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ABSTRACT: Nanohybrids composed of "onion-like" carbon, single-walled (SWCNTs) or multi-walled carbon nanotubes (MWCNTs) fused to silica or alumina particles have been compared as stabilizers of water/oil emulsions and interfacial catalysts. The amphiphilic character of these nanohybrids makes them effective in stabilizing emulsions (up to 85 % of total volume) comprising of small droplets (less than 40 μm). Furthermore, these nanohybrids have been used as supports for transition metal particles (palladium and copper) to catalyze reactions at the water/oil interface. Three different reaction systems have been conducted in the emulsions to demonstrate the principle: 1) hydrogenation of phenanthrene; 2) hydrogenation of glutaraldehyde and benzaldehyde; 3) oxidation of tetralin. Comparison of the maximum conversions achieved in emulsions as opposed to the single phase, together with much better control of selectivity in the two-phase system shows the benefits of using these nanohybrid catalysts.
ChemSusChem 07/2011; 4(7):964-74. · 6.83 Impact Factor
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ABSTRACT: A recoverable catalyst that simultaneously stabilizes emulsions would be highly advantageous in streamlining processes such as biomass refining, in which the immiscibility and thermal instability of crude products greatly complicates purification procedures. Here, we report a family of solid catalysts that can stabilize water-oil emulsions and catalyze reactions at the liquid/liquid interface. By depositing palladium onto carbon nanotube-inorganic oxide hybrid nanoparticles, we demonstrate biphasic hydrodeoxygenation and condensation catalysis in three substrate classes of interest in biomass refining. Microscopic characterization of the emulsions supports localization of the hybrid particles at the interface.
Science 01/2010; 327(5961):68-72. · 31.20 Impact Factor
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ABSTRACT: A novel system has been developed to catalyze reactions at the oil/water interface of a biphasic liquid system. Stabilization of emulsions was accomplished through the use of nanohybrids composed of hydrophilic oxide particles and hydrophobic Single-Walled Carbon Nanotubes (SWNT), generated in the CoMoCAT process. These nanohybrids are inherently amphiphilic, and tend to adsorb at the interface of a biphasic water/oil liquid system. When enough energy is added to the system, these particles stabilize emulsions by suppressing the coalescence of the droplets and increasing the viscoelastic or pseudoplastic character of the liquid film between droplets. , Depending on contact angle of the particles at the liquid-liquid interface it was possible to stabilize water-in-oil or oil-in-water emulsions. The resulting emulsions are remarkably stable against coalescence and sedimentation, and can be easily separated by filtration or centrifugation, which make them suitable for applications in interfacial catalytic processes in which the catalyst can be easily recovered after reaction. Catalytic activity was imparted by transition metal clusters supported onto the nanohybrids. These metals selectively catalyze reactions at the Oil/Water interface. The proof-of-concept of the biphasic hydrogenation and condensation catalysis was obtained with three reactions of interest in biorefining. The first example was the hydrodeoxygenation of vanillin (4-hydroxy-3-methoxybenzaldehyde). The second example was the conversion of molecules that were exclusively soluble in the aqueous or the organic phase, like glutaraldehyde (water phase) and octanal (oil phase). In the third example we explored a tandem reaction sequence in which Pd-catalyzed hydrogenation was paired with a preceding Aldol-condensation of 5- methylfurfural and acetone. It was demonstrated that with these nanohybrids it is possible to selectively accomplish hydrodeoxygenation and condensation reactions at the water/oil interface of a biphasic system, followed by migration of the products to the oil phase. This contribution provides a proof-of-concept for a promising catalytic system with many potential applications in the liquid phase, such as bio-oil upgrading, production of specialty chemicals, and pharmaceutical applications in which selective reaction and product separations, based on water solubility can be desirable.
MRS Proceedings. 12/2009; 1257.
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ABSTRACT: Emulsions have been stabilized by carbon nanotube-silica nanohybrids. The as-prepared nanotube-silica particles generate water-in-oil (w/o) emulsions, regardless of the water/oil volume ratio used. The emulsion volume fraction was much higher than that obtained with nanotubes only, and it was found to increase with water/oil ratio due to an increasing amount of water retained in the emulsion droplets. However, beyond a certain water/oil ratio, the emulsion fraction rapidly decreased. This point of collapse is a strong function of the amount of carbon nanotube-silica particles in the system. Oxidation of the nanohybrids by nitric acid can effectively modify the particle surfaces and change the resulting emulsion properties. The treatment in nitric acid increases the density of functional groups on the carbon nanotubes. Depending on the extent of functionalization, the effect of oxidation can vary from increasing the volume of emulsion stabilized to reversing the type of emulsion to oil-in-water (o/w). The emulsions are remarkably stable against coalescence and sedimentation and can be easily separated by filtration or centrifugation, which make them suitable for applications in interfacial catalytic processes in which the catalyst can be easily recovered after reaction.
Langmuir 10/2009; 25(18):10843-51. · 4.19 Impact Factor
