Reaction engineering of the hydrogenolysis of liquid n-Alkanes: Comparison of flow and batch reaction systems
Not Available
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Engineering topics
Gorte, Raymond J.
Publications and source records attributed to Gorte, Raymond J..
Modulating the Contact Angle between Nonpolar Polymers and SiO 2 Nanoparticles
Polymer–nanoparticle interactions play an important role in determining the morphology and properties of polymer nanocomposites and controlling the polymeric reactions involving heterogeneous catalysts. Here, in this study, we modulate the interactions between nonpolar polymers and nanoparticles by modifying the nanoparticle surface chemistry and quantify the interaction strength through direct contact angle measurements. We investigate the interactions of three nonpolar polymers, polystyrene, polyethylene, and polycyclooctene, with silica nanoparticles whose surface chemistry has been modified by atomic layer deposition of titania and calcium carbonate and by alkyl silanization. Significant differences in polymer–nanoparticle interactions are observed, which can be attributed to differences in the polarizability of the polymers and oxide surface composition. Compared to fully hydrogenated polycyclooctene, polycyclooctene is shown to have stronger interactions with most metal oxides; however, this trend is reversed following alkyl silanization of the silica nanoparticles, which makes the surface of the particles less polar. These differences in interactions can be leveraged to make polymer nanocomposites with unique properties and enable the selective conversion of polymers without the need for separations.
36 MATERIALS SCIENCE↗
Increase in the effective viscosity of polyethylene under extreme nanoconfinement
Understanding polymer transport in nanopores is crucial for optimizing heterogeneously catalyzed processes in polymer upcycling and fabricating high-performance nanocomposite films and membranes. Although confined polymer dynamics have been extensively studied, the behavior of polyethylene (PE)—the most widely used commodity polymer—in pores smaller than 20 nm remains largely unexplored. We investigate the effects of extreme nanoconfinement on PE transport using capillary rise infiltration in silica nanoparticle packings with average pore radii ranging from ~1 to ~9 nm. Using in situ ellipsometry and the Lucas–Washburn model, we discover a previously unknown inverse relationship between effective viscosity (η eff ) and average pore radius (R pore ). Additonally, we determine that PE transport under these extreme conditions is primarily governed by physical confinement, rather than pore surface chemistry. We refine an existing theory to provide a generalized formalism to describe the polymer transport dynamics over a wide range of pore radii (from 1 nm and larger). Our results offer valuable insights for optimizing catalyst supports in polymer upcycling and improving infiltration processes for nanocomposite fabrication.
36 MATERIALS SCIENCE↗
Determination of film thicknesses of metal oxides prepared by atomic layer deposition on SBA-15
ZrO 2 and CeO 2 films were grown in SBA-15 by Atomic Layer Deposition (ALD) to loadings of 0.92 g oxide/g SBA-15. Scanning Transmission Electron Microscopy (STEM) with Energy Dispersive Spectra (EDS) showed that the oxides grew uniformly inside the mesopores. Film thicknesses were then analyzed as a function of the number of ALD cycles using three methods: 1) mass changes assuming bulk densities for the films; 2) changes in pore size from Barret-Joyner-Halenda (BJH) analysis with N 2 adsorption isotherms; and 3) small-angle X-ray scattering (SAXS). Film thicknesses assuming bulk densities were between 6 and 8 times smaller than those obtained from BJH analysis. SAXS analysis gave film thicknesses that were approximately twice that obtained from bulk densities. Here, possible explanations of the discrepancies between these methods are discussed.
36 MATERIALS SCIENCE↗
Hydrodeoxygenation of m -Cresol over WO x -Pt/SBA-15 Using Alkanes as Hydrogen Carriers
Not provided.
Chemistry↗
Support Effect Studied on Thin-Film Perovskites
Some functional oxides exhibit strong support effects but typically have low surface areas and stabilities that negate the promotional effects. The primary goal of our work in the past three years was to develop high-surface-area versions of these supports by Atomic Layer Deposition onto stable supports, then use these to understand how the oxide supports affect the metal catalytic properties. The primary application targeted for these materials was methane oxidation and related reactions for emissions control. Systems of particular interest were supported, precious metals on thin-film perovskites in order to develop “intelligent” catalysts in which the metal can reversibly ex-solve from perovskite lattices. This following report lists the papers that were published with the support of this DOE grant, together with a brief summary of the results from each paper.
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Hydrogenolysis of n -eicosane over Ru-based catalysts in a continuous flow reactor
The hydrogenolysis of n-eicosane (C 20 H 42 ) was studied under differential conditions over Ru-based catalysts including Ru/SiO 2 , Ru/TiO 2 , and Ru/SBA-15, using a continuous flow reactor that was specially designed for large hydrocarbon reactants that are solids at room temperature. Similar rates and product distributions were obtained for Ru/SiO 2 and Ru/SBA-15 at 433 K, with the most abundant products being C 1 and C 19 hydrocarbons and smaller amounts of C 8 to C 18 also being produced. The higher yield of C 1 and C 19 indicates that cleavage of the terminal C-C bond is somewhat more facile than an internal C-C bond. At 473 K the product distribution shifted to mostly C 1 suggesting that, at this temperature, the adsorbed alkyl fragments undergo complete C-C bond scission prior to desorbing. Here, the conversion was also found to be inversely proportional to the H 2 pressure. Similar results were obtained for Ru/TiO 2 except this catalyst was found to be less active than both Ru/SiO 2 and Ru/SBA-15.
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Highly selective cross ketonization of renewable acids over magnesium oxide
The rising demand for linear alkylbenzene surfactants (LAS) poses an environmental threat as LAS are industrially produced from petroleum using corrosive acid catalysts. Cross ketonization is a promising route of converting furans and fatty acids to oleo-furansulfonates, precursors for renewable, performance-enhanced LAS replacements. Here, we explore various alkaline earth metals and mixed metal oxides for the cross-ketonization reaction and find that MgO achieves ~90% yield by minimizing the decarboxylation side reaction. Here, we illustrate the role of molecular structure on the cross-ketonization reaction and the role of complex formation over alkaline-earth metal oxides in minimizing side reactions. We overcome catalyst deactivation by regeneration over multiple runs. This research demonstrates the effectiveness of heterogeneous catalysts for cross ketonization toward developing renewable surfactants.
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