ABSTRACT
Organosulfonic acid-functionalized mesoporous silica is a class of heterogeneous acid catalysts used in esterification processes due to its high surface area, shape-selective properties, and strongly acidic sites. Since water is generated as a by-product of esterification, the surface of mesostructured silica is modified to enhance hydrophobicity and catalytic performance. In this study, a series of propylsulfonic acid-functionalized nanocomposites based on natural rubber and hexagonal mesoporous silica (NRHMS-SO3H) with different acidities were prepared via an in situ sol-gel process using tetraethyl orthosilicate as the silica source, dodecylamine as the nonionic templating agent, and (3-mercaptopropyl)trimethoxysilane as the acid-functional group precursor. Compared with conventional propylsulfonic acid-functionalized hexagonal mesoporous silica (HMS-SO3H), NRHMS-SO3H provided higher hydrophobicity, while retaining mesoporosity and high surface area. The catalytic activity of synthesized solid acids was then evaluated via batch esterification of levulinic acid (LA) with alcohols (ethanol, n-propanol, and n-butanol) to produce alkyl levulinate esters. NRHMS-SO3H exhibited higher catalytic activity than HMS-SO3H and ultra-stable Y (HUSY) zeolite owing to the synergistic effect between the strongly acidic-functional group and surface hydrophobicity. The activation energy of the reaction over the NRHMS-SO3H surface was lower than that of HUSY and HMS-SO3H, suggesting that tuning the hydrophobicity and acidity on a nanocomposite surface is a compelling strategy for energy reduction to promote catalysis.
ABSTRACT
This study is the first report on the preparation of mesoporous carbon/silica (MCS) nanocomposites with tunable mesoporosity and hydrophobicity using natural rubber (NR) as a renewable and cheap carbon source. A series of mesoporous nanocomposites based on NR and hexagonal mesoporous silica (HMS) were prepared via an in situ sol-gel process and used as precursors; then, they were converted into MCS materials by controlled carbonization. The NR/HMS precursors exhibited a high dispersion of rubber phase incorporated into the mesostructured silica framework as confirmed by small-angle X-ray scattering and high-resolution transmission electron microscopy. An increase in the carbonization temperature up to 700 °C resulted in MCS nanocomposites with a well-ordered mesostructure and uniform framework-confined wormhole-like channels. The NR/HMS nanocomposites possessed high specific surface area (500-675 m2 g-1) and large pore volume (1.14-1.44 cm3 g-1). The carbon content of MCS (3.0-16.1 wt%) was increased with an increase in the H2SO4 concentration. Raman spectroscopy and X-ray photoelectron spectroscopy revealed the high dispersion of graphene oxide-like carbonaceous moieties in MCS materials; the type and amount of oxygen-containing groups in obtained MCS materials were determined by H2SO4 concentration. The enhanced hydrophobicity of MCS nanocomposites was related to the carbon content and the depletion of surface silanol groups, as confirmed by the water sorption measurement. The study on the controlled release of diclofenac in simulated gastrointestinal environment suggests a potential application of MCS materials as drug carriers.
ABSTRACT
Natural rubber (NR)/hexagonal mesoporous silica (HMS) nanocomposites (NRHMS) with enhanced thermal and hydrophobic properties were facilely prepared via in situ sol-gel formation with pH adjustment using a low sulphuric acid (H2SO4) acid concentration. The effect of the amount of 0.5 M H2SO4 (2.5-10 g) added into the pre-synthesis mixture on the physicochemical properties of the obtained NRHMS nanocomposites was investigated. With a small addition of H2SO4 solution, the fabricated NRHMS nanocomposite possessed an improved wormhole-like mesostructure arrangement with a thicker silica wall, which retarded the thermal decomposition of the NR phase, as deduced from the auto-oxidation of NR by thermogravimetric analysis. The H2O adsorption-desorption measurement revealed an increased hydrophobicity of the NRHMS composites, explained by the acid-catalyzed bridging of free silanol groups to siloxane bonds, which was supported by the X-ray photoelectron spectroscopy analysis. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy elemental mapping revealed a good dispersion of the NR phase within the mesostructured silica. However, a high amount of added H2SO4 solution led to silica-NR phase separation due to the decreased hydrophobic interaction between the silica precursor and rubber chain, as well as an agglomeration of the NR phase itself. The mechanism of NRHMS nanocomposite formation under pH-controlled conditions was proposed to proceed via a cooperative self-assembly route.
