Date of Award

Spring 1-1-2014

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

First Advisor

James W. Medlin

Second Advisor

John L. Falconer

Third Advisor

Alan W. Weimer

Fourth Advisor

Charles B. Musgrave

Fifth Advisor

Gordana Dukovic

Abstract

Creating catalysts with enhanced selectivity and activity requires precise control over particle shape, composition, and size. Here we report the use of atomic layer deposition (ALD) to synthesize supported Ni, Pt, and Ni-Pt catalysts in the size regime (< 3 nm) where nanoscale properties can have a dramatic effect on reaction activity and selectivity.

This thesis presents the first ALD synthesis of non-noble metal nanoparticles by depositing Ni on Al2O3 with two half-reactions of Ni(Cp)2 and H2. By changing the number of ALD cycles, Ni weight loadings were varied from 4.7 wt% to 16.7 wt% and the average particle sizes ranged from 2.5 to 3.3 nm, which increased the selectivity for C3H6 hydrogenolysis by an order of magnitude over a much larger Ni/Al2O3 catalyst. Pt particles were deposited by varying the number of ALD cycles and the reaction chemistry (H2 or O2) to control the particle size from approximately 1 to 2 nm, which allowed lower-coordinated surface atoms to populate the particle surface. These Pt ALD catalysts demonstrated some of the highest oxidative dehydrogenation of propane selectivities (37%) of a Pt catalyst synthesized by a scalable technique.

Dry reforming of methane (DRM) is a reaction of interest due to the recent increased recovery of natural gas, but this reaction is hindered from industrial implementation because the Ni catalysts are plagued by deactivation from sintering and coking. This work utilized Ni ALD and NiPt ALD catalysts for the DRM reaction. These catalysts did not form destructive carbon whiskers and had enhanced reaction rates due to increased bimetallic interaction. To further limit sintering, the Ni and NiPt ALD catalysts were coated with a porous alumina matrix by molecular layer deposition (MLD). The catalysts were evaluated for DRM at 973 K, and the MLD-coated Ni catalysts outperformed the uncoated Ni catalysts in either activity (with 5 MLD cycles) or stability (with 10 MLD cycles).

In summary, this thesis developed a new Ni nanoparticle ALD chemistry, explored possibilities for changing Pt ALD particle size, brought the two techniques together to create enhanced bimetallic catalysts, and stabilized the catalysts using MLD.

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