Browsing by Subject "Mesoporous"

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    Lyotropic liquid crystalline mesophases made of salt-acid-surfactant systems for the synthesis of novel mesoporous lithium metal phosphates
    (Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim, 2019) Uzunok, Işıl; Kim, J.; Çolak, Tuluhan O.; Kim, D.; Kim, H.; Kim, M.; Yamauchi, Y.; Dağ, Ömer
    Mesoporous lithium metal phosphates are an important class of materials for the development of lithium ion batteries. However, there is a limited success in producing mesoporous lithium metal phosphates in the literature. Here, a lyotropic liquid crystalline (LLC) templating method was employed to synthesize the first examples of LiMPO4 (LMP) of Mn(II), Co(II), and Ni(II). A homogeneous aqueous solution of lithium and transition metal nitrate salts, phosphoric acid (PA), and surfactant (P123) can be spin coated or drop‐cast coated over glass slides to form the LLC mesophases which can be calcined into mesoporous amorphous LMPs (MA‐LMPs). The metal salts of Mn(II), Co(II) and Ni(II) produce MA‐LMPs that crystallize into olivine structures by heat treatment of the LLC mesophase. The Fe(II) compound undergoes air oxidation. Therefore, both Fe(II) and Fe(III) precursors produce a crystalline Li3Fe2(PO4)3 phase at over 400 °C. The MA‐LMPs show no reactivity towards lithium, however the crystalline iron compound exhibits electrochemical reactivity with lithium and a good electrochemical energy storage ability using a lithium‐ion battery test.
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    Morphological control of mesoporosity and nanoparticles within Co3O4-CuO electrospun nanofibers: quantum confinement and visible light photocatalysis performance
    (American Chemical Society, 2017-09) Pradhan, A. C.; Uyar, Tamer
    The one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co3O4-CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co3O4-CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co3O4-CuO NFs but also single mesoporous Co3O4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co3O4 nanofibers framework (Co3O4-CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co3O4-CuO NFs is due to the internal charge transfer between Co2+ to Co3+ and Cu2+, proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co3O4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co3O4-CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co3O4-CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co3O4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co3O4-CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.
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    One-pot preparation of fluorinated mesoporous silica nanoparticles for liquid marble formation and superhydrophobic surfaces
    (American Chemical Society, 2011) Yildirim, A.; Budunoglu, H.; Daglar, B.; Deniz, H.; Bayındır, Mehmet
    One-pot synthesis of fluorinated mesoporous silica nanoparticles (FMSNs) is reported. Uniform mesoporous nanoparticles are prepared by condensation of tetraethyl orthosilicate (TEOS) and fluoroalkyl containing organotriethoxy silane monomers, respectively. The method enables selective deposition of fluorine atoms on the surface of the particles. FMSNs are used to prepare stable liquid marbles with water. An organo-modified silica sol is used with FMSNs to prepare mechanically stable superhydrophobic surfaces (water contact angle of 161 degrees). The mechanical stability of the surface is investigated with water dripping and adhesive tape tests. The prepared FMSNs are promising building blocks for robust, large-area, and multifunctional self-cleaning surfaces.
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    Periodic mesoporous hydridosilica-synthesis of an "impossible" material and its thermal transformation into brightly photoluminescent periodic mesoporous nanocrystal silicon-silica composite
    (2011) Xie, Z.; Henderson, E. J.; Dag, Ö.; Wang, W.; Lofgreen, J. E.; Kübel, C.; Scherer, T.; Brodersen, P. M.; Gu, Zhong-Ze; Ozin, G. A.
    There has always been a fascination with "impossible" compounds, ones that do not break any rules of chemical bonding or valence but whose structures are unstable and do not exist. This instability can usually be rationalized in terms of chemical or physical restrictions associated with valence electron shells, multiple bonding, oxidation states, catenation, and the inert pair effect. In the pursuit of these "impossible" materials, appropriate conditions have sometimes been found to overcome these instabilities and synthesize missing compounds, yet for others these tricks have yet to be uncovered and the materials remain elusive. In the scientifically and technologically important field of periodic mesoporous silicas (PMS), one such "impossible" material is periodic mesoporous hydridosilica (meso-HSiO1.5). It is the archetype of a completely interrupted silica open framework material: its pore walls are comprised of a three-connected three-dimensional network that should be so thermodynamically unstable that any mesopores present would immediately collapse upon removal of the mesopore template. In this study we show that meso-HSiO1.5 can be synthesized by template-directed self-assembly of HSi(OEt)3 under aqueous acid-catalyzed conditions and after template extraction remains stable to 300 °C. Above this temperature, bond redistribution reactions initiate a metamorphic transformation which eventually yields periodic mesoporous nanocrystalline silicon-silica, meso-ncSi/SiO2, a nanocomposite material in which brightly photoluminescent silicon nanocrystallites are embedded within a silica matrix throughout the mesostructure. The integration of the properties of silicon nanocrystallinity with silica mesoporosity provides a wealth of new opportunities for emerging nanotechnologies.
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    Template-free synthesis of organically modified silica mesoporous thin films for TNT sensing
    (American Chemical Society, 2010) Yildirim, A.; Budunoglu, H.; Deniz, H.; Güler, Mustafa O.; Bayındır, Mehmet
    In this paper, we present a facile, template-free sol−gel method to produce fluorescent and highly mesoporous organically modified silica (ORMOSIL) thin films for vapor phase sensing of TNT. An alkyltrifunctional, methyltrimethoxysilane MTMS precursor was used to impart hydrophobic behavior to gel network in order to form the spring back effect. In this way, porous films (up to 74% porosity) are obtained at ambient conditions. Fluorescent molecules are physically encapsulated in the ORMOSIL network during gelation. Fluorescence of the films was found to be stable even after 3 months, proving the successful fixing of the dye into the ORMOSIL network. The functional ORMOSIL thin films exhibited high fluorescence quenching upon exposition to TNT and DNT vapor. Fluorescence quenching responses of the films are thickness-dependent and higher fluorescence quenching efficiency was observed for the thinnest film (8.6% in 10 s). The prepared mesoporous ORMOSIL thin films have great potential in new sensor and catalysis applications.