Supported Mono And Bimetallic Platinum And Iron Nanoparticles Electronic, Structural, Catalytic, And Vibrational Properties

Catalysis technologies are among the most important in the modern world. They are instrumental in the realization of a variety of products and processes including chemicals, polymers, foods, pharmaceuticals, fuels, and fuel cells. As such, interest in the catalysts that drive these processes is ongoing, and basic research has led to significant advances in the field, including the production of more environmentally friendly catalysts that can be tuned at the molecular/atomic level. However, there are many factors which influence the performance of a catalyst and many unanswered questions still remain. The first part of this work is concerned with the factors that influence the catalytic properties (activity, selectivity, and stability) of supported Pt and Pt-M nanoparticles (NPs). These factors are a synergistic combination of size, composition, support, oxidation state, and reaction environment (i.e. adsorbates, temperature, pressure, etc.). To probe the catalytic properties of complex and dynamic NP systems we have used MeOH decomposition and oxidation reactions, each of which has significant environmental and economic potential. We have given some emphasis to the state of NP oxidation, and with the aid of X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), have followed the formation and temperature-dependent evolution of oxide species on Pt NPs. Further, we have explored how these species behave under the conditions of our probe reactions using a packed-bed mass flow reactor coupled to a quadrupole mass spectrometer (QMS). To carry out our investigations we exploit a NP synthesis method which is rather novel to nanocatalysis, micelle encapsulation. Since most available experimental techniques give information on ensemble averages, control over size distributions in NP samples is critical if unambiguous results are to be obtained. Micelle encapsulation allows us this control with several unique, inherent iv advantages. It is to this end that micelle encapsulation has allowed us to probe the detailed structure of small (~1 nm), supported, Pt NPs with extended X-ray absorption fine structure spectroscopy (EXAFS). Furthermore, we were able to explore experimentally, for the first time, the vibrational density of states (VDOS) of supported, isolated, monodispersed, mono and bimetallic NP systems via nuclear resonant inelastic X-ray scattering (NRIX). These synchrotron-based techniques (EXAFS, NRIXS) rely heavily on the monodispersity of the NP ensemble for reliable informatio