• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1653-1668
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• 2005

Assembly of hybrid mesophases through the combination of amphiphilic block copolymers, acting as structuredirecting agents, and silicon sources using low acid catalyst concentration regimes is a versatile strategy to produce large quantities of high-quality ordered large-pore mesoporous silicas in a very reproducible manner. Controlling structural and textural properties is proven to be straightforward at low HCl concentrations with the adjustment of synthesis gel composition and the option of adding co-structure-directing molecules. In this account, we illustrate how various types of large-pore mesoporous silica can easily be prepared in high phase purity with tailored pore dimensions and tailored level of framework interconnectivity. Silica mesophases with two-dimensional hexagonal (p6mm) and three-dimensional cubi (Fm$\overline{3}$m, Im$\overline{3}$m and Ia$\overline{3}$d) symmetries are generated in aqueous solution by employing HCl concentrations in the range of 0.1−0.5 M and polyalkylene oxide-based triblock copolymers such as Pluronic P123 $(EO_{20}-PO_{70}-EO_{20})$ and Pluronic F127 $(EO_{106}-PO_{70}-EO_{106})$. Characterizations by powder X-ray diffraction, nitrogen physisorption, and transmission electron microscopy show that the mesoporous materials all possess high specific surface areas, high pore volumes and readily tunable pore diameters in narrow distribution of sizes ranging from 4 to 12 nm. Furthermore, we discuss our recent advances achieved in order to extend widely the phase domains in which single mesostructures are formed. Emphasis is put on the first synthetic product phase diagrams obtained in $SiO_2$-triblock copolymer-BuOH-$H_2O$ systems, with tuning amounts of butanol and silica source correspondingly. It is expected that the extended phase domains will allow designed synthesis of mesoporous silicas with targeted characteristics, offering vast prospects for future applications.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.215-221
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• 2005

A Fe-containing mesoporous silica (Fe-MCM-41) in which part of Si in the framework was replaced by Fe(Si-O-Fe) has been successfully prepared using $Fe^{3+}$ salt by a direct synthesis route. Physical properties of the material were characterized by XRD, $N_2$ adsorption, SEM/TEM, UV-vis and FT-IR spectroscopies. Fe-MCM-41 exhibited high catalytic activity in phenol hydroxylation using $H_2O_2$ as oxidant, giving phenol conversion of ca. 60% at $50^{\circ}C$ [phenol : $H_2O_2$ = 1:1, water solvent]. Fe-MCM-41 was also applied to the growth of CNTs, utilizing a thermal-CVD reactor using acetylene gas, which demonstrated that multi-wall CNTs could be prepared efficiently using the Fe-MCM-41 catalyst.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.369-374
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• 2006

A solid-state reaction of $V_2O_5$ with AlMCM-48 followed by calcination generated very weak paramagnetic $VO^{2+}$ species in the mesoporous material. Dehydration and subsequent reduction with CO result in the formation of vanadyl $VO^{2+}$ species that can be characterized by EPR. The chemical environment of vanadium centers in $VO^{2+}-AlMCM-48$ was investigated by XRD, EDX, DR-UV-Vis, EPR,$^{29}Si$ and $^{27}Al$ and $^{51}V$ NMR. Vanadium species in MCM-48 are existed as pseudotetrahedral $VO^{2+}$ state when they were dehydrated or reduced with CO. The coordination of water on vanadyl ions transformed their structure to distorted octahedral.

• Korean Journal of Materials Research
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• v.24 no.5
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• pp.243-248
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• 2014

Silicon-carbon composite was prepared by the magnesiothermic reduction of mesoporous silica and subsequent impregnation with a carbon precursor. This was applied for use as an anode material for high-performance lithium-ion batteries. Well-ordered mesoporous silica(SBA-15) was employed as a starting material for the mesoporous silicon, and sucrose was used as a carbon source. It was found that complete removal of by-products ($Mg_2Si$ and $Mg_2SiO_4$) formed by side reactions of silica and magnesium during the magnesiothermic reduction, was a crucial factor for successful formation of mesoporous silicon. Successful formation of the silicon-carbon composite was well confirmed by appropriate characterization tools (e.g., $N_2$ adsorption-desorption, small-angle X-ray scattering, X-ray diffraction, and thermogravimetric analyses). A lithium-ion battery was fabricated using the prepared silicon-carbon composite as the anode, and lithium foil as the counter-electrode. Electrochemical analysis revealed that the silicon-carbon composite showed better cycling stability than graphite, when used as the anode in the lithium-ion battery. This improvement could be due to the fact that carbon efficiently suppressed the change in volume of the silicon material caused by the charge-discharge cycle. This indicates that silicon-carbon composite, prepared via the magnesiothermic reduction and impregnation methods, could be an efficient anode material for lithium ion batteries.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3668-3674
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• 2010

Mesoporous SBA-15 was synthesized using tetraethylorthosilicate (TEOS) as the silica source and Pluronic (P123) as the structure-directing agent. The defective Si-OH groups present in SBA-15 were successively grafted with 3-chloropropyltrimethoxysilane (CPTMS) followed by tris-(2-aminoethyl) amine (TAEA) and/or tetraethylenepentamine (TEPA) for effective immobilization of silver nanoparticles. Grafting of TAEA and/or TEPA amine and immobilization of silver nanoparticles inside the channels of SBA-15 was verified by XRD, TEM, IR and BET techniques. The silver nanoparticles immobilized on TAEA and /or TEPA grafted SBA-15 was subjected for electrocatalytic reduction of hydrogen peroxide ($H_2O_2$). The TEPA stabilized silver nanoparticles show higher efficiency for reduction of $H_2O_2$ than that of TAEA, due to higher number of secondary amine groups present in TEPA. The amperometric analysis indicated that both the Ag/SBA-15/TAEA and Ag/SBA-15/TEPA modified electrodes required lower over-potential and hence possess high sensitivity towards the detection of $H_2O_2$. The reduction peak currents were linearly related to hydrogen peroxide concentration in the range between $3{\times}10^{-4}\;M$ and $2.5{\times}10^{-3}\;M$ with correlation coefficient of 0.997 and detection limit was $3{\times}10^{-4}\;M$.

• Membrane Journal
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• v.28 no.4
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• pp.221-232
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• 2018

The silica containing carbon ($C-SiO_2$) membranes were fabricated using poly(imide siloxane)(Si-PI) and polyvinylpyrrolidone (PVP) blended polymer. The characteristics of porous carbon structures prepared by the pyrolysis of polymer blends were related with the micro-phase separation behaviors of the two polymers. The glass transition temperatures ($T_g$) of the mixed polymer blends of Si-PI and PVP were observed with a single $T_g$ using differential scanning calorimetry. Furthermore, the nitrogen adsorption isotherms of the $C-SiO_2$ membranes were investigated to define the characteristics of porous carbon structures. The $C-SiO_2$ membranes derived from Si-PI/PVP showed the type IV isotherm and possessed the hysteresis loop, which was associated with the mesoporous carbon structures. For the molecular sieving probe, the $C-SiO_2$ membranes were prepared with the ratio of Si-PI/PVP and the pyrolysis conditions, such as the pyrolysis temperature and the isothermal times. Consequently, the $C-SiO_2$ membranes prepared by the pyrolysis of Si-PI/PVP at $550^{\circ}C$ with the isothermal time of 120 min showed the $O_2$ permeability of 820 Barrer ($1{\times}10^{-10}cm^3(STP)cm/cm^2{\cdot}s{\cdot}cmHg$) and $O_2/N_2$ selectivity of 14.

• Transactions on Electrical and Electronic Materials
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• v.12 no.3
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• pp.119-122
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• 2011

A series of mesoporous silicalites was synthesized using different compositions of tetraethylorthosilicate and methyltriethoxysilane (MTES) as the silica source. Cetyltrimethylammonium bromide was used as the organic template. Their detailed pore structures were investigated by transmission electron microscopy, X-ray diffraction, and N2 adsorption method. The thermal properties of these silicalites were studied by thermogravimetric analysis. The increased amount of MTES destroyed mesoporous channels and reduced pore sizes from 3.4 nm to 2.8 nm in calcined silicalites. The calcined silicalite transformed completely into an amorphous state at 30% MTES loading. Methyl pending groups of MTES hindered the structural ordering of ≡Si-O- frameworks, resulting in an amorphous structure. This was caused by the insufficient formation of supramolecular assembly with the organic template. No capillary condensation step was found in MS 7/3 silicalite. The other capillary condensation steps shifted toward the lower relative pressure with increasing MTES content, indicating the reduction of pore sizes.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1020-1027
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• 1999

Heteropoly acid(HPW) catalysts supported on three different carriers, an amorphous silica, MCM-41 and MCM-48, with different loadings and calcination temperatures have been prepared and characterized by X-ray diffraction, nitrogen physorption, infrared spectroscopy, and $^{31}P$ magic angle spinning NMR. From the result of IR and NMR, it was shown that HPW retains the Keggin structure on the supported catalysts. No HPW crystal phase was developed even at HPW loadings as high as 35 wt % on the MCM-41 and 65 wt % MCM-48. Thus, HPW appeared to form finely dispersed species. In the hydrolysis reaction of di, bis, tri-pentaerythritol, HPW/MCM-41, 48 exhibited higher catalytic activity than $HPW/SiO_2$ or HPW.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.217-217
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• 2011

Recently, demand for thermally stable metal nanoparticles suitable for chemical reactions at high temperatures has increased to the point to require a solution to nanoparticle coalescence. Thermal stability of metal nanoparticles can be achieved by adopting core-shell models and encapsulating supported metal nanoparticles with mesoporous oxides [1,2]. However, to understand the role of metal-support interactions on catalytic activity and for surface analysis of complex structures, we developed a novel catalyst design by coating an ultra-thin layer of titania on Pt supported silica ($SiO_2/Pt@TiO_2$). This structure provides higher metal dispersion (~52% Pt/silica), high thermal stability (~600$^{\circ}C$) and maximization of the interaction between Pt and titania. The high thermal stability of $SiO_2/Pt@TiO_2$ enabled the investigation of CO oxidation studies at high temperatures, including ignition behavior, which is otherwise not possible on bare Pt nanoparticles due to sintering [3]. It was found that this hybrid catalyst exhibited a lower activation energy for CO oxidation because of the metal-support interaction. The concept of an ultra-thin active metal oxide coating on supported nanoparticles opens-up new avenues for synthesis of various hybrid nanocatalysts with combinations of different metals and oxides to investigate important model reactions at high-temperatures and in industrial reactions.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.18 no.3
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• pp.1-6
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• 2017

Functional coatings, such as anti-reflection and self-cleaning, are frequently applied to cover glass for photovoltaic applications. Anti-reflection coatings made of mesoporous silica film have been shown to enhance the light transmittance. $TiO_2$ photocatalyst films are often applied as a self-cleaning coating. In this study, transparent hydrophobic anti-reflective and self-cleaning coatings made of $SiO_2/TiO_2$ thin layers were fabricated on a slide glass substrate by the sol-gel and dip-coating processes. The morphology of the functional coatings was characterized by field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). The optical properties of the functional coatings were investigated using an UV-visible spectrophotometer. Contact angle measurements were performed to confirm the hydrophobicity of the surface. The results showed that the $TiO_2$ films exhibit a high transmittance comparable to that of the bare slide glass substrate. The $TiO_2$ nanoparticles make the film more reflective and lead to a lower transmittance. However, the transmittance of the $SiO_2/TiO_2$ thin layers is 93.5% at 550 nm with a contact angle of $110^{\circ}$, which is higher than that of the bare slide glass (2.0%).