Understanding the Structure-Function Relationship of the Silica-Supported Silver and Zirconia Catalyst in the Lebedev Reaction

Author: ORCID icon orcid.org/0000-0003-2491-2509
Miyake, Naomi, Chemical Engineering - School of Engineering and Applied Science, University of Virginia
Davis, Robert, EN-Chem Engr Dept, University of Virginia

With rising concerns about the increasing concentration of greenhouse gases in the environment, interest in decreasing the environmental impact of industrial processes has gained traction. Comparisons of butadiene (1,3-butadiene) production using ethanol (known as the Lebedev reaction) instead of the current feedstock naphtha, showed that the ethanol-based process overall, has a lower environmental impact. In terms of economics, however, the ethanol-based process is less cost-efficient compared to the naphtha-based process due to a lack of technology development. To address this problem, researchers have focused on developing an efficient catalyst for the Lebedev reaction.
This work explores a multifunctional catalyst system composed of silica-supported Ag and ZrO2 used for the cascade reaction of ethanol to butadiene at 573 K. The Ag and ZrO2 components were synthesized on separate support particles enabling characterization of each component without interference from the other. High selectivity to butadiene (65%) at high ethanol conversion (75%) was achieved with an appropriate ratio of Ag and ZrO2 in the reactor. Silver catalyzed the initial dehydrogenation of ethanol to acetaldehyde while ZrO2 catalyzed the C-C coupling and subsequent dehydration reactions. The silica-supported ZrO2 exhibited superior selectivity relative to bulk ZrO2 in the Ag-promoted ethanol to butadiene reaction. Results from Zr K-edge X-ray absorption spectroscopy and UV-Vis spectroscopy showed that ZrO2 was highly dispersed on the silica support over a range of loadings. Infrared spectroscopy of adsorbed pyridine, CO, and CO2, and kinetics of probe reactions 1-butene double bond isomerization, 2-propanol decomposition, and ethanol hydrogenation of acetone were used to compare the acid-base nature and chemical reactivity of silica-supported ZrO2 to bulk ZrO2.

PHD (Doctor of Philosophy)
Acid, Base, Lebedev Reaction, Zirconia, Ethanol Coupling
Sponsoring Agency:
Department of Energy
Issued Date: