It is ideal to theoretically predict the activity of a catalyst. It has been recognized that not only the type of metal, but also its atomic size plays an important role in catalysis. In the past, atomic clusters have been created by sputtering from a sacrificial metal plate and then using a mass selector to choose cluster sizes from 1-233 atoms of gold. This approach has practical limitations. In this thesis, I describe a procedure by which atomic clusters of gold containing 1-8 atoms are deposited in polyaniline as an isolation matrix. My atomic deposition follows a cyclic pathway. Atomic clusters of palladium and atomic alloys of gold and palladium are also deposited in polyaniline using the same process. It is to show that this method will also work for other metals. These composite materials are characterized, and the catalytic activity for alcohol oxidation is evaluated.
This thesis is divided into seven chapters. The first chapter discusses the chemistry of polyaniline for using gold and palladium as catalysts. The technique developed to deposit the atomic clusters is discussed in the second chapter. This technique deposits one atom of metal per imine site on polyaniline, per cycle. The cycle is repeated n-times until a cluster of specified size, Mn, and composition has been synthesized. It is known that polyaniline plays an important role in stabilization of the formed clusters which prevents their aggregation. The optimization of this technique is the topic of the third chapter along with the description of how these composite films are produced. To end this chapter, the composite films are characterized by cyclic voltammetry, Kelvin probe, and X-ray photoelectron spectroscopy.
In chapters 4 and 5, the catalytic activity of the polyaniline/gold composites for the oxidation of alcohols in alkaline media using cyclic voltammetry is evaluated. In chapter 4, the correlation of the electrochemical activity for the oxidation of n-PrOH with the odd-even pattern from the calculated HOMO-LUMO gap energies for the same size clusters is shown. It is shown that the infrared spectrum of polyaniline with different sizes of atomic gold clusters also follows the odd-even pattern. Chapter 5 expands on the discussion of the catalytic oxidation of alcohols. The oxidation of methanol, ethanol, propanol, and butanol is surveyed. The peak currents are again dominated by the odd-even pattern.
In chapter 6, the versatility of the atomic deposition cycle is shown by depositing atomic palladium clusters. The peak currents for the oxidation of n-PrOH by these palladium composite films again follows the predicted pattern of the calculated HOMO-LUMO gap energies for atomic palladium clusters. This chapter also explores bimetallic atomic clusters of gold and palladium. The results indicate that the catalytic activity depends on the orientation of the cluster in the polyaniline matrix. Chapter 7 discusses the oxidation of methanol, ethanol, and isopropanol on AunPd1 bimetallic atomic clusters. The addition of palladium in the cluster increases the peak current densities for the oxidation of both alcohols except for the most stable of the atomic gold clusters, while it inactivated the electrodes for isopropanol. The possible future work for this project is discussed in chapter 8.
Overall, this thesis has developed a novel and unique technique for depositing atomic metal clusters into a polyaniline matrix. The technique is versatile enough to deposit atomic metal clusters other than gold, as shown by creating atomic palladium clusters and atomic bimetallic clusters of gold and palladium. This is extremely useful, since this single technique can produce many different types of atomic catalysts. The composite materials have been shown to be catalytically active for the oxidation of alcohols in alkaline media. This indicates a significant improvement to conserve precious metals while still retaining a high catalytic activity.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/49070 |
| Date | 20 September 2013 |
| Creators | Jonke, Alex P. |
| Contributors | Janata, Jiří |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation |
| Format | application/pdf |
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