Author: Beth Cheney

Publisher:

Published: 2010

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Synthesis of supported nanoparticles with consistent particle size is a bridge between what researchers refer to as the "materials gap," the gap in structure complexity between single crystals and supported catalysts. Controlling particle size during supported catalyst synthesis allows researchers to investigate optimal conditions for desired activity and/or selectivity toward specific chemical reactions. This information can lead to the possibility to tune catalyst synthesis to optimize efficiency and cost while minimizing the waste of precious, nonrenewable resources. This thesis investigates a procedure potentially capable of synthesizing supported catalysts with uniformly-sized nanoparticles. This combines the idealized environment of a model system with the increased complexity associated with nanoparticle size and support effects. To bridge the materials gap, extensive work has been performed to determine how metallic structures affect adsorbate interactions. Chapter 1 discusses density functional theory (DFT) calculations used to predict adsorbate binding energies on metal monolayer bimetallic surfaces and the correlation to single crystal surfaces and polycrystalline foils. Recently, the trends observed on these model systems have provided insight into enhanced reactivity on oxide-supported bimetallic catalysts. Due to limitations of particle size control with traditional catalyst synthesis procedures, there is motivation for a method to synthesize uniform particles to better represent model surfaces. Chapter 2 describes reverse micelle synthesis, a technique which has been shown to control nanoparticle size by chemically reducing metal precursors in surfactant-stabilized water droplets suspended in an oil phase. Techniques used to characterize catalysts synthesized using this method are also discussed in this chapter. Chapter 3 discusses synthesis of supported monometallic platinum (Pt) and bimetallic platinum-cobalt (Pt-Co) catalysts in aqueous/oil/surfactant microemulsions consisting of water/cyclohexane/Brij-30 reduced by sodium borohydride (NaBH4). Although reverse micelle synthesis produced small (~4 nm) reduced, unsupported nanoparticles, supported particles sintered after hightemperature pre-treatments. Extended X-ray absorption fine structure (EXAFS) measurements confirmed bimetallic bond formations between Pt and Co atoms; however, bimetallic catalysts did not exhibit enhanced hydrogenation activity compared to their monometallic Pt catalysts. A half-fractional factorial design of experiments was implemented to determine what synthesis parameters could be altered to decrease solvent quantities, thus decreasing residual carbon which may have inhibited catalytic activity. Statistical analysis could not be performed due to large scatter between repetitions. Due to unsatisfactory reproducibility involved with this synthesis, an alternative reverse micelle synthesis chemistry was investigated. The reverse micelle synthesis chemistry described in Chapter 4 incorporated a co-surfactant, which stabilizes surfactant molecules around water droplets and promotes uniformity. The composition was an aqueous/oil/surfactant/cosurfactant microemulsion consisting of water/cyclohexane/Triton X-100/2-propanol. The reducing agent was hydrazine (N2H4). Two impregnation methods, stepimpregnation and co-impregnation, were tested. Step-impregnation describes the procedure where nickel (Ni) nanoparticles were reduced in microemulsion and supported, followed by depositing Pt using incipient wetness impregnation. Co-impregnation is the procedure where Ni and Pt were reduced simultaneously in microemulsion and then supported. These methods were compared to catalysts synthesized by incipient wetness impregnation, either step-impregnation (supporting Ni then supporting Pt) or co-impregnation (supporting Pt and Ni simultaneously). Final particle sizes of all catalysts were similar; however, micelle catalysts resulted in a narrower distribution of particle size than those synthesized using only incipient wetness impregnation. Step-impregnated catalysts exhibited enhanced activity compared to monometallic Pt and Ni catalysts, suggesting bimetallic bond formation, which was later confirmed by EXAFS measurements. The co-impregnated micelle catalyst had low activity, comparable to data obtained for monometallic Ni. Bimetallic bond formation could not be measured for the co-impregnated micelle catalyst due to insufficient X-ray absorption during EXAFS measurements. Atomic absorption spectroscopy (AAS) revealed that Pt metal uptake for the co-impregnated micelle catalyst was only 25% of Pt uptake for the incipient wetness catalysts and the stepimpregnated micelle catalyst. The low Pt uptake was predicted to be the reason for the low activity and low X-ray absorption. Chapter 5 discusses challenges associated with reverse micelle synthesis including particle size control, effect of solution pH on metal reduction and adsorption on support, and the effect of pre-treatment conditions on nanoparticle size. To take advantage of the ability to create an idealized environment by controlling particle size to study adsorbate interactions, these challenges must be overcome.