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FUNDAMENTAL INSIGHTS OF PLANAR AND SUPPORTED CATALYSTS

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thesis
posted on 10.06.2019 by Cory A. Milligan

A fundamental understanding of heterogeneous catalysis requires analysis of model catalytic surfaces in tandem with complex technical catalysts. This work was divided in three areas, 1- preparation and characterization of model surfaces synthesized by vapor deposition techniques, 2- kinetic evaluation of model catalysts for formic acid decomposition and dry methane reforming, 3- characterization and kinetic evaluation of technical catalysts for the water gas shift reaction.

In the first project, model PdZn intermetallic surfaces, a relevant catalyst for propane dehydrogenation, were prepared using an ALD approach. In this work, model surfaces were synthesized by exposing Pd(111) and Pd(100) surfaces to diethylzinc at ca. 10-6 mbar. Several different surface structures were identified by careful control of the deposition temperature of the substrate. Modifications in the adsorption properties of these surfaces towards carbon monoxide and propylene coincided with the structure of the PdZn surface layer.

In the second project, formic acid decomposition kinetics were evaluated on model Pt catalysts. Formic acid decomposition was found to be structure-insensitive on Pt(111), Pt(100), and a polycrystalline foil under standard reaction conditions. CO selectivity remained < 1% for conversions <10%. Additionally, inverse Pd-Zr model catalysts were prepared by ALD of zirconium-t-butoxide (ZTB). Depending on treatment conditions, either ZrOxHy or ZrO2 overlayers or Zr as sub-nanometer clusters could be obtained. The activity of the model catalyst surface towards dry reforming of methane if the initial state of the zirconium is metallic.

In the third project, Au/Fe3O4 heterodimer catalysts were characterized for their thermal stability. In-situ TEM and XPS characterization demonstrates that the gold nanoparticles transform into gold thin films that wet the Fe3O4 surface as the reduction of the oxide proceeds. DFT calculations show that the adhesion energy between the Au film is increased on a partially reduced Fe3O4 surface. Additionally, Pt/Nb2CTx catalysts were characterized and kinetics evaluated for the water gas shift reaction. XPS and TEM characterization indicates that a Pt-Nb surface alloy is formed under moderate reduction temperatures, 350OC. Water-gas shift reaction kinetics reveal that the alloy-MXene interface exhibit high H2O activation ability compared to a non-reducible support or bulk niobium carbide.

Funding

DE-AC02-06CH11357

FUNDAMENTAL STUDIES OF OXIDATION REACTIONS ON MODEL CATALYSTS

Basic Energy Sciences

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DMREF/Collaborative Research: Design of Multifunctional Catalytic Interfaces from First Principles

Directorate for Engineering

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History

Degree Type

Doctor of Philosophy

Department

Chemical Engineering

Campus location

West Lafayette

Advisor/Supervisor/Committee Chair

Fabio H. Ribeiro

Additional Committee Member 2

Jeffrey P Greeley

Additional Committee Member 3

Jeffrey T Miller

Additional Committee Member 4

Dmitry Y Zemlyanov

Licence

Exports