Chemistry & Biochemistry Theses and Dissertations
Permanent URI for this collectionhttp://hdl.handle.net/1903/2752
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Item Bimetallic Nanoparticles for Advanced Energy Conversion Technologies(2015) Sims, Christopher; Eichhorn, Bryan W; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The increased demand for a more sustainable energy infrastructure has spurred the development of innovative energy conversion processes and devices, such as the proton exchange membrane fuel cell (PEMFC). PEMFCs are highly regarded as a clean alternative energy technology for various applications, such as motor vehicles or power generators. Factors limiting their commercial viability include the poisoning of the hydrogen oxidation reaction (HOR) electrocatalyst at the anode by carbon monoxide (CO), an impurity in the H2 fuel feedstocks derived from hydrocarbons, and the high expense and inefficiency of the oxygen reduction reaction (ORR) electrocatalyst at the cathode. The research described in this dissertation entails the synthesis and characterization of new bimetallic nanoparticle (NP) catalysts with controlled sizes, compositions, and architectures. By varying the NPs' compositions, structures, and electronic environments, we aimed to elucidate the physical and chemical relationships that govern their ability to catalyze chemical reactions pertinent to PEMFC operation. The ongoing research and development of these NP-based catalytic systems is essential to realizing the viability of this energy conversion technology. We describe the development of a simple method for synthesizing monometallic and bimetallic NPs supported on various reduced graphene oxide (rGO) supports. Electrochemical studies illustrate how the chemical nature of the rGO support impacts the catalytic behavior of the NP catalysts through unique metal-support interactions that differ depending on the elemental composition of the NP substrate. In another study, we present the synthesis and characterization of CoxPty NPs with alloy and intermetallic architectures and describe how their inherent characteristics impact their catalytic activities for electrochemical reactions. CoxPty NPs with alloy architectures were found to have improved CO tolerance compared to their intermetallic counterparts, while the performance of the CoxPty NPs for ORR catalysis was shown to be highly dependent on the NPs' crystal structure. Finally, we present the synthesis and characterization of various bimetallic core-shell NPs. Preliminary data for CO oxidation and PrOx catalysis demonstrated how subsurface metals modify the electronic structure of Ni and enhances its catalytic performance for CO oxidation and the PrOx reaction.Item Core/Shell and Alloy Nanoparticles of Transition Metals for Heterogeneous Catalysis: Bridging the Gap between Experiment and Theory(2008) Alayoglu, Selim; Eichhorn, Bryan W; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)This thesis describes the structural and catalytic properties of the architecturally-controlled bimetallic nanoparticles (NPs) of transition metals. In this study, bimetallic nanoparticles with well-defined architectures were synthesized, characterized and evaluated toward various heterogeneous reactions. Random alloy nanoparticles were compared to the core/shell nanoparticles (M@M' NPs where M is the core metal and M' is the shell metal), which is the synthetic counterpart of the theoretically well-studied Near Surface Alloys (NSAs). Thus, the long existing experimental gap with the theory can be bridged via the systematic evaluation of such architecturally-controlled bimetallic NPs. The M@Pt (M=Ru, Rh, Ir, Pd and Au) and Ru@M' (M'=Rh and Pd) core/shell NPs of tunable core sizes and shell thicknesses, and the PtRu alloy and PtRh alloy NPs of various compositions were prepared via poly-ol reduction reactions by using sequential deposition techniques. Seed NPs for the core/shell systems were synthesized via either poly-ol or NaBH4 reduction reactions. The wet-chemical co-deposition technique was employed to synthesize the alloy NPs. The core/shell and alloy NPs were characterized by using a combination of TEM, STEM-EDS, XRD, and FT-IR and Micro Raman -CO probe experiments. Full structural analysis employing techniques such as Extended X-Ray Absorption Fine Structure (EXAFS) and atomic Pair Distribution Function (PDF) was also performed for the 4.1 nm Ru@Pt NPs comprising of 3.0 nm cores and 1-2 MLs thick shells and the 4.4 nm Pt50Ru50 alloy NPs. Through collaborations, the nanoparticle structures were also modeled through EXAFS analyses, PDF fits, Rietveld Refinements and Debye Function simulations. The well-characterized core/shell and alloy NPs were evaluated for preferential oxidation of CO in H2 feeds (PROX). Catalytically, the core/shell NPs were superior to their alloy counterparts with similar particle sizes and identical compositions. The PROX reactivities of the M@Pt (M=Ru, Rh, Ir, Pd and Au) core/shell NPs increased in the order of Au@Pt < Pd@Pt < Ir@Pt < Rh@Pt < Ru@Pt, which is predicted by the NSA theory. Density Functional Theory (DFT) calculations performed by Prof. Mavrikakis at the University of Wisconsin helped elucidate the thermo-chemistry beyond the enhanced PROX activities and the observed surface reactivity trends for the core/shell architectures. The decreased equilibrium surface coverage of CO as well as the new H2-assisted O2 dissociation pathway on the electronically-altered Pt shells were suggested to bring on the room temperature CO oxidation and the subsequent H2 activation with enhanced PROX selectivity. The surface reactivities toward PROX and benzene hydrogenation reactions of the composition series of the PtRu alloy NPs exhibited the `Volcano' behavior, which invoked the Hammer-Norskov theory. The preliminary benzene hydrogenation results on the Ru@Pt NPs system presented in this study also showed a structure dependent correlation in surface activity.