Title

Electrochemical catalysis of styrene epoxidation with films of MnO2 nanoparticles, and, Synthesis of mixed metal oxides using ultrasonic nozzle spray and microwaves

Date of Completion

January 2005

Keywords

Engineering, Materials Science

Degree

Ph.D.

Abstract

Films of polyions and octahedral layered manganese oxide (OL-1) nanoparticles on carbon electrodes made by layer-by-layer alternate electrostatic adsorption were active for electrochemical catalysis of styrene epoxidation in solution in the presence of hydrogen peroxide and oxygen. The highest catalytic turnover was obtained by using applied voltage -0.6 V vs. SCE, O2, and 100 mM H2O2. 18O isotope labeling experiments suggested oxygen incorporation from three different sources: molecular oxygen, hydrogen peroxide and/or lattice oxygen from OL-1 depending on the potential applied and the oxygen and hydrogen peroxide concentrations. Oxygen and hydrogen peroxide activate the OL-1 catalyst for the epoxidation. The pathway for styrene epoxidation in the highest yields required oxygen, hydrogen peroxide and a reducing voltage, and may involve an activated oxygen species in the OL-1 matrix. ^ Multicomponent metal oxide (MMO) crystallites were prepared by spraying a reactant solution into a receiving solution or air under microwave radiation at atmospheric pressure. The injection of nitric acid solution through an ultrasonic nozzle into a receiving solution of metal precursor and the use of microwave radiation were combined to form a novel preparation technique called the nozzle-spray/microwave (NMW) method. The inclusion of an additional step, the in situ mixing of precursor solutions prior to their injection through the ultrasonic nozzle spray, led to another procedure called the in situ/nozzle-spray/microwave (INM) method. For comparison, MMO materials with the same metal constituents as those prepared by our novel techniques were prepared by conventional hydrothermal (CH) methods. Fresh materials prepared by NMW, INM and CH methods were heat treated to study the effect of calcination. All materials were characterized before and after calcination using XRD, SEM, Bet, and ICP. The NMW method produces particles with rod-like morphologies different from those obtained using CH methods. The INM method produces an amorphous material that crystallizes after calcination into small (∼200 nm) particles with interesting morphologies. Notably, calcination of materials prepared by both NMW and INM reduces particle size and increases surface area. The present work paves the way to use NMW and INM to prepare MMOs with unique morphologies. ^