexamethasone, and the incorporation of Sr(2+) improved structural properties, such as mesopore size, pore volume and specific surface area, as well as rate of dissolution and protein adsorption. The mesoporous Sr-Si glass had no cytotoxic effects and its release of Sr(2+) and SiO(4)(4-) ions enhanced alkaline phosphatase activity - a marker of osteogenic cell differentiation - in human bone mesenchymal stem cells. Mesoporous Sr-Si glasses can be prepared to porous scaffolds which show a more sustained drug release. This study suggests that incorporating Sr(2+) into mesoporous SiO(2) glass produces a material with a more optimal drug delivery profile coupled with improved bioactivity, making it an excellent material for bone repair applications. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  16. An ultrasensitive sandwich-type electrochemical immunosensor based on the signal amplification system of double-deck gold film and thionine unite with platinum nanowire inlaid globular SBA-15 microsphere.

    Wang, Ping; Li, Mingdang; Pei, Fubin; Li, Yueyun; Liu, Qing; Dong, Yunhui; Chu, Qingyan; Zhu, Hongjun

    2017-05-15

    A novel thionine unites with platinum nanowire inlaid globular SBA-15 (Pt NWs@g-SBA-15/Thi) not only utilizes as an efficient electrical signal probe but also constitutes an amplifying system with double-deck gold film (D-Au film) have been applied to the fabrication of sandwich-type immunosensor for detecting hepatitis B surface antigen (HBs Ag). The D-Au film can accelerate the electron transfer on the electrode interface due to the tunneling effect between the two Au films and can improve the load capacity of primary antibodies (Ab 1 ) because of the good biocompatibility. The Pt NWs@g-SBA-15/Thi with uniform globular morphology not only can effectively reduce the spatial limitation for loading the secondary antibodies (Ab 2 ) but also can provide outstanding pore accessibility of guest species from outside and offer catalytically active sites in a large scale. Besides, the presence of Thi can well enhance the electrical conductivity of Pt NWs@g-SBA-15/Thi. With the good cooperation between D-Au film and Pt NWs@g-SBA-15/Thi, a linear relationship between current signals and the concentrations of HBs Ag was obtained in the wide range from 10 fg/mL to 100ng/mL and the detection limit of HBs Ag was 3.3 fg/mL (signal-to-noise ratio of 3). Furthermore, the designed immunosensor with excellent selectivity, reproducibility and stability shows excellent performance in detection of human serum samples and provides a promising capacity for detecting a wide range of other tumor markers in clinical application. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Simple fabrication of solid phase microextraction fiber employing nitrogen-doped ordered mesoporous polymer by in situ polymerization.

    Zheng, Juan; Liang, Yeru; Liu, Shuqin; Jiang, Ruifen; Zhu, Fang; Wu, Dingcai; Ouyang, Gangfeng

    2016-01-04

    A combination of nitrogen-doped ordered mesoporous polymer (NOMP) and stainless steel wires led to highly sensitive, selective, and stable solid phase microextraction (SPME) fibers by in situ polymerization for the first time. The ordered structure of synthesized NOMP coating was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD), and microscopy analysis by scanning electron microscopy (SEM) confirmed a homogenous morphology of the NOMP-coated fiber. The NOMP-coated fiber was further applied for the extraction of organochlorine pesticides (OCPs) with direct-immersion solid-phase microextraction (DI-SPME) method followed by gas chromatography-mass spectrometry (GC-MS) quantification. Under the optimized conditions, low detection limits (0.023-0.77 ng L(-1)), a wide linear range (9-1500 ng L(-1)), good repeatability (3.5-8.1%, n=6) and excellent reproducibility (1.5-8.3%, n=3) were achieved. Moreover, the practical feasibility of the proposed method was evaluated by determining OCPs in environmental water samples with satisfactory recoveries. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Generation of Well-Defined Pairs of Silylamine on Highly Dehydroxylated SBA-15: Application to the Surface Organometallic Chemistry of Zirconium

    Azzi, Joachim

    2012-11-01

    Design of a new well-defined surface organometallic species [O-(=Si–NH)2Zr(IV)Np2] has been obtained by reaction of tetraneopentyl zirconium (ZrNp4) on SBA-15 surface displaying mainly silylamine pairs [O-(=Si–NH2)2]. These surface species have been achieved by an ammonia treatment of a highly dehydroxylated SBA-15 at 1000°C (SBA-151000). This support is known to contain mainly strained reactive siloxane bridges (≡Si-O-Si≡)[1] along with a small amount of isolated plus germinal silanols =Si(OH)2. Chemisorption of ammonia occurs primarily by opening these siloxane bridges[2] to generate silanol/silylamine pairs [O-(=Si–NH2)(=SiOH)] followed by substitution of the remaining silanol. Further treatment using hexamethyldisilazane (HMDS) results in the protection of the isolated remaining silanol groups by formation of ≡Si-O-SiMe3 and =Si(OSiMe3)2 but leaves ≡SiNH2 untouched. After reaction of this functionalized surface with ZrNp4, this latter displays mainly a bi-podal zirconium neopentyl organometallic complex [O-(=Si–NH)2Zr(IV)Np2] which has been fully characterized by diverse methods such as infrared transmission spectroscopy, magic angle spinning solid state nuclear magnetic resonance, surface elemental analysis, small angle X-ray powder diffraction (XRD), nitrogen adsorption and energy filtered transmission electron microscopy (EFTEM). These different characterization tools unambiguously prove that the zirconium organometallic complex reacts mostly with silylamine pairs to give a bi-podal zirconium bis-neopentyl complex, uniformly distributed into the channels of SBA-151000. Therefore this new material opens a new promising research area in Surface Organometallic Chemistry which, so far, was dealing mainly with O containing surface. It is expected that vicinal amine functions may play a very different role as compared with classical inorganic supports. Given the importance in the last decades of N containing ligands in catalysis, one may expect

  19. Mesoporous templated silicas: stability, pore size engineering and catalytic activation

    Vansant, Etienne

    2003-01-01

    The Laboratory of Adsorption and Catalysis has focused its research activities on the synthesis and activation of new porous materials. In the past few years, we have succeeded in developing easy and reproducible pathways to synthesize a huge variety of mesoporous crystalline materials. Points of interest in the synthesis of Mesoporous Templated Silicas are (i) stabilization of the structure, to withstand hydrothermal, thermal and mechanical pressure, (ii) pore size engineering to systematically control the pore size, pore volume and the ratio micro/mesopores and (iii) ease and reproducibility of the synthesis procedure, applying green principles, such as template recuperation. By carefully adapting the synthesis conditions and composition of the synthesis gel, using surfactants (long chain quaternary ammonium ions) and co-templates (long chain amines, alcohols or alkanes), the pore size of the obtained materials can be controlled from 1.5 to 7.0 nm, retaining the very narrow pore size distribution. Alternatively, materials with combined micro- and mesoporosity can be synthesized, using neutral surfactants (triblock copolymers). Hereby, the optimization of the SBA-15 and SBA-16 synthesis is being done in order to create mesoporous materials with microporous walls. The second research line is the controlled activation of MTS materials, by grafting or incorporation of catalytic active centers. We have developed for this purpose the Molecular Designed Dispersion method, which uses metal diketonate complexes as precursors. It is shown that in all cases the dispersion of the metal oxides on the surface is much better compared to the conventional grafting techniques. We have studied and published activation with V, Ti, Mo, Fe, Al and Cr species on different MTS materials. The structure and location of the active metal ion is the subject of an extensive spectroscopic investigation, using FT-IR, FT-Raman, UV-Vis DR coupled with selective chemisorption experiments and

  20. Electrochemical determination of bisphenol A at ordered mesoporous carbon modified nano-carbon ionic liquid paste electrode.

    Li, Yonghong; Zhai, Xiurong; Liu, Xinsheng; Wang, Ling; Liu, Herong; Wang, Haibo

    2016-02-01

    A simple bisphenol A (BPA) sensor was successfully fabricated based on ordered mesoporous carbon CMK-3 modified nano-carbon ionic liquid paste electrode (CMK-3/nano-CILPE). The nanostructure of CMK-3 and the surface morphologies of modified electrodes were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Electrochemical properties of the fabricated electrodes were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The fabricated sensor displayed excellent electroactivity towards bisphenol A using linear sweep voltammetry (LSV). Experimental conditions influencing the analytical performance of the modified electrode were optimized. Under optimal conditions, the oxidation peak current was proportional to BPA concentration in the range from 0.2 μM to 150 μM with a detection limit of 0.05 μM (S/N=3). This method was successfully used for determination of BPA leached from drinking bottle and plastic bag with good recoveries. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Thermo-sensitively and magnetically ordered mesoporous carbon nanospheres for targeted controlled drug release and hyperthermia application.

    Chen, Lin; Zhang, Huan; Zheng, Jing; Yu, Shiping; Du, Jinglei; Yang, Yongzhen; Liu, Xuguang

    2018-03-01

    A multifunctional nanoplatform based on thermo-sensitively and magnetically ordered mesoporous carbon nanospheres (TMOMCNs) is developed for effective targeted controlled release of doxorubicin hydrochloride (DOX) and hyperthermia in this work. The morphology, specific surface area, porosity, thermo-stability, thermo-sensitivity, as well as magnetism properties of TMOMCNs were verified by high resolution transmission electron microscopy, field emission scanning electron microscopy, thermo-gravimetric analysis, X-ray diffraction, Brunauer-Emmeltt-Teller surface area analysis, dynamic light scattering and vibrating sample magnetometry measurement. The results indicate that TMOMCNs have an average diameter of ~146nm with a lower critical solution temperature at around 39.5°C. They are superparamagnetic with a magnetization of 10.15emu/g at 20kOe. They generate heat when inductive magnetic field is applied to them and have a normalized specific absorption rate of 30.23W/g at 230kHz and 290Oe, showing good potential for hyperthermia. The DOX loading and release results illustrate that the loading capacity is 135.10mg/g and release performance could be regulated by changing pH and temperature. The good targeting, DOX loading and release and hyperthermia properties of TMOMCNs offer new probabilities for high effectiveness and low toxicity of cancer chemotherapy. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Morphology, microstructure, and magnetic properties of ordered large-pore mesoporous cadmium ferrite thin film spin glasses.

    Reitz, Christian; Suchomski, Christian; Chakravadhanula, Venkata Sai Kiran; Djerdj, Igor; Jagličić, Zvonko; Brezesinski, Torsten

    2013-04-01

    Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °C--the onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a "partially" inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T(f) ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.

  3. In-Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering

    Bridges, Craig A.; Paranthaman, Mariappan Parans; Sun, Xiao-Guang; Zhao, Jinkui; Dai, Sheng

    2012-01-01

    The aim of this work was to better understand the electrochemical processes occurring during the cycling of a lithium-ion half-cell containing ordered mesoporous hard carbon using time-resolved in situ small-angle neutron scattering (SANS). Utilizing electrolytes containing mixtures of deuterated (2H) and non-deuterated (1H) carbonates, we have addressed the challenging task of monitoring the formation and evolution of the solid-electrolyte interphase (SEI) layer. An evolution occurs in the SEI layer during discharge from a composition dominated by a higher scattering length density (SLD) lithium salt, to a lower SLD lithium salt for the ethylene carbonate/dimethyl carbonate (EC/DMC) mixture employed. By comparing half-cells containing different solvent deuteration levels, we show that it is possible to observe both SEI formation and lithium intercalation occurring concurrently at the low voltage region in which lithium intercalates into the hard carbon. These results demonstrate that SANS can be employed to monitor complicated electrochemical processes occurring in rechargeable batteries, in a manner that simultaneously provides information on the composition and microstructure of the electrode.

  4. Biodiesel from Hydrolyzed Waste Cooking Oil Using a S-ZrO2/SBA-15 Super Acid Catalyst under Sub-Critical Conditions

    Muhammad Nobi Hossain

    2018-01-01

    Full Text Available Due to rapid changes in food habits, a substantial amount of waste fat and used oils are generated each year. Due to strong policies, the disposal of this material into nearby sewers causes ecological and environmental problems in many parts of the world. For efficient management, waste cooking oil, a less expensive, alternative and promising feedstock, can be used as a raw material for producing biofuel. In the present study, we produced a biodiesel from hydrolyzed waste cooking oil with a subcritical methanol process using a synthesized solid super acid catalyst, a sulfated zirconium oxide supported on Santa Barbara Amorphous silica (S-ZrO2/SBA-15. The characterization of the synthesized catalyst was carried out using scanning electron microscopy (SEM, X-ray diffraction (XRD, and the Brunauer-Emmett-Teller (BET method. The catalytic effect on biodiesel production was examined by varying the parameters: temperatures of 120 to 200 °C, 5–20 min times, oil-to-methanol mole ratios between 1:5 to 1:20, and catalyst loadings of 1–2.5%. The maximum biodiesel yield was 96.383%, obtained under optimum reaction conditions of 140 °C, 10 min, and a 1:10 oil-to-methanol molar ratio with a 2.0% catalyst loading. We successfully reused the catalyst five times without regeneration with a 90% efficiency. The fuel properties were found to be within the limits set by the biodiesel standard.

  5. Synthesis of Hydrophobic Mesoporous Material MFS and Its Adsorption Properties of Water Vapor

    Guotao Zhao

    2014-01-01

    Full Text Available Fluorine-containing hydrophobic mesoporous material (MFS with high surface area is successfully synthesized with hydrothermal synthesis method by using a perfluorinated surfactant SURFLON S-386 template. The adsorption properties of water vapor on the synthesized MFS are also investigated by using gravimetric method. Results show that SEM image of the MFS depicted roundish morphology with the average crystal size of 1-2 μm. The BET surface area and total pore volume of the MFS are 865.4 m2 g−1 and 0.74 cm3 g−1 with a narrow pore size distribution at 4.9 nm. The amount of water vapor on the MFS is about 0.41 mmol g−1 at 303 K, which is only 52.6% and 55.4% of MCM-41 and SBA-15 under the similar conditions, separately. The isosteric adsorption heat of water on the MFS is gradually about 27.0–19.8 kJ mol−1, which decreases as the absorbed water vapor amount increases. The value is much smaller than that on MCM-41 and SBA-15. Therefore, the MFS shows more hydrophobic surface properties than the MCM-41 and SBA-15. It may be a kind of good candidate for adsorption of large molecule and catalyst carrier with high moisture resistance.

  6. Giant dielectric permittivity in interrupted silver nanowires grown within mesoporous silica

    Maity, Anupam; Samanta, Subha; Chatterjee, Soumi; Maiti, Ramaprasad; Biswas, Debasish; Saha, Shyamal K.; Chakravorty, Dipankar

    2018-06-01

    Nanoglasses in the system Ag2O–SiO2 were formed within the pores of mesoporous silica SBA-15 (Santa Barbara Amorphous). Silver nanowires of diameter 5 nm were grown within SBA-15 by the process of electrodeposition. The nanowires were disrupted by applying a suitable voltage pulse. Detailed transmission and scanning electron microscopy studies were carried out. The disrupted silver strands were found to have an average length of 90 nm. The density of interrupted strands was estimated from the electron micrographs and found to have values in the range (10–20)  ×  1010 cm‑2. Dielectric constant and dielectric loss factors of the nanocomposites of disrupted silver strand—containing Ag2O–SiO2 glass and SBA-15 were found to have values in the range 200–300 and 0.014–0.008 respectively at frequencies in the range 10 kHz–2 MHz. These values were found to be in satisfactory agreement with the theoretical model of Rice and Bernasconi emanating from the theory of Gorkhov and Eliashberg. These nanocomposites are expected to be useful in the fabrication of supercapacitors, after developing suitable electrode system for the material.

  7. Recovery of silica from electronic waste for the synthesis of cubic MCM-48 and its application in preparing ordered mesoporous carbon molecular sieves using a green approach

    Liou, Tzong-Horng, E-mail: thliou@mail.mcut.edu.tw [Ming Chi University of Technology, Department of Chemical Engineering, Taiwan (China)

    2012-07-15

    The electronics industry is one of the world's fastest growing manufacturing industries. However, e-waste has become a serious pollution problem. This study reports the recovery of e-waste for preparing valuable MCM-48 and ordered mesoporous carbon for the first time. Specifically, this study adopts an alkali-extracted method to obtain sodium silicate precursors from electronic packaging resin ash. The influence of synthesis variables such as gelation pH, neutral/cationic surfactant ratio, hydrothermal treatment temperature, and calcination temperature on the mesophase of MCM-48 materials is investigated. Experimental results confirm that well-ordered cubic MCM-48 materials were synthesized in strongly acidic and strongly basic media. The resulting mesoporous silica had a high surface area of 1,317 m{sup 2}/g, mean pore size of about 3.0 nm, and a high purity of 99.87 wt%. Ordered mesoporous carbon with high surface area (1,715 m{sup 2}/g) and uniform pore size of CMK-1 type was successfully prepared by impregnating MCM-48 template using the resin waste. The carbon structure was sensitive to the sulfuric acid concentration and carbonization temperature. Converting e-waste into MCM-48 materials not only eliminates the disposal problem of e-waste, but also transforms industrial waste into a useful nanomaterial.

  8. Functionalized mesoporous silicas with crown ether moieties for selective adsorption of lithium ions in artificial sea water.

    Sung, Soo Park; Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang-Sik

    2014-11-01

    Lithium ion has been increasingly recognized in a wide range of industrial applications. In this work, we studied on the adsorption of Li+ in the artificial seawater with high selectivity using methyl-crown ether (AC-SBA-15) and aza-crown ether (HMC-SBA-15) moieties-functionalized mesoporous silica materials. First, methyl-crown ether and aza-crown ether moieties-functionalized mesoporous silica materials were synthesized via two-step post-synthesis process using a grafting method. The functionalized materials were employed to the metal ion adsorption from aqueous solution (artificial seawater) containing Li+, Co2+, Cr3+ and Hg2+. The prepared hybrid material showed high selectivity for Li+ ion in the artificial seawater at pH 8.0. The absorbed amount of Li+ was 73 times higher than Cr3+ for aza-crown ether containing AC-SBA-15 as an absorbent. The absorbed amount of Co2+ (4.5 x 10(-5) mol/g), Cr3+ (1.5 x 10(-5) mol/g) and Hg2+ (2.25 x 10(-4) mol/g) were remarkably lower than the case of Li+. On the other hand, the absorbed amount of various metal ions of HMC-SBA-15 with amine groups in alky chains and crown ether moieties were 1.1 x 10(-3) mol/g for Li+, 5.0 x 10(-5) mol/g for Co2+, 2.9 x 10(-4) mol/g for Cr3+, 2.8 x 10(-4) mol/g for Hg2+ mol/g, respectively.

  9. A novel, efficient and facile method for the template removal from mesoporous materials

    Chen, Lu

    2014-11-12

    © 2014, Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH. A new catalytic-oxidation method was adopted to remove the templates from SBA-15 and MCM-41 mesoporous materials via Fenton-like techniques under microwave irradiation. The mesoporous silica materials were treated with different Fenton agents based on the template’s property and textural property. The samples were characterized by powder X-ray diffraction(XRD) measurement, N2 adsorption-desorption isotherms, infrared spectroscopy, 29Si MAS NMR and thermo gravimetric analysis(TGA). The results reveal that this is an efficient and facile approach to the thorough template-removal from mesoporous silica materials, as well as to offering products with more stable structures, higher BET surface areas, larger pore volumes and larger quantity of silanol groups.

  10. Synthesis and characterization of nanometal-ordered mesoporous carbon composites as heterogeneous catalysts for electrooxidation of aniline

    Duan, Xiaoyue; Chen, Yawen; Liu, Xinyue; Chang, Limin

    2017-01-01

    Highlights: •NM-OMC catalysts were prepared for electrochemical oxidation of aniline. •The oxidation of aniline was studied with NM-OMC catalysts suspended in solution. •The Cu-OMC exhibited the highest catalytic activity for aniline degradation. •The mineralization current efficiency was improved by 2 times with Cu-OMC catalyst. •An electrochemical mineralization pathway of aniline was proposed. -- Abstract: The Cu, Co and Ni nanometal embedded ordered mesoporous carbons (NM-OMCs) were fabricated by a soft-template method using phenol/formaldehyde as carbon source and triblock copolymer F127 as template agent. The morphology, structure, surface physicochemical properties and pore structure of the NM-OMCs were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption-desorption isotherms. Their potential application to the electrocatalytic degradation of aniline was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and ·OH radicals generation test. Furthermore, the electrochemical oxidation process of aniline was also investigated in the presence of the OMC-based catalyst particles suspended in a Na 2 SO 4 solution using a PbO 2 anode. Results revealed that the NM-OMCs inherited the ordered mesostructure of pristine OMC and the metal nanoparticles (Cu, Co or Ni) were embedded in the carbon framework. The Cu-OMC exhibited significantly higher catalytic activity than OMC and other NM-OMCs for the electrooxidation of aniline. In electrochemical oxidation process of aniline, nearly all of aniline could be degraded after 120 min of electrolysis with Cu-OMC particles as catalyst, while 89%, 92%, and 97% with OMC, Co-OMC and Ni-OMC catalysts, respectively, obviously higher than 76% of electrochemical oxidation without assistance of catalysts. After

  11. Insignificant influence of the matrix on the melting of ice confined in decorated mesoporous silica

    Xu, Yunbo; Zhao, Zhenyan; Wang, Lianwen

    2018-01-01

    For a critical examination of matrix effect on the melting of confined ice, mesoporous silica (SBA-15) are synthesised and decorated with n-Alkyl and aminopropyl groups to tune the surface hydrophobicity. Water contact angle to these decorated surfaces are estimated to be about 100° and 60°, respectively. By examining the melting of ice confined in these decorated samples, we find that the influence of the matrix is indeed not significant. The reported apparent matrix effect is more likely method effect in the determination of pore diameters as was demonstrated in our previous studies (Philos. Mag. 93 (2013), p. 1827).

  12. Synthesis and characterization of mesoporous silica modified with chiral auxiliaries for their potential application as chiral stationary phase.

    Mayani, Vishal J; Abdi, S H R; Kureshy, R I; Khan, N H; Agrawal, Santosh; Jasra, R V

    2008-05-16

    Novel chiral stationary phase (CSP) based on chiral aminoalcohol immobilized on ordered mesoporous silica SBA-15 1a and standard silica 1b and their copper complexes 1a' and 1b', respectively, was synthesized as potential material for chiral ligand exchange chromatography (CLEC). Microanalysis, inductively coupled plasma spectroscopy (ICP), thermo-gravimetric analysis (TGA), cross polarized magic angle spinning (CP-MAS) (13)C NMR, Powder X-ray diffraction (PXRD), FTIR, N(2) adsorption isotherm, scanning electron microscopy (SEM), transmitted electron microscope (TEM) and solid reflectance UV-vis spectroscopy were used to characterize these materials. All the chiral stationary phases thus synthesized were used for the separation of different racemic compounds such as mandelic acid, 2,2'-dihydroxy-1,1'-binaphthalene BINOL) and diethyl tartrate by simple medium-pressure column chromatography. Successful enantio-separation of racemic mandelic acid was achieved with all the stationary phases but 1a and 1b gave slightly better resolution than their copper complexes 1a' and 1b'. Remarkably these materials are stable under the given experimental conditions and can be used repeatedly for several cycles of enantioresolution. It was observed that the porosity and surface area of the stationary phase play an important role in the chiral separation.

  13. An insight into the removal of Cu (II) and Pb (II) by aminopropyl-modified mesoporous carbon CMK-3: Adsorption capacity and mechanism

    Hamad, Hussein, E-mail: hussein.hamad@ul.edu.lb [Platform for Research and Analysis in Environmental Sciences (PRASE), Lebanese University, Beirut (Lebanon); Ezzeddine, Zeinab; Lakis, Fatima; Rammal, Hassan [Platform for Research and Analysis in Environmental Sciences (PRASE), Lebanese University, Beirut (Lebanon); Srour, Mortada [Lebanese University, Faculty of Sciences (I), Hadath, Beirut (Lebanon); Hijazi, Akram [Platform for Research and Analysis in Environmental Sciences (PRASE), Lebanese University, Beirut (Lebanon)

    2016-08-01

    In this study, the adsorption of heavy metal ions onto ordered mesoporous carbon CMK-3 was investigated. CMK-3 has been synthesized using SBA-15 as the hard template and then directly amino-functionalized by the treatment with 3-aminopropyltrimethoxysilane (APTMS) without the need of oxidation before. The thus obtained modified mesoporous carbon has been characterized by nitrogen sorption, X-ray diffraction and infrared spectroscopy. Its adsorption efficiency for the removal of Cu{sup 2+} and Pb{sup 2+} from aqueous solutions was tested. The effects of contact time, pH and initial metal ions concentration were investigated as well. The adsorption capacities were very high (3.5 mmol g{sup −1} and 8.6 mmol g{sup −1} for Pb{sup 2+} and Cu{sup 2+} respectively). These values depend largely on the speciation of metal ions as a function of pH. The selectivity was also dependent on the nature of metal ions rather than the adsorbent used. The mechanism of adsorption is complex where several types of interaction between metal ions and the adsorbent surface are involved. - Highlights: • Mesoporous carbon CMK-3 was successfully synthesized and functionalized. • No oxidation treatment was done prior to aminopropyl functionalization. • The adsorbent adsorption capacity is high (3.5 mmol g{sup −1} for Cu{sup 2+} and 8.6 mmol g{sup −1} for Pb{sup 2+}). • The maximum Cu{sup 2+} adsorption capacity is related to its speciation as a function of pH. • The mechanism of adsorption is complex including different types of interaction.

  14. Preparation of Cerium (III) 12-tungstophosphoric acid/ordered mesoporous carbon composite modified electrode and its electrocatalytic properties

    Liu Lin; Ndamanisha, Jean Chrysostome; Bai Jing; Guo Liping

    2010-01-01

    In this work, a novel structured Cerium (III) 12-tungstophosphoric acid (CePW)/ordered mesoporous carbon (OMC) composite is synthesized. The characterization of the material by the Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical characterization shows that the novel CePW/OMC composite has improved properties based on the combination of CePW and OMC properties. CePW/OMC can be used to modify the glassy carbon (GC) electrode and the CePW/OMC/GC modified electrode shows an enhanced electrocatalytic activity. This property can be applied in the determination of some biomolecules. Especially, the detection and determination of the guanine (G) in the presence of adenine (A) is achieved. The catalytic current of G versus its concentration shows a good linearity with two good linear ranges from 4.0 x 10 -6 to 8.0 x 10 -5 M and from 8.0 x 10 -5 to 1.9 x 10 -3 M (correlation coefficient = 0.999 and 0.996) with a detection limit of 5.7 x 10 -9 M (S/N = 3). The linear range for adenine is 4.0 x 10 -6 -7.0 x 10 -4 M with a detection limit of 7.45 x 10 -8 M. With good stability and reproducibility, the present CePW/OMC/GC modified electrode should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules.

  15. Free-standing, well-aligned ordered mesoporous carbon nanofibers on current collectors for high-power micro-supercapacitors.

    Kang, Eunae; Jeon, Gumhye; Kim, Jin Kon

    2013-07-21

    The mesoporous carbon nanofiber arrays that stand on carbon-gold double-layer current collectors are synthesized by self-assembly of a PS-b-PEO copolymer and resol in AAO templates for a high-power micro-supercapacitor at high current densities.

  16. A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer-Tropsch synthesis.

    Sun, Zhenkun; Sun, Bo; Qiao, Minghua; Wei, Jing; Yue, Qin; Wang, Chun; Deng, Yonghui; Kaliaguine, Serge; Zhao, Dongyuan

    2012-10-24

    The organization of different nano objects with tunable sizes, morphologies, and functions into integrated nanostructures is critical to the development of novel nanosystems that display high performances in sensing, catalysis, and so on. Herein, using acetylacetone as a chelating agent, phenolic resol as a carbon source, metal nitrates as metal sources, and amphiphilic copolymers as a template, we demonstrate a chelate-assisted multicomponent coassembly method to synthesize ordered mesoporous carbon with uniform metal-containing nanoparticles. The obtained nanocomposites have a 2-D hexagonally arranged pore structure, uniform pore size (~4.0 nm), high surface area (~500 m(2)/g), moderate pore volume (~0.30 cm(3)/g), uniform and highly dispersed Fe(2)O(3) nanoparticles, and constant Fe(2)O(3) contents around 10 wt %. By adjusting acetylacetone amount, the size of Fe(2)O(3) nanoparticles is readily tunable from 8.3 to 22.1 nm. More importantly, it is found that the metal-containing nanoparticles are partially embedded in the carbon framework with the remaining part exposed in the mesopore channels. This unique semiexposure structure not only provides an excellent confinement effect and exposed surface for catalysis but also helps to tightly trap the nanoparticles and prevent aggregating during catalysis. Fischer-Tropsch synthesis results show that as the size of iron nanoparticles decreases, the mesoporous Fe-carbon nanocomposites exhibit significantly improved catalytic performances with C(5+) selectivity up to 68%, much better than any reported promoter-free Fe-based catalysts due to the unique semiexposure morphology of metal-containing nanoparticles confined in the mesoporous carbon matrix.

  17. Green Synthesis of Acetals/Ketals: Efficient Solvent-Free Process for the Carbonyl/Hydroxyl Group Protection Catalyzed by SBA-15 Materials

    Pérez-Mayoral, E.; Martín-Aranda, R. M.; López-Peinado, A. J.; Ballesteros, P.; Zukal, Arnošt; Čejka, Jiří

    2009-01-01

    Roč. 52, 1-2 (2009), s. 148-152 ISSN 1022-5528 R&D Projects: GA AV ČR 1QS400400560 Institutional research plan: CEZ:AV0Z40400503 Keywords : acid and basic heterogeneous catalysts * mesoporous molecular sieves * acatalation reactions * fine chemicals Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.379, year: 2009

  18. Immobilization of Nafion-ordered mesoporous carbon on a glassy carbon electrode: Application to the detection of epinephrine

    Zhou Ming; Guo Liping; Hou Ying; Peng Xiaojuan

    2008-01-01

    A stable suspension of ordered mesoporous carbon (OMC) was obtained by dispersing OMC in a solution of Nafion. By coating the suspension onto glassy carbon (GC) electrode, cyclic voltammetry was used to evaluate the electrochemical behaviors of Nafion-OMC-modified GC (Nafion-OMC/GC) electrode in 0.1 mmol L -1 hexaammineruthenium(III) chloride (Ru(NH 3 ) 6 Cl 3 )/0.1 mol L -1 KCl solution, where Nafion-OMC/GC electrode shows a faster electron transfer rate as compared with OMC/GC, Nafion/GC and GC electrodes. Due to the unique properties of Nafion-OMC, an obvious decrease in the overvoltage of the epinephrine (EP) oxidation (ca. 100 mV at pH 4.1 and 115 mV at pH 7.0) as well as a dramatic increase in the peak current (12 times at pH 4.1 and 6 times at pH 7.0) was observed at Nafion-OMC/GC electrode compared to that seen at GC electrode. By combining the advantages of OMC with those of Nafion, the anodic peak of EP and that of ascorbic acid (AA) were separated successfully (by ca. 144-270 mV) in the pH range of 2.0-10.0, which may make Nafion-OMC/GC electrode potential for selective determination of EP in the presence of AA at a broad pH range. As an EP sensor, the EP amperometric response at Nafion-OMC/GC electrode in pH 7.0 PBS is extremely stable, with 99% of the initial activity remaining (compared to 32% at GC surface) after 120 min stirring of 0.20 mmol L -1 EP. And Nafion-OMC/GC electrode can be used to readily detect the physiological concentration of EP at pH 7.0. These make Nafion-OMC/GC electrode potential candidates for stable and efficient electrochemical sensor for the detection of EP. The solubilization of OMC by Nafion may provide a route to more precise manipulation, and functionalization for the construction of OMC-based sensors, as well as allowing OMC to be introduced to biologically relevant systems

  19. Immobilization of Nafion-ordered mesoporous carbon on a glassy carbon electrode: Application to the detection of epinephrine

    Zhou Ming [Faculty of Chemistry, Northeast Normal University, Renmin Street 5268, Changchun 130024 (China); Guo Liping [Faculty of Chemistry, Northeast Normal University, Renmin Street 5268, Changchun 130024 (China)], E-mail: guolp078@nenu.edu.cn; Hou Ying; Peng Xiaojuan [Faculty of Chemistry, Northeast Normal University, Renmin Street 5268, Changchun 130024 (China)

    2008-05-01

    A stable suspension of ordered mesoporous carbon (OMC) was obtained by dispersing OMC in a solution of Nafion. By coating the suspension onto glassy carbon (GC) electrode, cyclic voltammetry was used to evaluate the electrochemical behaviors of Nafion-OMC-modified GC (Nafion-OMC/GC) electrode in 0.1 mmol L{sup -1} hexaammineruthenium(III) chloride (Ru(NH{sub 3}){sub 6}Cl{sub 3})/0.1 mol L{sup -1} KCl solution, where Nafion-OMC/GC electrode shows a faster electron transfer rate as compared with OMC/GC, Nafion/GC and GC electrodes. Due to the unique properties of Nafion-OMC, an obvious decrease in the overvoltage of the epinephrine (EP) oxidation (ca. 100 mV at pH 4.1 and 115 mV at pH 7.0) as well as a dramatic increase in the peak current (12 times at pH 4.1 and 6 times at pH 7.0) was observed at Nafion-OMC/GC electrode compared to that seen at GC electrode. By combining the advantages of OMC with those of Nafion, the anodic peak of EP and that of ascorbic acid (AA) were separated successfully (by ca. 144-270 mV) in the pH range of 2.0-10.0, which may make Nafion-OMC/GC electrode potential for selective determination of EP in the presence of AA at a broad pH range. As an EP sensor, the EP amperometric response at Nafion-OMC/GC electrode in pH 7.0 PBS is extremely stable, with 99% of the initial activity remaining (compared to 32% at GC surface) after 120 min stirring of 0.20 mmol L{sup -1} EP. And Nafion-OMC/GC electrode can be used to readily detect the physiological concentration of EP at pH 7.0. These make Nafion-OMC/GC electrode potential candidates for stable and efficient electrochemical sensor for the detection of EP. The solubilization of OMC by Nafion may provide a route to more precise manipulation, and functionalization for the construction of OMC-based sensors, as well as allowing OMC to be introduced to biologically relevant systems.

  20. Modified mesoporous silica materials for on-line separation and preconcentration of hexavalent chromium using a microcolumn coupled with flame atomic absorption spectrometry

    Wang Zheng, E-mail: wangzheng@mail.sic.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Fang Dongmei; Li Qing [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); East China University of Science and Technology, Shanghai 200237 (China); Zhang Lingxia; Qian Rong; Zhu Yan; Qu Haiyun [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Du Yiping [East China University of Science and Technology, Shanghai 200237 (China)

    2012-05-06

    Highlights: Black-Right-Pointing-Pointer A modified SBA-15 mesoporous silica material (NH{sub 2}-SBA-15) was synthesized as sorbent. Black-Right-Pointing-Pointer The material was used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Black-Right-Pointing-Pointer The NH{sub 2}-SBA-15 enables retain Cr (VI) with an enrichment factor of 44. Black-Right-Pointing-Pointer The micro-column of NH{sub 2}-SBA-15 underwent more than 100 adsorption/desorption cycles. - Abstract: A modified SBA-15 mesoporous silica material NH{sub 2}-SBA-15 was synthesized successfully by grafting {gamma}-aminopropyl-triethoxysilane. The material was characterized using transmission electron microscopy (TEM) and Fourier transform infrared/Raman (FT-IR/Raman) spectroscopy, and used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Effective sorption of Cr (VI) was achieved at pH 2.0 with no interference from Cr (III) and other ions and 0.5 mol L{sup -1} NH{sub 3}{center_dot}H{sub 2}O solution was found optimal for the complete elution of Cr (VI). An enrichment factor of 44 and was achieved under optimized experimental conditions at a sample loading of 2.0 mL min{sup -1} sample loading (300 s) and an elution flow rate of 2.0 mL min{sup -1} (24 s). The precision of the 11 replicate Cr (VI) measurements was 2.1% at the 100 {mu}g L{sup -1} level with a detection limit of 0.2 {mu}g L{sup -1} (3 s, n = 10) using the FAAS. The developed method was successfully applied to trace chromium determination in waste water. The accuracy was validated using a certified reference material of riverine water (GBW08607).

  1. Cr(VI) adsorption on functionalized amorphous and mesoporous silica from aqueous and non-aqueous media

    Perez-Quintanilla, Damian; Hierro, Isabel del; Fajardo, Mariano; Sierra, Isabel

    2007-01-01

    A mesoporous silica (SBA-15) and amorphous silica (SG) have been chemically modified with 2-mercaptopyridine using the homogeneous route. This synthetic route involved the reaction of 2-mercaptopyridine with 3-chloropropyltriethoxysilane prior to immobilization on the support. The resulting material has been characterized by powder X-ray diffraction, nitrogen gas sorption, FT-IR and MAS NMR spectroscopy, thermogravimetry and elemental analysis. The solid was employed as a Cr(VI) adsorbent from aqueous and non-aqueous solutions at room temperature. The effect of several variables (stirring time, pH, metal concentration and solvent polarity) has been studied using the batch technique. The results indicate that under the optimum conditions, the maximum adsorption value for Cr(VI) was 1.83 ± 0.03 mmol/g for MP-SBA-15, whereas the adsorption capacity of the MP-SG was 0.86 ± 0.02 mmol/g. On the basis of these results, it can be concluded that it is possible to modify chemically SBA-15 and SG with 2-mercaptopyridine and to use the resulting modified silicas as effective adsorbents for Cr(VI)

  2. Controlled synthesis of ordered mesoporous TiO{sub 2}-supported on activated carbon and pore-pore synergistic photocatalytic performance

    Liu, Chen; Li, Youji, E-mail: bcclyj@163.com; Xu, Peng; Li, Ming; Zeng, Mengxiong

    2015-01-15

    Ordered mesoporous titania/activated carbon (OMTAC) were prepared by the template technique with the aid of an ultrasonic method. To explore the relationship between the structure and properties of OMTAC, the ultrasonic-sol-gel technique was applied to synthesize titania dioxide/activated carbon (USTAC). The obtained material structure was characterized by X-ray diffraction (XRD), nitrogen adsorption – desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV diffuse reflectance (DRS) and Photoluminescence (PL) emission spectra. OMTAC photocatalytic performance was evaluated by means of acid red B (ARB) degradation. The pore-pore synergistic amplification mechanism of photocatalysis was proposed and the effects of catalytic conditions on synergistic amplification were explored. The results show that compared to OMT, OMTAC has a small particle size, low electron-hole recombination rate and high surface areas, due to the hindering effect of activated carbon on crystalline grain growth and an ordered mesoporous structure of titania. OMTAC has higher catalytic activity than USTAC, OMT and P25, due to pore-pore synergistic amplification effect of photocatalysis. The OMT content is strongly affected OMTAC photocatalytic activity, and OMTAC-3 (loading 3 times of OMT on AC) has the highest photocatalytic activity due to high hydroxyl concentration, surface area and low electron-hole recombination rate. When ARB is degraded by OMTAC-3, the optimum catalytic conditions are a catalyst concentration of 1 g/L, an ARB concentration of 15 mg/L and a pH of 5. - Graphical abstract: We investigate the influence of mesoporous titania content upon the photocatalytic performance of OMTAC in acid red B degradation. - Highlights: • OMTAC were fabricated by a template technique with the aid of an ultrasonic method. • OMTAC show high photoactivity for acid red B (ARB) degradation. • OMTAC also show pore-pore synergistic photocatalytic

  3. A facile one-pot self-assembly approach to incorporate SnOx nanoparticles in ordered mesoporous carbon with soft templating for fuel cells

    Huang, Yingqiang; Zhai, Zhicheng; Luo, Zhigang; Liu, Yingju; Liang, Zhurong; Fang, Yueping

    2014-04-01

    Unique SnOx (x = 1,2)/ordered mesoporous carbon nanocomposites (denoted as SnOx/OMC) are firstly synthesized through a ‘one-pot’ synthesis together with the soft template self-assembly approach. The obtained SnOx/OMC nanocomposites with various SnOx contents exhibit uniform pore sizes between 3.9 and 4.2 nm, high specific surface areas between 497 and 595 m2 g-1, and high pore volumes between 0.39 and 0.48 cm3 g-1. With loading of Pt, Pt-SnOx/OMC with relatively low SnOx content exhibits superior electrocatalytic performance, long-term durability, and resistance to CO poisoning for methanol oxidation, as compared to Pt/OMC, PtRu/C and Pt-SnOx/C, which may be attributed not only to the synergetic effect of embedded SnOx, but also to the highly ordered mesostructure with high specific surface areas and large pore volumes affording plenty of surface area for support of Pt nanoparticles. This work supplies an efficient way to synthesize novel ordered mesoporous carbon self-supported metallic oxide as catalyst support and its further potential application to reduce the cost of catalysts in direct methanol fuel cells.

  4. A facile one-pot self-assembly approach to incorporate SnOx nanoparticles in ordered mesoporous carbon with soft templating for fuel cells

    Huang, Yingqiang; Zhai, Zhicheng; Luo, Zhigang; Liu, Yingju; Liang, Zhurong; Fang, Yueping

    2014-01-01

    Unique SnO x  (x = 1,2)/ordered mesoporous carbon nanocomposites (denoted as SnO x /OMC) are firstly synthesized through a ‘one-pot’ synthesis together with the soft template self-assembly approach. The obtained SnO x /OMC nanocomposites with various SnO x contents exhibit uniform pore sizes between 3.9 and 4.2 nm, high specific surface areas between 497 and 595 m 2  g −1 , and high pore volumes between 0.39 and 0.48 cm 3  g −1 . With loading of Pt, Pt–SnO x /OMC with relatively low SnO x content exhibits superior electrocatalytic performance, long-term durability, and resistance to CO poisoning for methanol oxidation, as compared to Pt/OMC, PtRu/C and Pt–SnO x /C, which may be attributed not only to the synergetic effect of embedded SnO x , but also to the highly ordered mesostructure with high specific surface areas and large pore volumes affording plenty of surface area for support of Pt nanoparticles. This work supplies an efficient way to synthesize novel ordered mesoporous carbon self-supported metallic oxide as catalyst support and its further potential application to reduce the cost of catalysts in direct methanol fuel cells. (paper)

  5. High electrochemical performance of RuO_2–Fe_2O_3 nanoparticles embedded ordered mesoporous carbon as a supercapacitor electrode material

    Xiang, Dong; Yin, Longwei; Wang, Chenxiang; Zhang, Luyuan

    2016-01-01

    The electrode materials RuO_2 or RuO_2–Fe_2O_3 nanoparticle embedded OMC (ordered mesoporous carbon) are prepared by the method of impregnation and heating in situ. The mesoporous structure optimized the electron and proton conducting pathways, leading to the enhanced capacitive performances of the composite materials. The average nanoparticle size of RuO_2 and RuO_2–Fe_2O_3 is 2.54 and 1.96 nm, respectively. The fine RuO_2–Fe_2O_3 nanoparticles are dispersed evenly in the pore channel wall of the two-dimensional mesoporous carbon without blocking the mesoporous channel, and they have a higher specific surface area, a larger pore volume, a proper pore size and a small charge transfer impedance value. The special electrochemical capacitance of RuO_2–Fe_2O_3/OMC tested in acid electrolyte (H_2SO_4) is measured to be as high as 1668 F g"−"1, which is higher than that of RuO_2/OMC. Meanwhile, the supercapacitor properties of the RuO_2–Fe_2O_3/OMC composites show a good cycling performance of 93% capacitance retention (3000 cycles), a better reversibility, a higher energy density (134 Wh kg"−"1) and power density (4000 W kg"−"1). The composite electrode of RuO_2–Fe_2O_3/OMC, which combines a double layer capacitance with pseudo-capacitance, is proved to be suitable for ideal high performance electrode material of a hybrid supercapacitor application. - Highlights: • The nanocomposites of RuO_2–Fe_2O_3/OMC are prepared by impregnation and heating in situ. • The fine RuO_2–Fe_2O_3 nanoparticles distribute in the pore channel wall of OMC. • We discuss a reversible redox reaction mechanism of RuO_2–Fe_2O_3/OMC in acid solutions. • RuO_2–Fe_2O_3 nanoparticles embedded OMC shows a higher supercapacitive performance.

  6. Ordered Mesoporous Titania/Carbon Hybrid Monoliths for Lithium-ion Battery Anodes with High Areal and Volumetric Capacity.

    Dörr, Tobias S; Fleischmann, Simon; Zeiger, Marco; Grobelsek, Ingrid; de Oliveira, Peter W; Presser, Volker

    2018-04-25

    Free-standing, binder-free, and conductive additive-free mesoporous titanium dioxide/carbon hybrid electrodes were prepared from co-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) block copolymer and a titanium alkoxide. By tailoring an optimized morphology, we prepared macroscopic mechanically stable 300 μm thick monoliths that were directly employed as lithium-ion battery electrodes. High areal mass loading of up to 26.4 mg cm -2 and a high bulk density of 0.88 g cm -3 were obtained. This resulted in a highly increased volumetric capacity of 155 mAh cm -3 , compared to cast thin film electrodes. Further, the areal capacity of 4.5 mAh cm -2 represented a 9-fold increase compared to conventionally cast electrodes. These attractive performance metrics are related to the superior electrolyte transport and shortened diffusion lengths provided by the interconnected mesoporous nature of the monolith material, assuring superior rate handling, even at high cycling rates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Co{sub 3}O{sub 4} nanoparticles embedded in ordered mesoporous carbon with enhanced performance as an anode material for Li-ion batteries

    Park, Junsu; Kim, Gil-Pyo [Seoul National University (SNU), World Class University (WCU) Program of Chemical Convergence for Energy and Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Institute of Chemical Processes (Korea, Republic of); Umh, Ha Nee [Kwangwoon University, Department of Chemical Engineering (Korea, Republic of); Nam, Inho; Park, Soomin [Seoul National University (SNU), World Class University (WCU) Program of Chemical Convergence for Energy and Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Institute of Chemical Processes (Korea, Republic of); Kim, Younghun [Kwangwoon University, Department of Chemical Engineering (Korea, Republic of); Yi, Jongheop, E-mail: jyi@snu.ac.kr [Seoul National University (SNU), World Class University (WCU) Program of Chemical Convergence for Energy and Environment C2E2, School of Chemical and Biological Engineering, College of Engineering, Institute of Chemical Processes (Korea, Republic of)

    2013-09-15

    A Co{sub 3}O{sub 4}/ordered mesoporous carbon (OMC) nanocomposite, in which Co{sub 3}O{sub 4} nanoparticles (NPs), with an average size of about 10 nm homogeneously embedded in the OMC framework, are prepared for use as an anode material in Li-ion batteries. The composite is prepared by a one-pot synthesis based on the solvent evaporation-induced co-self-assembly of a phenolic resol, a triblock copolymer F127, and Co(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O, followed by carbonization and oxidation. The resulting material has a high reversible capacity of {approx}1,025 mA h g{sup -1} after 100 cycles at a current density of 0.1 A g{sup -1}. The enhanced cycling stability and rate capability of the composite can be attributed to the combined mesoporous nanostructure which provides efficient pathways for Li-ion transport and the homogeneous distribution of the Co{sub 3}O{sub 4} NPs in the pore wall of the OMC, which prevents aggregation. These findings suggest that the OMC has promise for use as a carbon metric for metals and metal oxides as an anode material in high performance Li-ion batteries.

  8. Mesoporous aluminum phosphite

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

    2009-01-01

    High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S + I - 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 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.

  9. Structural analysis and characterization of synthesized ordered mesoporous silicate (MCM-41) using small angle X-rays scattering and complementary techniques

    Akinlalu, Ademola V.

    Mesoporous silicate have widespread potential applications, such as drug delivery, supports for catalysis, selective adsorption and host to guest molecules. Most important in the area of scientific research and industrial applications is their demand due to its extremely high surface areas (> 800m 2g-1) and larger pores with well defined structures. Mesoporous silicate (MCM-41) samples were prepared by hydrothermal method under various chemo-physical conditions and various experimental methods such as small angle X-rays scattering (SAXS), Nitrogen adsorption-desorption analysis at 77 K, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were employed to investigate the changes in the structural morphology and subtle lattice parameter changes. With regards to the subtle changes in the structural characteristics of the synthesized mesoporous silicate, we seek to understand the electron density function changes as the synthesis parameter are varied from low molar concentration of ATAB/Si to higher concentration, the system becoming more acidity due to increase in the hydrolysis time of pH regulator as a result of increased production of ethanol and acetic acid and the changes due to extended reaction time. This Ph.D. research tries to understand the influence of various parameters like surfactant-Si molar ratio, reaction time, and the hydrolysis of the pH regulator on the orderliness/disorderliness of the lattice order, lattice spacing and electron density function. The stages during synthesis are carefully selected to better understand where the greater influence on the overall structural morphology exist so as to be able to ne tune this parameter for any desired specification and application. The SAXS measurement were conducted on a HECUS S3-Micro X-ray system at Rensselaer Polytechnic Institute, Troy, NY. while the data evaluation and visualization were carried in 3DView 4.2 and EasySWAXS software. The electron density functions

  10. Nitrogen-doped ordered mesoporous carbon with a high surface area, synthesized through organic-inorganic coassembly, and its application in supercapacitors.

    Song, Yanfang; Li, Li; Wang, Yonggang; Wang, Congxiao; Guo, Zaipin; Xia, Yongyao

    2014-07-21

    A new nitrogen-doped ordered mesoporous carbon (N-doped OMC) is synthesized by using an organic-inorganic coassembly method, in which resol is used as the carbon precursor, dicyandiamide as the nitrogen precursor, silicate oligomers as the inorganic precursors, and F127 as the soft template. The N-doped OMC possesses a surface area as high as 1374 m(2)  g(-1) and a large pore size of 7.4 nm. As an electrode material for supercapacitors, the obtained carbon exhibits excellent cycling stability and delivers a reversible specific capacitance as high as 308 F g(-1) in 1 mol L(-1) H(2)SO(4) aqueous electrolyte, of which 58 % of the capacity is due to pseudo-capacitance. The large specific capacitance is attributed to proper pore size distributions, large surface area, and high nitrogen content. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Low-cost fabrication of highly sensitive room temperature hydrogen sensor based on ordered mesoporous Co-doped TiO2 structure

    Li, Zhong; Haidry, Azhar Ali; Wang, Tao; Yao, Zheng Jun

    2017-07-01

    The development of cost-effective gas sensors with improved sensing properties and minimum power consumption for room temperature hydrogen leakage monitoring is in increasing demand. In this context, this report focus on the facile fabrication of ordered mesoporous TiO2 via evaporation-induced self-assembly route. With the controlled doping threshold (3%Co-TiO2), the output resistance change to 1000 ppm H2 is ˜4.1 × 103 with the response time of 66 s. The sensor response exhibits power law dependence with an increase in the hydrogen concentration, where the power law coefficient was found not only specific to the kind of target gas but also related to temperature. Further, the effect of structure integrity with doping level and humidity on sensing characteristics is interpreted in terms of variation in surface potential eVS and depletion region w caused by the adsorption of molecular oxygen O2-.

  12. Prussian blue mediated amplification combined with signal enhancement of ordered mesoporous carbon for ultrasensitive and specific quantification of metolcarb by a three-dimensional molecularly imprinted electrochemical sensor.

    Yang, Yukun; Cao, Yaoyu; Wang, Xiaomin; Fang, Guozhen; Wang, Shuo

    2015-02-15

    In this work, we presented a three-dimensional (3D) molecularly imprinted electrochemical sensor (MIECS) with novel strategy for ultrasensitive and specific quantification of metolcarb based on prussian blue (PB) mediated amplification combined with signal enhancement of ordered mesoporous carbon. The molecularly imprinted polymers were synthesized by electrochemically induced redox polymerization of para aminobenzoic acid (p-ABA) in the presence of template metolcarb. Ordered mesoporous carbon material (CMK-3) was introduced to enhance the electrochemical response by improving the structure of the modified electrodes and facilitating charge transfer processes of PB which was used as an inherent electrochemical active probe. The modification process for the working electrodes of the MIECS was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV), and several important parameters controlling the performance of the MIECS were investigated and optimized in detail. The MIECS with 3D structure had the advantages of ease of preparation, high porous surface structure, speedy response, ultrasensitivity, selectivity, reliable stability, good reproducibility and repeatability. Under the optimal conditions, the MIECS offered an excellent current response for metolcarb in the linear response range of 5.0 × 10(-10)-1.0 × 10(-4) mol L(-1) and the limit of detection (LOD) was calculated to be 9.3 × 10 (-11)mol L(-1) (S/N = 3). The proposed MIECS has been successfully applied for the determination of metolcarb in real samples with satisfactory recoveries. Furthermore, the construction route of this ultrasensitive 3D MIECS may provide a guideline for the determination of non-electroactive analytes in environmental control and food safety. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Encapsulation of valproic acid and sodic phenytoin in ordered mesoporous SiO 2 solids for the treatment of temporal lobe epilepsy

    López, T.; Basaldella, E. I.; Ojeda, M. L.; Manjarrez, J.; Alexander-Katz, R.

    2006-10-01

    Temporal lobe epilepsy is one of the most frequent types of human neurological diseases, and a variety of surgical procedures have been developed for the treatment of intractable cases. An alternative is the use of drug-containing reservoirs based on nanostructured materials of controlled pore sizes in order to deliver the drug without causing secondary effects. Ordered SiO 2 nanostructures were developed as drug reservoirs. The latter were prepared by the sol-gel process using tetraethyl orthosilicate TEOS as precursor to form the "sol" and P123 surfactant as the organic structure-directing agent. In addition to the nontoxic nature of amorphous silica, uniform and tunable pore sizes between 2.5 and 30 nm can be obtained in this way. The aim of this study is to investigate the potential of these materials for the storage and release of drugs in the brain. For that, we loaded valproic acid (VH) and sodic phenytoin (PH) molecules into an ordered mesoporous SiO 2 by impregnation and characterized the drug impregnated SiO 2 by standard physical and spectroscopic techniques to identify the parameters necessary to improve the capacity and quality of the reservoirs. Finally, a study of neurohistopathology of the effects of these reservoirs on brain tissue is presented.

  14. Synthesis of magnetic CoFe2O4/ordered mesoporous carbon nanocomposites and application in Fenton-like oxidation of rhodamine B.

    Deng, Jing; Chen, Yi-Jing; Lu, Yu-An; Ma, Xiao-Yan; Feng, Shan-Fang; Gao, Naiyun; Li, Jun

    2017-06-01

    CoFe 2 O 4 /ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFe 2 O 4 nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFe 2 O 4 /OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO 4 - ·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFe 2 O 4 and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFe 2 O 4 /OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFe 2 O 4 /OMC nanocomposites compared to that of CoFe 2 O 4 nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).

  15. Silver-containing mesoporous bioactive glass with improved antibacterial properties.

    Gargiulo, Nicola; Cusano, Angela Maria; Causa, Filippo; Caputo, Domenico; Netti, Paolo Antonio

    2013-09-01

    The aim of the present work is the study of the bacteriostatic/bactericidal effect of a silver-containing mesoporous bioactive glass obtained by evaporation-induced self-assembly and successive thermal stabilization. Samples of the manufactured mesophase were characterized by means of transmission electron microscopy and N₂ adsorption/desorption at 77 K, revealing structural and textural properties similar to SBA-15 mesoporous silica. Glass samples used for bioactivity experiments were put in contact with a standardized, commercially available cell culture medium instead of lab-produced simulated body fluid, and were then characterized by means of X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. All these analyses confirmed the development of a hydroxyl carbonate apatite layer on glass particles. Moreover, the investigated mesostructure showed a very good antibacterial effect against S. aureus strain, with a strong evidence of bactericidal activity already registered at 0.5 mg/mL of glass concentration. A hypothesis about the mechanism by which Ag affects the bacterial viability, based on the intermediate formation of crystalline AgCl, was also taken into account. With respect to what already reported in the literature, these findings claim a deeper insight into the possible use of silver-containing bioactive glasses as multifunctional ceramic coatings for orthopedic devices.

  16. Synthesis of non-siliceous mesoporous oxides.

    Gu, Dong; Schüth, Ferdi

    2014-01-07

    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.

  17. Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

    Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

    2015-01-01

    Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

  18. Effect of ordered mesoporous carbon contact layer on the sensing performance of sputtered RuO2 thin film pH sensor.

    Lonsdale, W; Maurya, D K; Wajrak, M; Alameh, K

    2017-03-01

    The effect of contact layer on the pH sensing performance of a sputtered RuO 2 thin film pH sensor is investigated. The response of pH sensors employing RuO 2 thin film electrodes on screen-printed Pt, carbon and ordered mesoporous carbon (OMC) contact layers are measured over a pH range from 4 to 10. Working electrodes with OMC contact layer are found to have Nernstian pH sensitivity (-58.4mV/pH), low short-term drift rate (5.0mV/h), low hysteresis values (1.13mV) and fast reaction times (30s), after only 1h of conditioning. A pH sensor constructed with OMC carbon contact layer displays improved sensing performance compared to Pt and carbon-based counterparts, making this electrode more attractive for applications requiring highly-accurate pH sensing with reduced conditioning time. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Hierarchically ordered macro-mesoporous ZnS microsphere with reduced graphene oxide supporter for a highly efficient photodegradation of methylene blue

    Sookhakian, M., E-mail: m.sokhakian@gmail.com [Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia); Amin, Y.M. [Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia); Basirun, W.J. [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Centre of Research in Nanotechnology and Catalysis (NanoCat), Institute of Postgraduate Studies, University Malaya, Kuala Lumpur 50603 (Malaysia)

    2013-10-15

    A facile one-pot method for the fabrication of high quality self-assembled hierarchically ordered macro-mesoporous ZnS microsphere–reduced graphene oxide (RGO) composite without the use of templates or surfactants is described. During the hydrothermal process, reduced graphene oxide (RGO) was loaded into the ZnS microsphere by in situ reduction of graphene oxide added in the self-assembly system. The morphology and structure of the as-prepared composites were confirmed by X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy and Raman spectroscopy. Incorporation of reduced graphene oxide as an excellent electron-transporting material effectively suppresses the charge recombination. Hence, a significant enhancement in the photocatalytic efficiency for the photodegradation of methylene blue was observed with the ZnS–RGO composite, compared to the pure ZnS. Overall, this research results may lay down new vistas for the in situ fabrication of the ZnS–RGO composite as a highly efficient photocatalysis under visible-light irradiation and their applications in environmental protection.

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

    Werghi, Baraa

    2016-09-26

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

  1. A novel method for preparation of 8-hydroxyquinoline functionalized mesoporous silica: Aluminum complexes and photoluminescence studies

    Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Goldooz, Hassan [Department of Chemistry, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Ziarani, Ghodsi Mohammadi [Department of Chemistry, Faculty of Science, Alzahra University, Tehran (Iran, Islamic Republic of)

    2011-03-15

    8-Hydroxyquinoline (8-HQ) was attached to mesoporous silica by sulfonamide bond formation between 8-hydroxyquinoline-5-sulfonyl chloride (8-HQ-SO{sub 2}Cl) and aminopropyl functionalized SBA-15 (designated as SBA-SPS-Q) and then aluminum complexes of 8-HQ was covalently bonded to SBA-SPS-Q using coordinating ability of grafted 8-HQ.The prepared materials were characterized by powder X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FT-IR), thermal analysis (TGA-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis and fluorescence spectra. The environmental effects on the emission spectra of grafted 8-HQ and its complexes were studied and discussed in details.

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

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

    2016-01-01

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

  3. Innovative preparation of Au/C by replication of gold-containing mesoporous silica catalysts

    Kerdi, Fatmé

    2010-01-01

    A new strategy, based on the nanocasting concept, has been used to prepare gold nanoparticles (NPs) highly dispersed in meso-structured carbons. Gold is first introduced in various functionalized mesostructured silicas (MCM-48 and SBA-15) and particles are formed inside the porosity upon reduction of Au 3+ cations. Silica pores are then impregnated with a carbon precursor and the composite material is heated at 900°C under vacuum. Silica is then removed by acid leaching, leading to partially encapsulated gold particles in mesoporous carbon. Carbon prevents aggregation of gold particles at high temperature, both the mean size and distribution being similar to those observed in silica. However, while Au@SiO2 exhibit significant catalytic activity in the aerobic oxidation of trans-stilbene in the liquid phase, its Au@C mesostructured replica is quite inactive. © 2010 Elsevier B.V. All rights reserved.

  4. [In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

    Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

    2009-05-01

    Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0SBA-15 and Ni2P/SBA-16 catalysts. The absorbance observed at 2051-2055 cm(-1) for CO adsorption on Ni2P/MCM-48, Ni2P/SBA-15 and Ni2P/SBA-16 catalysts is due to the formation of Ni(CO)4 species. The other upsilon absorbances observed at 2093-2096 cm(-1) was attributed to CO terminally bonded to cus Ni(delta+) (0

  5. Synthesis Mechanism and Thermal Optimization of an Economical Mesoporous Material Using Silica: Implications for the Effective Removal or Delivery of Ibuprofen.

    Shanmuga Kittappa

    Full Text Available Mesoporous silica materials (MSMs were synthesized economically using silica (SiO2 as a precursor via a modified alkaline fusion method. The MSM prepared at 500°C (MSM-500 had the highest surface area, pore size, and volume, and the results of isotherms and the kinetics of ibuprofen (IBP removal indicated that MSM-500 had the highest sorption capacity and fastest removal speed vs. SBA-15 and zeolite. Compared with commercial granular activated carbon (GAC, MSM-500 had a ~100 times higher sorption rate at neutral pH. IBP uptake by MSM-500 was thermodynamically favorable at room temperature, which was interpreted as indicating relatively weak bonding because the entropy (∆adsS, -0.07 J mol(-1 K(-1 was much smaller. Five times recycling tests revealed that MSM-500 had 83-87% recovery efficiencies and slower uptake speeds due to slight deformation of the outer pore structure. In the IBP delivery test, MSM-500 drug loading was 41%, higher than the reported value of SBA-15 (31%. The in vitro release of IBP was faster, almost 100%, reaching equilibrium within a few hours, indicating its effective loading and unloading characteristics. A cost analysis study revealed that the MSM was ~10-70 times cheaper than any other mesoporous silica material for the removal or delivery of IBP.

  6. Cellular membrane trafficking of mesoporous silica nanoparticles

    Fang, I-Ju [Iowa State Univ., Ames, IA (United States)

    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

  7. Conductivity of liquid lithium electrolytes with dispersed mesoporous silica particles

    Sann, K.; Roggenbuck, J.; Krawczyk, N.; Buschmann, H.; Luerßen, B.; Fröba, M.; Janek, J.

    2012-01-01

    Highlights: ► The conductivity of disperse lithium electrolytes with mesoporous fillers is studied. ► In contrast to other investigations in literature, no conductivity enhancement could be observed for standard battery electrolytes and typical mesoporous fillers in various combinations. ► Disperse electrolytes can become relevant in terms of battery safety. ► Dispersions of silicas and electrolyte with LiPF 6 as conducting salt are not stable, although the silicas were dried prior to preparation and the electrolyte water content was controlled. Surface modification of the fillers improved the stability. ► The observed conductivity decrease varied considerably for various fillers. - Abstract: The electrical conductivity of disperse electrolytes was systematically measured as a function of temperature (0 °C to 60 °C) and filler content for different types of fillers with a range of pore geometry, pore structure and specific surface area. As fillers mesoporous silicas SBA-15, MCM-41 and KIT-6 with pore ranges between 3 nm and 15 nm were dispersed in commercially available liquid lithium electrolytes. As electrolytes 1 M of lithium hexafluorophosphate (LiPF 6 ) in a mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) at the ratio 3:7 (wt/wt) and the same solvent mixture with 0.96 M lithium bis(trifluoromethanesulfon)imide (LiTFSI) were used. No conductivity enhancement could be observed, but with respect to safety aspects the highly viscous disperse pastes might be useful. The conductivity decrease varied considerably for the different fillers.

  8. Preparation of a Si/SiO2 -Ordered-Mesoporous-Carbon Nanocomposite as an Anode for High-Performance Lithium-Ion and Sodium-Ion Batteries.

    Zeng, Lingxing; Liu, Renpin; Han, Lei; Luo, Fenqiang; Chen, Xi; Wang, Jianbiao; Qian, Qingrong; Chen, Qinghua; Wei, Mingdeng

    2018-04-03

    In this work, an Si/SiO 2 -ordered-mesoporous carbon (Si/SiO 2 -OMC) nanocomposite was initially fabricated through a magnesiothermic reduction strategy by using a two-dimensional bicontinuous mesochannel of SiO 2 -OMC as a precursor, combined with an NaOH etching process, in which crystal Si/amorphous SiO 2 nanoparticles were encapsulated into the OMC matrix. Not only can such unique porous crystal Si/amorphous SiO 2 nanoparticles uniformly dispersed in the OMC matrix mitigate the volume change of active materials during the cycling process, but they can also improve electrical conductivity of Si/SiO 2 and facilitate the Li + /Na + diffusion. When applied as an anode for lithium-ion batteries (LIBs), the Si/SiO 2 -OMC composite displayed superior reversible capacity (958 mA h g -1 at 0.2 A g -1 after 100 cycles) and good cycling life (retaining a capacity of 459 mA h g -1 at 2 A g -1 after 1000 cycles). For sodium-ion batteries (SIBs), the composite maintained a high capacity of 423 mA h g -1 after 100 cycles at 0.05 A g -1 and an extremely stable reversible capacity of 190 mA h g -1 was retained even after 500 cycles at 1 A g -1 . This performance is one of the best long-term cycling properties of Si-based SIB anode materials. The Si/SiO 2 -OMC composites exhibited great potential as an alternative material for both lithium- and sodium-ion battery anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Substituent effect on the oxidation peak potentials of phenol derivatives at ordered mesoporous carbons modified electrode and its application in determination of acidity coefficients (pKa)

    Zhang, Tingting; Lang, Qiaolin; Zeng, Lingxing; Li, Tie; Wei, Mingdeng; Liu, Aihua

    2014-01-01

    In this paper, the relationship between the electrochemical characteristics and the structure of a series of substituted phenol derivatives with electron-donating or electron-withdrawing groups were studied by voltammetry using ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). p-Nitrophenol (p-NP) and p-methylphenol were selected as models of electron-withdrawing and electron-donating groups, respectively, to illustrate the electrochemical behavior and reaction mechanism of substituted phenols. Voltammetric study showed that the oxidation peak potential (E pa ) of substituted phenols with an electron-withdrawing group was systematically higher than that of substituted phenols with an electron-donating group. That is, the direct electrochemical oxidation of substituted phenol with an electron-withdrawing group is more difficult than that of substituted phenol with an electron-donating group. The E pa value shifted negatively with the increase of pKa for both p-substituted phenols and o-substituted phenols with the equations of pKa = −6.986 E pa + 13.261 (for p-substituted phenols) and pKa = −7.929 E pa + 13.831 (for o-substituted phenols). Thus, a simple and novel method was proposed for the precise prediction of the pKa of substituted phenols by determining E pa values with voltammetry at OMCs/GCE, which matched fairly with the results calculated from Hammett's constants. Thus, the present work may provide additional strategy to determine pKa values and investigate possible mechanisms of some organic reactions. In addition, by making use of the substituent effect, different p-substituted phenols (or o-substituted phenols) can be well separated and identified at OMCs/GCE by voltametry, which may find possible applications in simultaneous detection of p-substituted phenols (or o-substituted phenols)

  10. Hydrothermal stability investigation of micro- and mesoporous silica containing long-range ordered cobalt oxide clusters by XAS.

    Liu, Liang; Wang, David K; Kappen, Peter; Martens, Dana L; Smart, Simon; Diniz da Costa, João C

    2015-07-15

    This work investigates the hydrothermal stability of cobalt doped silica materials with different Co/Si molar ratios (0, 0.05, 0.10, and 0.25). The resultant materials were characterized by N2 sorption and chemical structures by Raman and X-ray absorption spectroscopy before and after a harsh hydrothermal exposure (550 °C, 75 mol% vapour and 40 h). The cobalt silica materials showed a lower surface area loss from 48% to 12% with increasing Co/Si molar ratio from 0.05 to 0.25 and relatively maintaining their pore size distribution, while pure silica exhibited significant surface area reduction (80%) and pore size broadening. For low cobalt loading sample (Co/Si = 0.05), the cobalt was highly dispersed in the silica network in a tetrahedral coordination with oxygen and a small proportion of Co-Co interaction in the second shell. Long range order Co3O4 was observed when Co/Si molar ratio increased to 0.10 and 0.25. The hydrothermal exposure did not affect the local cobalt environments and no cobalt-silicon interaction was observed by X-ray absorption spectroscopy. The hydrothermal stability of the silica matrix was attributed to the physical barrier of cobalt oxide in opposing densification and silica mobility under harsh hydrothermal conditions.

  11. Comparison of different mesoporous silicas for off-line solid phase extraction of 17β-estradiol from waters and its determination by HPLC-DAD.

    Gañán, Judith; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Sierra, Isabel

    2013-09-15

    Functionalized (SBA-C₁₈ and SM-C₁₈) and non-functionalized (SBA-15 and SM) mesoporous silicas were then examined as sorbents for solid-phase extraction of 17β-estradiol in aqueous media. Experiments were run in order to test critical factors affecting the procedure extraction efficiency, including the type of sorbent, the analyte concentration, the solvent and volume used for elution and the sample volume. Among the prepared materials, SBA-C₁₈ had the highest adsorption affinity towards 17β-estradiol and under optimized conditions (200mg of sorbent, 150 mL of water sample, elution with 3 × 2 mL of methanol) this sorbent proved good extraction capacity and elution efficiency for this hormone from aqueous media (recovery near 100%). To evaluate the analytical applicability of the proposed method, it was applied to the determination of 17β-estradiol in drinking water by high performance liquid chromatography with a photodiode array detector. Calibration curves were shown to be linear between 1.25 and 100 mg L(-1)with correlation coefficients ≥0.999 (n=5) for 17β-estradiol. The instrumental detection and quantitation limits calculated were 0.38 and 1.25 mg L(-1), respectively. The relative standard deviation obtained values were ≤3% and the mean recoveries obtained were of 82%. The results suggest that SBA-C18 is a promising material for the off-line solid phase extraction of 17β-estradiol from waters. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Mesoporous carbon materials

    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.

  13. Mesoporous Silicate Materials in Sensing

    Paul T. Charles

    2008-08-01

    Full Text Available 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 cocondensation 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.

  14. 软模法磁性有序介孔炭的合成与表征%Synthesis and characterization of magnetic ordered mesoporous carbon materials using soft templating method

    王加; 林汉森; 王秀芳

    2012-01-01

    Magnetic ordered mesoporous carbon is synthesized through soft templating method by using triblock-copolymer Pluronic F127 as soft template,resorcinol-formaldehyde (RF) as carbon precursor and ferric nitrate as an iron source. HC1 is used as the catalyst for RF polymerization. The resultant materials are characterized by X-ray diffraction, N2 sorption and vibrating-sample magnetometer measurements. The results show that magnetic ordered mesoporous carbons are obtained when the Fe/R ratio is 0. 025. For those with Fe/R ratios greater than this value,the ordering,the BET surface area,pore volume and pore size decrease. N2 sorption isotherms of all the samples show representative type IV curves with HI hysteresis loops, which indicates a typical mesoporous material. Magnetic hysteresis loops show that the remanent magnetization of Fe/OMC samples increases with the increase of the content of Fe. This research can provide scientific proof for the optimized synthesis and application in magnetic separation for magnetic ordered mesoporous carbons.%以三嵌段共聚物为软模,间苯二酚-甲醛为炭前躯体,硝酸铁为铁源合成了磁性有序介孔炭,用XRD、氮气吸附、磁性测试等方法对样品进行表征.结果表明,当硝酸铁与间苯二酚摩尔比为0.025、0.05及0.10时得到的介孔炭具有有序性,随着铁质量分数的增加,有序性降低,比表面积、孔容都相应减小.基本磁化曲线结果表明,随着铁质量分数的增加,饱和磁化强度随之增加(0.01~0.10 emu/g),材料具有较好的磁性,容易从溶液中分离,表现出良好的分离性能.为磁性有序介孔炭的优化合成及磁性分离应用提供科学依据.

  15. Tunable conductivity in mesoporous germanium

    Beattie, Meghan N.; Bioud, Youcef A.; Hobson, David G.; Boucherif, Abderraouf; Valdivia, Christopher E.; Drouin, Dominique; Arès, Richard; Hinzer, Karin

    2018-05-01

    Germanium-based nanostructures have attracted increasing attention due to favourable electrical and optical properties, which are tunable on the nanoscale. High densities of germanium nanocrystals are synthesized via electrochemical etching, making porous germanium an appealing nanostructured material for a variety of applications. In this work, we have demonstrated highly tunable electrical conductivity in mesoporous germanium layers by conducting a systematic study varying crystallite size using thermal annealing, with experimental conductivities ranging from 0.6 to 33 (×10‑3) Ω‑1 cm‑1. The conductivity of as-prepared mesoporous germanium with 70% porosity and crystallite size between 4 and 10 nm is shown to be ∼0.9 × 10‑3 Ω‑1 cm‑1, 5 orders of magnitude smaller than that of bulk p-type germanium. Thermal annealing for 10 min at 400 °C further reduced the conductivity; however, annealing at 450 °C caused a morphological transformation from columnar crystallites to interconnecting granular crystallites and an increase in conductivity by two orders of magnitude relative to as-prepared mesoporous germanium caused by reduced influence of surface states. We developed an electrostatic model relating the carrier concentration and mobility of p-type mesoporous germanium to the nanoscale morphology. Correlation within an order of magnitude was found between modelled and experimental conductivities, limited by variation in sample uniformity and uncertainty in void size and fraction after annealing. Furthermore, theoretical results suggest that mesoporous germanium conductivity could be tuned over four orders of magnitude, leading to optimized hybrid devices.

  16. Mesoporous Carbon Produced from Tri-constituent Mesoporous Carbon-silica Composite for Water Purification

    Yu, Yanjie

    2012-01-01

    Highly ordered mesoporous carbon-silica nanocomposites with interpenetrating carbon and silica networks were synthesized by the evaporation-induced tri-constituent co- assembly approach. The removal of silica by concentrated NaOH solution produced mesoporous carbons, which contained not only the primary large pores, but also the secondary mesopores in the carbon walls. The thus synthesized mesoporous carbon was further activated by using ZnCl2. The activated mesoporous carbon showed an improved surface area and pore volume. The synthesized mesoporous carbon was tested for diuron removal from water and the results showed that the carbon gave a fast diuron adsorption kinetics and a high diuron removal capacity, which was attributable to the primary mesopore channels being the highway for mass transfer, which led to short diffusion path length and easy accessibility of the interpenetrated secondary mesopores. The optimal adsorption capacity of the porous carbon was determined to be 390 mg/g, the highest values ever reported for diuron adsorption on carbon-based materials.

  17. Mesoporous Carbon Produced from Tri-constituent Mesoporous Carbon-silica Composite for Water Purification

    Yu, Yanjie

    2012-05-01

    Highly ordered mesoporous carbon-silica nanocomposites with interpenetrating carbon and silica networks were synthesized by the evaporation-induced tri-constituent co- assembly approach. The removal of silica by concentrated NaOH solution produced mesoporous carbons, which contained not only the primary large pores, but also the secondary mesopores in the carbon walls. The thus synthesized mesoporous carbon was further activated by using ZnCl2. The activated mesoporous carbon showed an improved surface area and pore volume. The synthesized mesoporous carbon was tested for diuron removal from water and the results showed that the carbon gave a fast diuron adsorption kinetics and a high diuron removal capacity, which was attributable to the primary mesopore channels being the highway for mass transfer, which led to short diffusion path length and easy accessibility of the interpenetrated secondary mesopores. The optimal adsorption capacity of the porous carbon was determined to be 390 mg/g, the highest values ever reported for diuron adsorption on carbon-based materials.

  18. A membrane electrode assembled photoelectrochemical cell with a solar-responsive cadmium sulfide-zinc sulfide-titanium dioxide/mesoporous silica photoanode

    Chen, Ming; Chen, Rong; Zhu, Xun; Liao, Qiang; An, Liang; Ye, Dingding; Zhou, Yuan; He, Xuefeng; Zhang, Wei

    2017-12-01

    In this work, a membrane electrode assembled photoelectrochemical cell (PEC) is developed for the electricity generation by degrading the organic compounds. The photocatalyst is prepared by the incorporation of mesoporous silica SBA-15 into TiO2 and the photosensitization of CdS-ZnS to enhance the photoanode performance, while the cathode employs the air-breathing mode to enhance the oxygen transport. The experimental results show that the developed PEC exhibits good photoresponse to the illumination and the appropriate SBA-15 mass ratio in the photoanode enables the enhancement of the performance. It is also shown that the developed PEC yields better performance in the alkaline environment than that in the neutral environment. Increasing the KOH concentration can improve the cell performance. There exist optimal liquid flow rate and organics concentration leading to the best performance. Besides, it is found that increasing the light intensity can generate more electron-hole pairs and thus enhance the cell performance. These results are helpful for optimizing the design.

  19. Highly improved sensibility and selectivity ethanol sensor of mesoporous Fe-doped NiO nanowires

    Li, X. Q.; Wei, J. Q.; Xu, J. C.; Jin, H. X.; Jin, D. F.; Peng, X. L.; Hong, B.; Li, J.; Yang, Y. T.; Ge, H. L.; Wang, Xinqing

    2017-12-01

    In this paper, nickel oxides (NiO) and iron (Fe)-doped NiO nanowires (NWs) with the various doping content (from 1 to 9 at%) were synthesized by using SBA-15 templates with the nanocasting method. All samples were synthesized in the same conditions and exhibited the same mesoporous-structures, uniform diameter, and defects. Mesoporous-structures with high surface area created more active sites for the adsorption of oxygen on the surface of all samples, resulting in the smaller surface resistance in air. The impurity energy levels from the donor Fe-doping provided electrons to neutralize the holes of p-type Fe-doped NiO NWs, which greatly enhanced the total resistance. The comparative gas-sensing study between NiO NWs and Fe-doped NiO NWs indicated that the high-valence donor Fe-doping obviously improved the ethanol sensitivity and selectivity for Fe-doped NiO NWs. And Ni0.94Fe0.06O1.03 NWs sensor presented the highest sensitivity of 14.30 toward ethanol gas at 320 °C for the high-valence metal-doping.

  20. Journal of Chemical Sciences | Indian Academy of Sciences

    Vapor phase hydrogenation of levulinic acid using formic acid as a hydrogen source has been conducted over ordered mesoporous Cu/Fe2O3 catalysts prepared by hard template method using mesoporous silica, SBA-15. X-ray diffraction result reveals the absence of copper peaks because of either highly dispersed state, ...

  1. Functionalized Mesoporous Silica Membranes for CO2 Separation Applications

    Hyung-Ju Kim

    2015-01-01

    Full Text Available Mesoporous silica molecular sieves are emerging candidates for a number of potential applications involving adsorption and molecular transport due to their large surface areas, high pore volumes, and tunable pore sizes. Recently, several research groups have investigated the potential of functionalized mesoporous silica molecular sieves as advanced materials in separation devices, such as membranes. In particular, mesoporous silica with a two- or three-dimensional pore structure is one of the most promising types of molecular sieve materials for gas separation membranes. However, several important challenges must first be addressed regarding the successful fabrication of mesoporous silica membranes. First, a novel, high throughput process for the fabrication of continuous and defect-free mesoporous silica membranes is required. Second, functionalization of mesopores on membranes is desirable in order to impart selective properties. Finally, the separation characteristics and performance of functionalized mesoporous silica membranes must be further investigated. Herein, the synthesis, characterization, and applications of mesoporous silica membranes and functionalized mesoporous silica membranes are reviewed with a focus on CO2 separation.

  2. Nanostructured Mesoporous Silicas for Bone Tissue Regeneration

    Isabel Izquierdo-Barba

    2008-01-01

    Full Text Available The research on the development of new biomaterials that promote bone tissue regeneration is receiving great interest by the biomedical scientific community. Recent advances in nanotechnology have allowed the design of materials with nanostructure similar to that of natural bone. These materials can promote new bone formation by inducing the formation of nanocrystalline apatites analogous to the mineral phase of natural bone onto their surfaces, i.e. they are bioactive. They also stimulate osteoblast proliferation and differentiation and, therefore, accelerate the healing processes. Silica-based ordered mesoporous materials are excellent candidates to be used as third generation bioceramics that enable the adsorption and local control release of biological active agents that promote bone regeneration. This local delivery capability together with the bioactive behavior of mesoporous silicas opens up promising expectations in the bioclinical field. In this review, the last advances in nanochemistry aimed at designing and tailoring the chemical and textural properties of mesoporous silicas for biomedical applications are described. The recent developed strategies to synthesize bioactive glasses with ordered mesopore arrangements are also summarized. Finally, a deep discussion about the influence of the textural parameters and organic modification of mesoporous silicas on molecules adsorption and controlled release is performed.

  3. The impact of framework organic functional groups on the hydrophobicity and overall stability of mesoporous silica materials

    Smeulders, Geert; Meynen, Vera; Silvestre-Albero, Ana; Houthoofd, Kristof; Mertens, Myrjam; Silvestre-Albero, Joaquin; Martens, Johan A.; Cool, Pegie

    2012-01-01

    Graphical abstract: The stability (hydrothermal, mechanical and chemical) of PMOs is studied in a systematic way and ranks them between classic and other hybrid mesoporous silica materials. Highlights: ► The stability (hydrothermal, mechanical and chemical) of PMOs is studied. ► Compared stability of PMOs with classic and other hybrid mesoporous silica materials. ► Immersion calorimetry to study the effect of hydrophobicity. ► PMOs show superior stability. - Abstract: The hydrothermal, mechanical and chemical stability of various mesoporous materials have been studied in detail, using X-ray diffraction and nitrogen sorption. Pure siliceous nanoporous powders (MCM-41 and SBA-15) are evaluated against their hybrid counterparts; namely 2 types of periodic mesoporous organosilicas (benzene and ethane bridged PMOs) and an organosilane grafted MCM-41 material. In primary tests, the stability of the hybrid materials is found to be superior compared to that of the pure siliceous ones. The stability of the materials was correlated to their hydrophobicity via immersion calorimetry, applied for the first time in this context. Based on these results, a clear correlation between the hydrophobicity of a material and its stability has been revealed. In addition, with 29 Si-MAS-NMR and vacuum experiments, the mechanism of the structural deterioration in the three different stability treatments could be unambiguously identified as the hydrolyzation of the siloxane bonds. The homogeneity of the hydrophobic groups throughout the entire network was found to be of great importance, irrespective of the hydrophobic nature at the surface as determined by calorimetric measurements. The results reveal that the most stable material can withstand (a) a pressure of 740 MPa during 5 min, (b) a 2 h stirring in a 2 M NaOH solution and (c) a 3 day steaming treatment at 393 K.

  4. The impact of framework organic functional groups on the hydrophobicity and overall stability of mesoporous silica materials

    Smeulders, Geert, E-mail: geert.smeulders@ua.ac.be [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium); Meynen, Vera [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium); Silvestre-Albero, Ana [Universidad de Alicante, Laboratorio de Materiales Avanzados, Apartado 99, 03080 Alicante (Spain); Houthoofd, Kristof [KULeuven, Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Mertens, Myrjam [Flemish Institute for Technological Research (VITO N.V.), Boeretang 200, 2400 Mol (Belgium); Silvestre-Albero, Joaquin [Universidad de Alicante, Laboratorio de Materiales Avanzados, Apartado 99, 03080 Alicante (Spain); Martens, Johan A. [KULeuven, Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Cool, Pegie [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium)

    2012-02-15

    Graphical abstract: The stability (hydrothermal, mechanical and chemical) of PMOs is studied in a systematic way and ranks them between classic and other hybrid mesoporous silica materials. Highlights: Black-Right-Pointing-Pointer The stability (hydrothermal, mechanical and chemical) of PMOs is studied. Black-Right-Pointing-Pointer Compared stability of PMOs with classic and other hybrid mesoporous silica materials. Black-Right-Pointing-Pointer Immersion calorimetry to study the effect of hydrophobicity. Black-Right-Pointing-Pointer PMOs show superior stability. - Abstract: The hydrothermal, mechanical and chemical stability of various mesoporous materials have been studied in detail, using X-ray diffraction and nitrogen sorption. Pure siliceous nanoporous powders (MCM-41 and SBA-15) are evaluated against their hybrid counterparts; namely 2 types of periodic mesoporous organosilicas (benzene and ethane bridged PMOs) and an organosilane grafted MCM-41 material. In primary tests, the stability of the hybrid materials is found to be superior compared to that of the pure siliceous ones. The stability of the materials was correlated to their hydrophobicity via immersion calorimetry, applied for the first time in this context. Based on these results, a clear correlation between the hydrophobicity of a material and its stability has been revealed. In addition, with {sup 29}Si-MAS-NMR and vacuum experiments, the mechanism of the structural deterioration in the three different stability treatments could be unambiguously identified as the hydrolyzation of the siloxane bonds. The homogeneity of the hydrophobic groups throughout the entire network was found to be of great importance, irrespective of the hydrophobic nature at the surface as determined by calorimetric measurements. The results reveal that the most stable material can withstand (a) a pressure of 740 MPa during 5 min, (b) a 2 h stirring in a 2 M NaOH solution and (c) a 3 day steaming treatment at 393 K.

  5. Ordered mesoporous MFe(2)O(4) (M = Co, Cu, Mg, Ni, Zn) thin films with nanocrystalline walls, uniform 16 nm diameter pores and high thermal stability: template-directed synthesis and characterization of redox active trevorite.

    Haetge, Jan; Suchomski, Christian; Brezesinski, Torsten

    2010-12-20

    In this paper, we report on ordered mesoporous NiFe(2)O(4) thin films synthesized via co-assembly of hydrated ferric nitrate and nickel chloride with an amphiphilic diblock copolymer, referred to as KLE. We establish that the NiFe(2)O(4) samples are highly crystalline after calcination at 600 °C, and that the conversion of the amorphous inorganic framework comes at little cost to the ordering of the high quality cubic network of pores averaging 16 nm in diameter. We further show that the synthesis method employed in this work can be readily extended to other ferrites, such as CoFe(2)O(4), CuFe(2)O(4), MgFe(2)O(4), and ZnFe(2)O(4), which could pave the way for innovative device design. While this article focuses on the self-assembly and characterization of these materials using various state-of-the-art techniques, including electron microscopy, grazing incidence small-angle X-ray scattering (GISAXS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), as well as UV-vis and Raman spectroscopy, we also examine the electrochemical properties and show the benefits of combining a continuous mesoporosity with nanocrystalline films. KLE-templated NiFe(2)O(4) electrodes exhibit reasonable levels of lithium ion storage at short charging times which stem from facile pseudocapacitance.

  6. Isomeric periodic mesoporous organosilicas with controllable properties

    Vercaemst, C.; Ide, I.; Friedrich, H.; de Jong, K.P.; Verpoort, F.; van der Voort, P.

    2009-01-01

    The synthesis procedure for isomeric periodic mesoporous organosilicas with E-configured ethenylene bridges was investigated using the homemade pure E-isomer of 1,2-bis(triethoxysilyl)ethene. The pH, aging temperature and the presence of cosolvents played a key role in obtaining well-ordered

  7. High drug load, stable, manufacturable and bioavailable fenofibrate formulations in mesoporous silica: a comparison of spray drying versus solvent impregnation methods.

    Hong, Shiqi; Shen, Shoucang; Tan, David Cheng Thiam; Ng, Wai Kiong; Liu, Xueming; Chia, Leonard S O; Irwan, Anastasia W; Tan, Reginald; Nowak, Steven A; Marsh, Kennan; Gokhale, Rajeev

    2016-01-01

    Encapsulation of drugs in mesoporous silica using co-spray drying process has been recently explored as potential industrial method. However, the impact of spray drying on manufacturability, physiochemical stability and bioavailability in relation to conventional drug load processes are yet to be fully investigated. Using a 2(3) factorial design, this study aims to investigate the effect of drug-loading process (co-spray drying and solvent impregnation), mesoporous silica pore size (SBA-15, 6.5 nm and MCM-41, 2.5 nm) and percentage drug load (30% w/w and 50% w/w) on material properties, crystallinity, physicochemical stability, release profiles and bioavailability of fenofibrate (FEN) loaded into mesoporous silica. From the scanning electronic microscopy (SEM) images, powder X-ray diffraction and Differential scanning calorimetry measurements, it is indicated that the co-spray drying process was able to load up to 50% (w/w) FEN in amorphous form onto the mesoporous silica as compared to the 30% (w/w) for solvent impregnation. The in vitro dissolution rate of the co-spray dried formulations was also significantly (p = 0.044) better than solvent impregnated formulations at the same drug loading. Six-month accelerated stability test at 40 °C/75 RH in open dish indicated excellent physical and chemical stability of formulations prepared by both methods. The amorphous state of FEN and the enhanced dissolution profiles were well preserved, and very low levels of degradation were detected after storage. The dog data for the three selected co-spray-dried formulations revealed multiple fold increment in FEN bioavailability compared to the reference crystalline FEN. These results validate the viability of co-spray-dried mesoporous silica formulations with high amorphous drug load as potential drug delivery systems for poorly water soluble drugs.

  8. Templating mesoporous zeolites

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

    2008-01-01

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

  9. Interface chemistry of nanostructured materials: ion adsorption on mesoporous alumina.

    Wang, Yifeng; Bryan, Charles; Xu, Huifang; Pohl, Phil; Yang, Yi; Brinker, C Jeffrey

    2002-10-01

    This paper presents a part of our work on understanding the effect of nanoscale pore space confinement on ion sorption by mesoporous materials. Acid-base titration experiments were performed on both mesoporous alumina and alumina particles under various ionic strengths. The point of zero charge (PZC) for mesoporous alumina was measured to be approximately 9.1, similar to that for nonmesoporous alumina materials, indicating that nanoscale pore space confinement does not have a significant effect on the PZC of pore surfaces. However, for a given pH deviation from the PZC, (pH-PZC), the surface charge per mass on mesoporous alumina was as much as 45 times higher than that on alumina particles. This difference cannot be fully explained by the surface area difference between the two materials. Our titration data have demonstrated that nanoscale confinement has a significant effect, most likely via the overlap of the electric double layer (EDL), on ion sorption onto mesopore surfaces. This effect cannot be adequately modeled by existing surface complexation models, which were developed mostly for an unconfined solid-water interface. Our titration data have also indicated that the rate of ion uptake by mesoporous alumina is relatively slow, probably due to diffusion into mesopores, and complete equilibration for sorption could take 4-5 min. A molecular simulation using a density functional theory was performed to calculate ion adsorption coefficients as a function of pore size. The calculation has shown that as pore size is reduced to nanoscales (<10 nm), the adsorption coefficients of ions can vary by more than two orders of magnitude relative to those for unconfined interfaces. The prediction is supported by our experimental data on Zn sorption onto mesoporous alumina. Owing to their unique surface chemistry, mesoporous materials can potentially be used as effective ion adsorbents for separation processes and environmental cleanup.

  10. 一步法合成载铁有序介孔碳材料的形成机理%Mechanism of the synthesis of ordered Fe-containing mesoporous carbon composite materials in one-pot

    凌晓凤; 顾娟; 李健生; 孙秀云; 韩卫清; 沈锦优; 王连军

    2012-01-01

    采用软模板路线以三嵌段共聚物F127为模板剂,间苯二酚-甲醛缩聚所形成酚醛树脂(RF)为碳源,与酚羟基有络合作用的无机铁盐为金属前体,在无外加酸碱催化剂的条件下,利用铁盐的水解反应形成酚醛缩聚所需酸性环境,多组分共组装一步合成了载铁有序介孔碳材料(Fe/OMC)。对Fe/OMC合成各阶段过程进行了分析,利用X射线衍射、透射电子显微镜等手段对材料进行表征,比较了不同老化时间、硝酸铁投加量及酚醛比例等合成条件对材料结构的影响规律。结果表明,在较长的老化时间(≥60 h)、适宜的n(Fe)/n(R)比(0.05~0.2)和n(R)/n(F)比[(1/1.5)~(1/2)]条件下,均可形成有序的介孔结构。在此基础上,提出了载铁有序介孔碳材料的形成机理。%Ordered Fe-containing mesoporous carbon composite materials(Fe/OMC)have been synthesized via soft-templating routes by using triblock copolymer F127 as a template agent,resorcinol(R)-formaldehyde(F)as a carbon precursor,inorganic iron salts having complex reaction with phenols as a metal precursor in one-pot.The main strategy of this approach was to utilize the acidity self-generated from the hydrolysis of inorganic salts in the aqueous solutions as the catalyst for RF polymerization,where no addition of mineral acids was necessary.The resultant Fe/OMC materials were characterized by X-ray diffraction,Transmission electron microscopy.The influences of the aging time,the dosage of iron nitrate and the molar ratio of R/F on the structure of the obtained materials were investigated.Results show that the ordered mesoporous structure can be obtained under the synthetic condition of the aging time≥60 h,n(Fe)/n(R)=0.05— 0.2,n(R)/n(F)=1/1.5— 1/2.0.Moreover,a possible mechanism of the synthesis of Fe/OMC was proposed.

  11. Simple synthesis of mesoporous FeNi/graphitic carbon nanocomposite catalysts and study on their activities in catalytic cracking of toluene

    Wang, Yangang, E-mail: ygwang8136@gmail.com [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Chen, Yuting; Yao, Mingcui [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Qin, Hengfei; Kang, Shifei; Li, Xi [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China); Zuo, Yuanhui; Zhang, Xiaodong [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Cui, Li-Feng, E-mail: lifeng.cui@gmail.com [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China)

    2015-11-01

    Mesoporous FeNi alloy/graphitic carbon nanocomposite catalysts with different Fe/Ni molar ratios have been synthesized through a simple solid–liquid grinding/templating method using mesoporous silica SBA-15 as the template. Metal nitrates and natural soybean oil were respectively used as the magnetic particle precursors and carbon source, which can be infiltrated into the silica template after simple impregnation, grinding and subsequent heat treatment. X-ray diffraction, nitrogen adsorption–desorption, transmission electron microscopy and thermogravimetric analysis techniques were used to characterize the samples. It is observed that high contents of FeNi alloy nanoparticles with the sizes of 3–6 nm are well dispersed into the walls of graphitic mesoporous carbon matrix, and the resulting nanocomposites have a uniform mesostructure with a high specific surface area and large pore volume. Because of these properties, the obtained FeNi/graphitic carbon nanocomposites can be used as novel catalysts for the catalytic cracking of toluene and exhibit a higher activity and stability than FeNi/commercial activated carbon (AC) catalyst. After a period of 810 min reaction at 700 °C, the toluene conversion on the FeNi/graphitic carbon nanocomposites can be maintained at a level of more than 75% and this value is 2.5 times as high as that of the FeNi/AC catalyst. - Highlights: • Mesoporous FeNi alloy/graphitic carbon nanocomposites (FeNi/GCN) were synthesized. • High contents of FeNi alloy nanoparticles are well embedded into the graphitic carbon walls. • The obtained FeNi/GCN catalysts have a high surface area and uniform mesostructure. • The FeNi/GCN catalysts exhibited excellent catalytic performance in the cracking of toluene.

  12. Mesoporous carbon incorporated metal oxide nanomaterials as supercapacitor electrodes

    Jiang, Hao [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ma, Jan [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Chunzhong [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2012-08-08

    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. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Efficient visible-light photocatalytic activity by band alignment in mesoporous ternary polyoxometalate-Ag2S-CdS semiconductors

    Kornarakis, I.; Lykakis, I. N.; Vordos, N.; Armatas, G. S.

    2014-07-01

    anions with different reduction potentials, such as PW12O403-, SiW12O404- and PMo12O403-, were employed as electron acceptors in these ternary heterojunction photocatalysts. Characterization by small-angle X-ray scattering, X-ray diffraction, transmission electron microscopy and N2 physisorption measurements showed hexagonal arrays of POM-Ag2S-CdS hybrid nanorods with large internal BET surface areas and uniform mesopores. The Keggin structure of the incorporated POM clusters was also verified by elemental X-ray spectroscopy microanalysis, infrared and diffuse-reflectance ultraviolet-visible spectroscopy. These new porous materials were implemented as visible-light-driven photocatalysts, displaying exceptional high activity in aerobic oxidation of various para-substituted benzyl alcohols to the corresponding carbonyl compounds. Our experiments show that the spatial separation of photogenerated electrons and holes at CdS through the potential gradient along the CdS-Ag2S-POM interfaces is responsible for the increased photocatalytic activity. Electronic supplementary information (ESI) available: EDS spectra of STA/CdS and STA/Ag2S/CdS samples, SAXS patterns and N2 physisorption isotherms of SBA-15 silica, IR spectra of meso-CdS and POM-Ag2S-CdS materials, catalytic data of the as-prepared CdS based mesostructures and TiO2 (Degussa P25) nanoparticles, PL spectra of meso-CdS, Ag2S-CdS, CuS/CdS and STA/Ag2S/CdS samples, N2 physisorption isotherms of b-STA/Ag2S/CdS and STA/CuS/CdS, 1H NMR spectra of 8 oxidation products, and EDS and IR spectra and N2 physisorption isotherms of the reused STA/Ag2S/CdS catalyst. See DOI: 10.1039/c4nr01094a

  14. Amperometric carbohydrate antigen 19-9 immunosensor based on three dimensional ordered macroporous magnetic Au film coupling direct electrochemistry of horseradish peroxidase

    Zhang, Qi [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Chen, Xiaojun, E-mail: chenxj_njut@126.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China); Tang, Yin [Zhangjiagang Hospital of Traditional Chinese Medicine, Zhangjiagang 215600 (China); Ge, Lingna; Guo, Buhua [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Yao, Cheng, E-mail: yaochengnjut@163.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China)

    2014-03-01

    Highlights: • Three dimensional ordered macroporous magnetic electrode was newly used in electrochemical immunosensor. • The large surface area of macroporous magnetic electrode could improve the immobilized amount of antibody. • Au nanoparticles functionalized SBA-15 was used to immobilize enzyme labeled Ab₂ and enzyme. • Macroporous magnetic electrode and Au nanoparticles composite facilitated the direct electron transfer of enzyme. • The immunoassay avoided adding electron transfer mediator, simplifying the procedure. Abstract: A sandwich-type electrochemical immunosensor for the detection of carbohydrate antigen 19-9 (CA 19-9) antigen based on the immobilization of primary antibody (Ab₁) on three dimensional ordered macroporous magnetic (3DOMM) electrode, and the direct electrochemistry of horseradish peroxidase (HRP) that was used as both the label of secondary antibody (Ab₂) and the blocking reagent. The 3DOMM electrode was fabricated by introducing core–shell Au–SiO₂@Fe₃O₄ nanospheres onto the surface of three dimensional ordered macroporous (3DOM) Au electrode via the application of an external magnet. Au nanoparticles functionalized SBA-15 (Au@SBA-15) was conjugated to the HRP labeled secondary antibody (HRP-Ab₂) through the Au–SH or Au–NH₃⁺ interaction, and HRP was also used as the block reagent. The formation of antigen–antibody complex made the combination of Au@SBA-15 and 3DOMM exhibit remarkable synergistic effects for accelerating direct electron transfer (DET) between HRP and the electrode. Under the optimal conditions, the DET current signal increased proportionally to CA 19-9 concentration in the range of 0.05 to 15.65 U mL⁻¹ with a detection limit of 0.01 U mL⁻¹. Moreover, the immunosensor showed high selectivity, good stability, satisfactory reproducibility and regeneration. Importantly, the developed method was used to assay clinical serum specimens, achieving a good relation with those obtained from

  15. Improvement of the Derjaguin-Broekhoff-de Boer theory for the capillary condensation/evaporation of nitrogen in spherical cavities and its application for the pore size analysis of silicas with ordered cagelike mesopores.

    Kowalczyk, Piotr; Jaroniec, Mietek; Kaneko, Katsumi; Terzyk, Artur P; Gauden, Piotr A

    2005-11-08

    In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method.

  16. Synthesis of mesoporous silica-coated magnetic nanoparticles modified with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole and its application as Cu(II) adsorbent from aqueous samples

    Wondracek, Marcos Henrique P., E-mail: marcoswondracek@gmail.com [Faculdade de Ciências Exatas e Tecnologia – UFGD, C.P.533, 79804-970 Dourados, MS (Brazil); Institute of Chemistry-UNESP, 14800-060 Araraquara, SP (Brazil); Jorgetto, Alexandre Oliveira [Institute of Biosciences of Botucatu-UNESP – Chemistry and Biochemistry Department, C.P. 510, 18618-000 Botucatu, SP (Brazil); Institute of Chemistry-UNESP, 14800-060 Araraquara, SP (Brazil); Silva, Adrielli Cristina P. [Institute of Biosciences of Botucatu-UNESP – Chemistry and Biochemistry Department, C.P. 510, 18618-000 Botucatu, SP (Brazil); Ivassechen, Janaíne do Rocio [Institute of Biosciences of Botucatu-UNESP – Chemistry and Biochemistry Department, C.P. 510, 18618-000 Botucatu, SP (Brazil); Institute of Chemistry-UNESP, 14800-060 Araraquara, SP (Brazil); Schneider, José Fabián [Department of Physics and Interdisciplinary Science, Institute of Physics of Sao Carlos – USP C.P. 369, 13560-970 Sao Carlos, SP (Brazil); Saeki, Margarida Juri; Pedrosa, Valber Albuquerque [Institute of Biosciences of Botucatu-UNESP – Chemistry and Biochemistry Department, C.P. 510, 18618-000 Botucatu, SP (Brazil); Yoshito, Walter Kenji [Centro de Ciência e Tecnologia de Materiais – IPEN, 05508-000 São Paulo, SP (Brazil); Colauto, Fabiano; Ortiz, Wilson A. [Departamento de Física-UFsCar, C.P. 676, 13565-905 São Carlos, SP (Brazil); Castro, Gustavo Rocha [Institute of Biosciences of Botucatu-UNESP – Chemistry and Biochemistry Department, C.P. 510, 18618-000 Botucatu, SP (Brazil)

    2016-03-30

    Graphical abstract: - Highlights: • Groups of interest to perform metal complexation could be detected in the material. • Adsorption isotherms are in agreement with Langmuir model. • The material has a typical behavior of superparamagnetic material with high magnetization. - Abstract: This study presents an alternative, rapid, and environment-friendly synthesis procedure of a magnetic core–shell mesoporous SBA-15 silica composite, its functionalization with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald), and its application in dispersive solid-phase microextraction (DSPME) for Cu(II) from water. The materials were characterized through magnetization measurements, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) of {sup 29}Si and {sup 13}C, elemental analysis, and surface area measurements. FTIR and NMR analyses indicated the presence of the ligand on the functionalized material and that it was coupled through a C−S bond. TEM images clearly show that the magnetite core particles were effectively coated with a silica shell. The material presented a surface area of 287.99 m{sup 2} g{sup −1} and an average pore diameter of approximately 15.1 nm. The material had its point of zero charge (PZC) determined (6.17) and its adsorption capacity was evaluated as a function of time, pH, and metal concentration. Dynamic adsorption equilibrium was reached in 120 min, and it had a good correlation with the pseudo-second-order kinetic model (r{sup 2} = 0.9997). The maximum experimental adsorption capacity (0.0786 mmol g{sup −1}) and the value calculated by the linearized Langmuir model (0.0799 mmol g{sup −1}) are very approximate, indicating the formation of a monolayer over the material. Furthermore, the material proved to be very stable, because their adsorption capacity remained greater than 95% even after 10 cycles of adsorption

  17. Synthesis of mesoporous silica-coated magnetic nanoparticles modified with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole and its application as Cu(II) adsorbent from aqueous samples

    Wondracek, Marcos Henrique P.; Jorgetto, Alexandre Oliveira; Silva, Adrielli Cristina P.; Ivassechen, Janaíne do Rocio; Schneider, José Fabián; Saeki, Margarida Juri; Pedrosa, Valber Albuquerque; Yoshito, Walter Kenji; Colauto, Fabiano; Ortiz, Wilson A.; Castro, Gustavo Rocha

    2016-01-01

    Graphical abstract: - Highlights: • Groups of interest to perform metal complexation could be detected in the material. • Adsorption isotherms are in agreement with Langmuir model. • The material has a typical behavior of superparamagnetic material with high magnetization. - Abstract: This study presents an alternative, rapid, and environment-friendly synthesis procedure of a magnetic core–shell mesoporous SBA-15 silica composite, its functionalization with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald), and its application in dispersive solid-phase microextraction (DSPME) for Cu(II) from water. The materials were characterized through magnetization measurements, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) of "2"9Si and "1"3C, elemental analysis, and surface area measurements. FTIR and NMR analyses indicated the presence of the ligand on the functionalized material and that it was coupled through a C−S bond. TEM images clearly show that the magnetite core particles were effectively coated with a silica shell. The material presented a surface area of 287.99 m"2 g"−"1 and an average pore diameter of approximately 15.1 nm. The material had its point of zero charge (PZC) determined (6.17) and its adsorption capacity was evaluated as a function of time, pH, and metal concentration. Dynamic adsorption equilibrium was reached in 120 min, and it had a good correlation with the pseudo-second-order kinetic model (r"2 = 0.9997). The maximum experimental adsorption capacity (0.0786 mmol g"−"1) and the value calculated by the linearized Langmuir model (0.0799 mmol g"−"1) are very approximate, indicating the formation of a monolayer over the material. Furthermore, the material proved to be very stable, because their adsorption capacity remained greater than 95% even after 10 cycles of adsorption/desorption. A high enrichment factor of 98

  18. Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

    Kang, Taewook; Oh, Seogil; Kim, Honggon; Yi, Jongheop

    2005-06-21

    A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.

  19. C-H and C-C activation of n -butane with zirconium hydrides supported on SBA15 containing N-donor ligands: [(≡SiNH-)(≡SiX-)ZrH2], [(≡SiNH-)(≡SiX-)2ZrH], and[(≡SiN=)(≡SiX-)ZrH] (X = -NH-, -O-). A DFT study

    Pasha, Farhan Ahmad

    2014-07-01

    Density functional theory (DFT) was used to elucidate the mechanism of n-butane hydrogenolysis (into propane, ethane, and methane) on well-defined zirconium hydrides supported on SBA15 coordinated to the surface via N-donor surface pincer ligands: [(≡SiNH-)(≡SiO-)ZrH2] (A), [(≡SiNH-)2ZrH2] (B), [(≡SiNH-)(≡SiO-) 2ZrH] (C), [(≡SiNH-)2(≡SiO-)ZrH] (D), [(≡SiN=)(≡Si-O-)ZrH] (E), and [(≡SiN=)(≡SiNH-)ZrH] (F). The roles of these hydrides have been investigated in C-H/C-C bond activation and cleavage. The dihydride A linked via a chelating [N,O] surface ligand was found to be more active than B, linked to the chelating [N,N] surface ligand. Moreover, the dihydride zirconium complexes are also more active than their corresponding monohydrides C-F. The C-C cleavage step occurs preferentially via β-alkyl transfer, which is the rate-limiting step in the alkane hydrogenolysis. The energetics of the comparative pathways over the potential energy surface diagram (PES) reveals the hydrogenolysis of n-butane into propane and ethane. © 2014 American Chemical Society.

  20. Highly improved ethanol gas-sensing performance of mesoporous nickel oxides nanowires with the stannum donor doping

    Wei, Junqi; Li, Xiaoqing; Han, Yanbing; Xu, Jingcai; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Jing; Yang, Yanting; Ge, Hongliang; Wang, Xinqing

    2018-06-01

    Mesoporous nickel oxides (NiO) and stannum(Sn)-doped NiO nanowires (NWs) were synthesized by using SBA-15 templates with the nanocasting method. X-ray diffraction, transmission electron microscope, energy dispersive spectrometry, nitrogen adsorption/desorption isotherm and UV–vis spectrum were used to characterize the phase structure, components and microstructure of the as-prepared samples. The gas-sensing analysis indicated that the Sn-doping could greatly improve the ethanol sensitivity for mesoporous NiO NWs. With the increasing Sn content, the ethanol sensitivity increased from 2.16 for NiO NWs up to the maximum of 15.60 for Ni0.962Sn0.038O1.038, and then decreased to 12.24 for Ni0.946Sn0.054O1.054 to 100 ppm ethanol gas at 340 °C. The high surface area from the Sn-doping improved the adsorption of oxygen on the surface of NiO NWs, resulting in the smaller surface resistance in air. Furthermore, owing to the recombination of the holes in hole-accumulation lay with the electrons from the donor impurity level and the increasing the body defects for Sn-doping, the total resistance in ethanol gas enhanced greatly. It was concluded that the sensitivity of Sn-doped NiO NWs based sensor could be greatly improved by the higher surface area and high-valence donor substitution from Sn-doping.

  1. Innovative preparation of Au/C by replication of gold-containing mesoporous silica catalysts

    Kerdi, Fatmé ; Caps, Valerie; Tuel, Alain

    2010-01-01

    A new strategy, based on the nanocasting concept, has been used to prepare gold nanoparticles (NPs) highly dispersed in meso-structured carbons. Gold is first introduced in various functionalized mesostructured silicas (MCM-48 and SBA-15

  2. Rational design of mesoporous metals and related nanomaterials by a soft-template approach.

    Yamauchi, Yusuke; Kuroda, Kazuyuki

    2008-04-07

    We review recent developments in the preparation of mesoporous metals and related metal-based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore-size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct-template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct-template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal-based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia\\3d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.

  3. Near-field radiative heat transfer in mesoporous alumina

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

    2015-01-01

    The thermal conductivity of mesoporous material has aroused the great interest of scholars due to its wide applications such as insulation, catalyst, etc. Mesoporous alumina substrate consists of uniformly distributed, unconnected cylindrical pores. Near-field radiative heat transfer cannot be ignored, when the diameters of the pores are less than the characteristic wavelength of thermal radiation. In this paper, near-field radiation across a cylindrical pore is simulated by employing the fluctuation dissipation theorem and Green function. Such factors as the diameter of the pore, and the temperature of the material are further analyzed. The research results show that the radiative heat transfer on a mesoscale is 2∼4 orders higher than on a macroscale. The heat flux and equivalent thermal conductivity of radiation across a cylindrical pore decrease exponentially with pore diameter increasing, while increase with temperature increasing. The calculated equivalent thermal conductivity of radiation is further developed to modify the thermal conductivity of the mesoporous alumina. The combined thermal conductivity of the mesoporous alumina is obtained by using porosity weighted dilute medium and compared with the measurement. The combined thermal conductivity of mesoporous silica decreases gradually with pore diameter increasing, while increases smoothly with temperature increasing, which is in good agreement with the experimental data. The larger the porosity, the more significant the near-field effect is, which cannot be ignored. (paper)

  4. Bulk Concentration Dependence of Electrolyte Resistance Within Mesopores of Carbon Electrodes in Electric Double-Layer Capacitors

    Kim, Jaekwang; Kim, Daeun; Lee, Ilbok; Son, Hyungbin; Lee, Donghyun; Yoon, Songhun [Chung-Ang University, Seoul (Korea, Republic of); Shim, Hyewon [Korea Institute of Nuclear Nonproliferation and Control, Daejeon (Korea, Republic of); Lee, Jinwoo [POSTECH, Pohang (Korea, Republic of)

    2016-02-15

    Hexagonally ordered mesoporous carbon materials were prepared and used as electrode materials in an electric double-layer capacitor. Using this electrode, the change of electrolyte resistance within the mesopores was investigated according to the bulk electrolyte concentration. Using three different electrochemical transient experiments-imaginary capacitance analysis, chronoamperometry, and hronopotentiometry-the time constant associated with electrolyte transport was determined, which was then used to obtain the electrolyte resistance within the mesopores. With decreasing electrolyte concentration, the increase in electrolyte resistance was smaller than the increase in the resistivity of the bulk electrolyte, which is indicative of a different environment for ionic transport within the mesopores. On using the confinement effect within the mesopores, the predicted higher concentration within mesopore probably results in lower electrolyte resistance, especially under low bulk concentrations.

  5. General strategy for fabricating thoroughly mesoporous nanofibers

    Hou, Huilin; Wang, Lin; Gao, Fengmei; Wei, Guodong; Tang, Bin; Yang, Weiyou; Wu, Tao

    2014-01-01

    mesoporous nanofibers with high purity and uniformity. Here, we report a general, simple and cost-effective strategy, namely, foaming-assisted electrospinning, for producing mesoporous nanofibers with high purity and enhanced specific surface areas. As a

  6. Aromatization of alkanes over Pt promoted conventional and mesoporous gallosilicates of MEL zeolite

    Akhtar, M. N.; Al-Yassir, N.; Al-Khattaf, S.; Čejka, Jiří

    2012-01-01

    Aromatization of hexane and propane was investigated over Pt promoted mesoporous gallium-containing HZSM-11 with controlled mesoporosity generated by desilication. Prepared catalysts were characterized by nitrogen adsorption, X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared of chemisorbed pyridine, and NH 3 temperature programmed desorption confirming the development of intracrystalline mesoporosity of Ga-containing HZSM-11. The catalytic activities, which were compared in the aromatization of n-hexane and propane, increased upon desilication. The aromatization of n-hexane decreased in the following order, Pt/mesoporous GaZSM-11 Pt/conventional GaZSM-11 mesoporous GaZSM-11 > conventional GaZSM-11. Hexane conversion reached 70.1% over mesoporous Pt/GaZSM-11 with Si/Ga of 61, as compared with 29.6 and 24.9% for corresponding mesoporous and conventional GaZSM-11 (Si/Ga = 94), respectively, for experiments at liquid hour space velocity of 3.6 h -1, and 540 °C. Comparison of BTX (benzene-toluene-xylene) selectivity at the conversion level of ∼21.0% revealed that Pt/mesoporous GaZSM-11 is more selective than corresponding mesoporous and conventional GaZSM-11. The BTX selectivity over Pt/mesoporous GaZSM-11 (Si/Ga = 94), which showed strong dependence on the conversion, reached 28.2%, whereas over corresponding mesoporous and conventional GaZSM-11catalysts reached 19.1% and 5.5%, respectively. A higher conversion and better selectivity can be attributed to the improved accessibility to the active extra-framework Ga species owing to the generation of mesopores inside the zeolite particles and shortening the contact time. It is worth mentioning that the prepared catalysts exhibited quite low activity in propane aromatization but exhibiting similar trends as for hexane aromatization. © 2011 Elsevier B.V. All rights reserved.

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

    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.

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

    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.

  9. Polypyrrole/hexagonally ordered silica nanocomposite as a novel fiber coating for solid-phase microextraction

    Gholivand, Mohammad Bagher; Abolghasemi, Mir Mahdi; Fattahpour, Peyman

    2011-01-01

    Highlights: → The polypyrrole/SBA15) nanocomposite was used as a novel coating for SPME fiber. → The proposed fiber was used for the extraction of polycyclic aromatic hydrocarbons. → The proposed SPME fiber is thermal stable, and it has a low limit of detection. → The SPME fiber was applied in polluted river water and wastewater samples. - Abstract: A highly porous fiber coated polypyrrole/hexagonally ordered silica (PPy/SBA15) materials were prepared for solid-phase microextraction (SPME). The PPy/SBA15 nanocomposite was synthesized by an in situ polymerization technique. The resulting material was characterized by the scanning electron microscopy, thermogravimetric analysis and differential thermal analysis. The prepared nanomaterial was immobilized onto a stainless steel wire for fabrication of the SPME fiber. The fiber was evaluated for the extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions in combination with gas chromatography-mass spectrometry (GC-MS). A one at-the-time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, stirring rate, desorption time and desorption temperature. In optimum conditions (extraction temperature 70 deg. C, extraction time 20 min, ionic strength 20% (W V -1 ), stirring rate 500 rpm, desorption temperature 270 deg. C, desorption time 5 min) the repeatability for one fiber (n = 3), expressed as relative standard deviation (R.S.D. %), was between 5.0% and 9.3% for the tested compounds. The quantitation limit for the studied compounds were between 13.3 and 66.6 pg mL -1 . The life span and stability of the PPy/SBA15 fiber are good, and it can be used more than 50 times at 260 deg. C without any significant change in sorption properties. The developed method offers the advantage of being simple to use, with shorter analysis times, lower cost of equipment, thermal stability of fiber and high

  10. Application of mesoporous carbon and modified mesoporous carbon for treatment of DMF sewage

    Liu, Fang, E-mail: liufangfw@163.com; Gao, Ya; Zhang, Shuang; Yan, Xi; Fan, Fengtao; Zhao, Chaocheng; Sun, Juan [China University of Petroleum(East China), Department of Chemical Engineering (China)

    2016-02-15

    Mesoporous carbon (MC) was prepared in soft template, and potassium ferricyanide was added into MC to prepare the modified mesoporous carbon (MMC). TEM, SEM, FT-IR, and N{sub 2} adsorption–desorption were used to characterize the textural properties of mesoporous materials. The BET specific surface area, pore volume, and the pore size of MC and MMC were 607.6321 and 304.7475 m{sup 2}/g, 0.313552 and 0.603573 cm{sup 3}/g, and 5.4356 and 7.9227 nm, respectively. The adsorption capabilities of MC and MMC were compared with the silica mesoporous material MCM-41. The influences of different adsorption conditions were optimized. For MC, the optimums of adsorbent dose, DMF initial concentration, rotating speed, and pH were 0.002 mg/50 mL, 200 mg/L, 200 r/min, and 4, respectively. MMC showed the highest DMF adsorption capacity at adsorbent dose 0.002 g/50 mL, DMF initial concentration 1000 mg/L, rotating speed 1000 r/min, pH more than 9, and contact time of less than 20 min. Meanwhile for MC, MMC, Pseudo-second-order equation was used to fit adsorption kinetics data. And adsorption process could be well fitted by Langmuir and Freundlich adsorption isotherms of MC, MMC. The results showed that MMC was a perfect adsorbent for DMF, and it was easy to separation and recycle. The recycling property of MMC was still relatively better than other two adsorbents.

  11. Hierarchical activated mesoporous phenolic-resin-based carbons for supercapacitors.

    Wang, Zhao; Zhou, Min; Chen, Hao; Jiang, Jingui; Guan, Shiyou

    2014-10-01

    A series of hierarchical activated mesoporous carbons (AMCs) were prepared by the activation of highly ordered, body-centered cubic mesoporous phenolic-resin-based carbon with KOH. The effect of the KOH/carbon-weight ratio on the textural properties and capacitive performance of the AMCs was investigated in detail. An AMC prepared with a KOH/carbon-weight ratio of 6:1 possessed the largest specific surface area (1118 m(2) g(-1)), with retention of the ordered mesoporous structure, and exhibited the highest specific capacitance of 260 F g(-1) at a current density of 0.1 A g(-1) in 1 M H2 SO4 aqueous electrolyte. This material also showed excellent rate capability (163 F g(-1) retained at 20 A g(-1)) and good long-term electrochemical stability. This superior capacitive performance could be attributed to a large specific surface area and an optimized micro-mesopore structure, which not only increased the effective specific surface area for charge storage but also provided a favorable pathway for efficient ion transport. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Mesoporous amorphous tungsten oxide electrochromic films: a Raman analysis of their good switching behavior

    Chatzikyriakou, Dafni; Krins, Natacha; Gilbert, Bernard; Colson, Pierre; Dewalque, Jennifer; Denayer, Jessica; Cloots, Rudi; Henrist, Catherine

    2014-01-01

    Graphical abstract: - Highlights: • Mesoporous films exhibit better electrochemical kinetics compared to the dense films. • Mesoporous films exhibit better reversibility compared to the dense films. • Li + cations disrupt WO 3 network in a reversible way in the mesoporous film. • Li + irreversibly intercalate in the voids of crystallites in the dense film. - Abstract: The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics. In this study, we prepared two types of amorphous films via the sol-gel technique: one dense and one mesoporous in order to compare their response upon lithium intercalation and de-intercalation. According to chronoamperometric measurements, Li + intercalates/de-intercalates faster in the mesoporous film (24s/6s) than in the dense film (48s/10s). The electrochemical measurements (cyclic voltammetry and chronoamperometry) also showed worse reversibility for the dense film compared to the mesoporous film, giving rise to important Li + trapping and remaining coloration of the film. Raman analysis showed that the mesoporous film provides more accessible and various W-O surface bonds for Li + intercalation. On the contrary, in the first electrochemical insertion and de-insertion in the dense film, Li + selectively reacts with a few surface W-O bonds and preferentially intercalates into pre-existing crystallites to form stable irreversible Li x WO 3 bronze

  13. A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

    Qu Fengyu; Zhu Guangshan; Lin Huiming; Zhang Weiwei; Sun Jinyu; Li Shougui; Qiu Shilun

    2006-01-01

    A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N 2 adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N 2 adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers

  14. Research Update: Mesoporous sensor nanoarchitectonics

    Katsuhiko Ariga

    2014-03-01

    Full Text Available In this short review, we have selected three main subjects: (i mesoporous materials, (ii sensing applications, and (iii the concept of nanoarchitectonics, as examples of recent hot topics in nanomaterials research. Mesoporous materials satisfy the conditions necessary not only for a wide range of applications but also for ease of production, by a variety of simple processes, which yield bulk quantities of materials without loss of their well-defined nanometric structural features. Sensing applications are of general importance because many events arise from interaction with external stimuli. In addition to these important features, nanoarchitectonics is a concept aimed at production of novel functionality of whole units according to concerted interactions within nanostructures. For the combined subject of mesoporous sensor nanoarchitectonics, we present recent examples of research in the corresponding fields categorized according to mechanism of detection including optical, electrical, and piezoelectric sensing.

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

    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. Copyright © 2013 Elsevier Inc. All rights reserved.

  16. Phospholipid-Coated Mesoporous Silica Nanoparticles Acting as Lubricating Drug Nanocarriers

    Tao Sun; Yulong Sun; Hongyu Zhang

    2018-01-01

    Osteoarthritis (OA) is a severe disease caused by wear and inflammation of joints. In this study, phospholipid-coated mesoporous silica nanoparticles (MSNs@lip) were prepared in order to treat OA at an early stage. The phospholipid layer has excellent lubrication capability in aqueous media due to the hydration lubrication mechanism, while mesoporous silica nanoparticles (MSNs) act as effective drug nanocarriers. The MSNs@lip were characterized by scanning electron microscope, transmission el...

  17. Probing Structural and Catalytic Characteristics of Galactose Oxidase Confined in Nanoscale Chemical Environments

    Ikemoto, Hideki; Mossin, Susanne; Ulstrup, Jens

    2014-01-01

    Galactose oxidase (GAOX) is a special metalloenzyme in terms of its active site structure and catalytic mechanisms. This work reports a study where the enzyme confined in a nanoscale chemical environment provided by mesoporous silicas (MPS) is probed. Two types of MPS, i.e. SBA-15 and MCF, were...... synthesized and used to accommodate GAOX. SBA-15-ROD is rod-shaped particles with periodically ordered nanopores (9.5 nm), while MCF has a mesocellular foam-like structure with randomly distributed pores (23 nm) interconnected by smaller windows (8.8 nm). GAOX is non-covalently confined in SBA-15- ROD, while...... it is covalently immobilized in MCF. Relatively high loadings in the range of 50–60 mg g1 are achieved. Electron spin resonance (ESR) spectroscopy is used to probe the active site structures of the enzyme. The similar ESR spectra observed for GAOX in the free and immobilized states support that the electronic...

  18. A flexible, bolaamphiphilic template for mesoporous silicas.

    Yuen, Alexander K L; Heinroth, Falk; Ward, Antony J; Masters, Anthony F; Maschmeyer, Thomas

    2013-08-28

    A novel symmetrical bolaamphiphile, containing two N-methylimidazolium head-groups bridged by a 32-methylene linker, was synthesized and characterized. A variety of mesoporous silicas was prepared using the bolaamphiphile as a "soft template". The effects of absolute surfactant concentration and synthesis conditions upon the morphologies of these silicas were investigated. For a given surfactant concentration, particle morphology; pore size; and pore ordering were modified through control of the template to silica-precursor ratio and synthesis conditions. Observed morphologies included: lenticular core-shell nanoparticles and decorticated globules, truncated hexagonal plates, and sheets. In all cases the mesopores are aligned along the shortest axis of the nanomaterial. Decorticated materials displayed surface areas of up to 1200 m(2) g(-1) and pore diameters (D(BJH)) of 24-28 Å. Small-angle X-ray diffraction and transmission electron microscopy measurements revealed that the majority of the materials has elliptical pores arranged in rectangular lattices (c2mm). Adoption of this symmetry group is a result of the template aggregate deformation from a regular hexagonal phase of cylindrical rods to a ribbon phase under the synthetic conditions.

  19. Magnetic mesoporous material for the sequestration of algae

    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.

  20. A tri-continuous mesoporous material with a silica pore wall following a hexagonal minimal surface

    Han, Yu

    2009-04-06

    Ordered porous materials with unique pore structures and pore sizes in the mesoporous range (2-50nm) have many applications in catalysis, separation and drug delivery. Extensive research has resulted in mesoporous materials with one-dimensional, cage-like and bi-continuous pore structures. Three families of bi-continuous mesoporous materials have been made, with two interwoven but unconnected channels, corresponding to the liquid crystal phases used as templates. Here we report a three-dimensional hexagonal mesoporous silica, IBN-9, with a tri-continuous pore structure that is synthesized using a specially designed cationic surfactant template. IBN-9 consists of three identical continuous interpenetrating channels, which are separated by a silica wall that follows a hexagonal minimal surface. Such a tri-continuous mesostructure was predicted mathematically, but until now has not been observed in real materials. © 2009 Macmillan Publishers Limited. All rights reserved.

  1. Synthesis and Textural Characterization of Mesoporous and Meso-/Macroporous Silica Monoliths Obtained by Spinodal Decomposition

    Anne Galarneau

    2016-04-01

    Full Text Available Silica monoliths featuring either mesopores or flow-through macropores and mesopores in their skeleton are prepared by combining spinodal phase separation and sol-gel condensation. The macroporous network is first generated by phase separation in acidic medium in the presence of polyethyleneoxides while mesoporosity is engineered in a second step in alkaline medium, possibly in the presence of alkylammonium cations as surfactants. The mesoporous monoliths, also referred as aerogels, are obtained in the presence of alkylpolyethylene oxides in acidic medium without the use of supercritical drying. The impact of the experimental conditions on pore architecture of the monoliths regarding the shape, the ordering, the size and the connectivity of the mesopores is comprehensively discussed based on a critical appraisal of the different models used for textural analysis.

  2. A tri-continuous mesoporous material with a silica pore wall following a hexagonal minimal surface

    Han, Yu; Zhang, Daliang; Chng, Leng Leng; Sun, Junliang; Zhao, L. J.; Zou, Xiaodong; Ying, Jackie

    2009-01-01

    Ordered porous materials with unique pore structures and pore sizes in the mesoporous range (2-50nm) have many applications in catalysis, separation and drug delivery. Extensive research has resulted in mesoporous materials with one-dimensional, cage-like and bi-continuous pore structures. Three families of bi-continuous mesoporous materials have been made, with two interwoven but unconnected channels, corresponding to the liquid crystal phases used as templates. Here we report a three-dimensional hexagonal mesoporous silica, IBN-9, with a tri-continuous pore structure that is synthesized using a specially designed cationic surfactant template. IBN-9 consists of three identical continuous interpenetrating channels, which are separated by a silica wall that follows a hexagonal minimal surface. Such a tri-continuous mesostructure was predicted mathematically, but until now has not been observed in real materials. © 2009 Macmillan Publishers Limited. All rights reserved.

  3. Synthesis of mesoporous TiO2 in aqueous alcoholic medium and evaluation of its photocatalytic activity

    Kumaresan, L.; Prabhu, A.; Palanichamy, M.; Murugesan, V.

    2011-01-01

    Research highlights: → Mesoporous TiO 2 synthesized using P123 as soft template in sol-gel method. → Nanoparticle aggregates are better for photocatalytic activity than free nanoparticles. → Particle to particle transport of electrons in the conduction band of aggregates are important factor. - Abstract: Mesoporous TiO 2 was synthesized using triblock copolymer as the structure directing template in ethanol/water, isopropanol/water or 1-butanol/water medium by sol-gel method. The presence of intense peak at low angle in the XRD patterns confirmed the orderly arrangement of mesopores in the material. Among the three different alcohols, ethanol had influenced better in controlling the particle size than others. The enhanced specific surface area also revealed the formation of mesopores. Aggregates of particles were clearly seen in the TEM images and the size of the particles was approximately 10 nm. The photocatalytic activity of mesoporous TiO 2 was evaluated using aqueous alachlor as a model pollutant. The activity of mesoporous TiO 2 synthesized in ethanol/water mole ratio of 50 was higher than other mesoporous TiO 2 and commercial TiO 2 (Degussa P-25). The transport of excited electrons from one particle to its neighboring nanoparticles of mesoporous TiO 2 is suggested to be the cause for enhanced photocatalytic activity.

  4. Fluorescent Functionalized Mesoporous Silica for Radioactive Material Extraction

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

    2012-01-01

    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.

  5. Mesoporous Silica: A Suitable Adsorbent for Amines

    Abdollahzadeh-Ghom Sara

    2009-01-01

    Full Text Available Abstract 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.

  6. Plutonium sorption to nanocast mesoporous carbon

    Parsons-Moss, Tashi; Wang, Deborah; Jones, Stephen; Olive, Daniel; Nitsche, Heino [California Univ., Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Laboratory, Berkeley, CA (United States). Nuclear Science Div.; Tueysuez, Harun [Lawrence Berkeley National Laboratory, Berkeley, CA (United States). Nuclear Science Div.; Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    2014-09-01

    Nanocast ordered mesoporous carbons are attractive as sorbents because of their extremely high surface areas and large pore volumes. This paper compares Pu uptake, added as Pu(VI), to both untreated and chemically oxidized CMK-(carbon molecular sieves from KAIST) type mesoporous carbon with that to a commercial amorphous activated carbon. The CMK was synthesized via nanocasting by using cubic ordered mesoporous silica KIT-6 as a hard template, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption. A portion of the CMK was oxidized by treatment with nitric acid, and will be called OX CMK. The three carbon powders have similar particle morphology, and high BET surface areas. The activated carbon is disordered, while the CMK materials show large domains of ordered cubic mesostructure. The CMK material seems to have more oxygen-containing functional groups than the activated carbon, and the oxidation of the CMK increased the density of these groups, especially - COOH, thus lowering the point of zero charge (PZC) of the material. Batch studies of all 3 materials with plutonium solutions, in a 0.1 M NaClO{sub 4} matrix were performed to investigate pH dependence, sorption kinetics, Pu uptake capacities, competition with ethylenediaminetetraacetic acid (EDTA) in solution, and Pu desorption. Both CMK materials demonstrated high Pu sorption from solutions of pH 3 or greater, and the oxidized CMK also showed high sorption from pH 2 solutions. The activated carbon bound less Pu, and at a much slower rate than CMK. All other batch experiments were carried out in pH 4 solutions. The Pu uptake from low-concentration solutions was faster for the oxidized CMK than for untreated CMK, but in more concentrated samples (∝ 250 μM Pu), the Pu uptake kinetics and apparent capacity were the same for oxidized and untreated CMK. The 23-h Pu uptake capacity of the CMK

  7. Mesoporous Silica Supported Au Nanoparticles with Controlled Size as Efficient Heterogeneous Catalyst for Aerobic Oxidation of Alcohols

    Xuefeng Chu

    2015-01-01

    Full Text Available A series of Au catalysts with different sizes were synthesized and employed on amine group functionalized ordered mesoporous silica solid supports as catalyst for the aerobic oxidation of various alcohols. The mesoporous silica of MCM-41 supported Au nanoparticles (Au-1 exhibited the smallest particle size at ~1.8 nm with superior catalytic activities owing to the confinement effect of the mesoporous channels. Au-1 catalyst is also very stable and reusable under aerobic condition. Therefore, this presented work would obviously provide us a platform for synthesizing more size-controlled metal catalysts to improve the catalytic performances.

  8. Designing advanced functional periodic mesoporous organosilicas for biomedical applications

    Dolores Esquivel

    2014-03-01

    Full Text Available Periodic mesoporous organosilicas (PMOs, reported for the first time in 1999, constitute a new branch of organic-inorganic hybrid materials with high-ordered structures, uniform pore size and homogenous distribution of organic bridges into a silica framework. Unlike conventional mesoporous silicas, these materials offer the possibility to adjust the surface (hydrophilicity/hydrophobicity and physical properties (morphology, porosity as well as their mechanical stability through the incorporation of different functional organic moieties in their pore walls. A broad variety of PMOs has been designed for their subsequent application in many fields. More recently, PMOs have attracted growing interest in emerging areas as biology and biomedicine. This review provides a comprehensive overview of the most recent breakthroughs achieved for PMOs in biologic