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.
HY zeolites hydrophobized by functionalization with organosilanes are much more stable in hot liquid water than the corresponding untreated zeolites. Silylation of the zeolite increases hydrophobicity without significantly reducing the density of acid sites. This hydrophobization with organosilanes makes the zeolites able to stabilize water/oil emulsions and catalyze reactions of importance in biofuel upgrading, i.e., alcohol dehydration and alkylation of m-cresol and 2-propanol in the liquid phase, at high temperatures. While at 200 °C the crystalline structure of an untreated HY zeolite collapses in a few hours in contact with a liquid medium, the functionalized hydrophobic zeolites keep their structure practically unaltered. Detailed XRD, SEM, HRTEM, and BET analyses indicate that even after reaction under severe conditions, the hydrophobic zeolites retain their crystallinity, surface area, microporosity, and acid density. It is proposed that by preferentially anchoring hydrophobic functionalities on the external surface, the direct contact of bulk liquid water and the zeolite is hindered, thus preventing the collapse of the framework during the reaction in liquid hot water.
Metal-containing Janus particles are used as interfacial catalyst/emulsifiers that catalyze reactions in biphasic systems with controlled "phase selectivity", that is, conversion of the desired reaction on one side of the emulsion. The reaction may affect the solubility of the molecule in one phase, causing migration to the opposite phase. As a result, combined reaction and separation can be achieved in a single reaction vessel.
A new type of catalyst has been designed to adjust the basicity and level of molecular confinement of KNaX faujasites by controlled incorporation of Mg through ion exchange and precipitation of extraframework MgO clusters at varying loadings. The catalytic performance of these catalysts was compared in the conversion of C2 and C4 aldehydes to value-added products. The product distribution depends on both the level of acetaldehyde conversion and the fraction of magnesium as extraframework species. These species form rather uniform and highly dispersed nanostructures that resemble nanopetals. Specifically, the sample containing Mg only in the form of exchangeable Mg(2+) ions has much lower activity than those in which a significant fraction of Mg exists as extraframework MgO. Both the (C6+C8)/C4 and C8/C6 ratios increase with additional extraframework Mg at high acetaldehyde conversion levels. These differences in product distribution can be attributed to 1) higher basicity density on the samples with extraframework species, and 2) enhanced confinement inside the zeolite cages in the presence of these species. Additionally, the formation of linear or aromatic C8 aldehyde compounds depends on the position on the crotonaldehyde molecule from which abstraction of a proton occurs. In addition, catalysts with different confinement effects result in different C8 products.
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.
A novel technique is proposed for potential use in oil reservoirs. The technique consists in incorporating amphiphilic nanoparticles into the water injection. These hybrid nanoparticles can simultaneously act as emulsion stabilizers as well as carriers for catalytic species, e.g., metals. They can be active for in situ reactions, such as partial oxidation and hydrogenation, which may result in changes in rheological and interfacial properties of the oil, as well as modifying the wettability of the walls. These changes might be efficiently used to improve the oil recovery process. Specifically, partial oxidation of organic compounds lowers the water−oil interfacial tension and consequently increases the capillary number (N c ) of the system. Alternatively, partial hydrogenation of polynuclear aromatics can enhance the viscosity of the oil phase in the emulsion, thus improving the mobility ratio (MR). In addition, partial hydrogenation can be an effective pretreatment of the oil to favor the subsequent partial oxidation.
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