Date of Award

2015

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Graduate Group

Chemistry

First Advisor

Christopher B. Murray

Abstract

The d-block elements are very important in magnetics, electronics, catalysis, and biological systems. The synthesis and characterization of nearly monodisperse d-block element based nanocrystals with a precise control over the size, composition, and shape are important to utilize the nanocrystals in such applications. The goals of my thesis are to synthesize d-block transition metal based nanocrystals and understand their magnetic and catalytic properties. I present the size- and composition-dependent AC magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency applications. The nanocrystals are synthesized through high-temperature solvothermal decomposition, and their stoichiometry is determined by Mossbauer spectroscopy. Size-dependent magnetic permeability is observed in maghemite nanocrystals, while as-synthesized, magnetite-rich, iron oxide nanocrystals do not show size dependence due to the inhomogeneous crystal structure of the as-synthesized nanocrystals. The saturation magnetization of iron oxide nanocrystals is increased by doping of non-magnetic Zn2+ into A site of ferrite, resulting the enhancement of the real part of the magnetic permeability of Zn0.25Fe2.75O4 nanocrystals by twofold compared to that of similarly sized ferrite nanocrystals. The integration of 12.3 nm Zn0.25Fe2.75O4 nanocrystals into a microfabricated toroidal inductor and a solenoid inductor yield higher quality factors than air core inductors with the same geometries. The ligand exchange with dendrimers reduces the blocking temperature of Mn0.08Zn0.33Fe2.59O4 nanocrystal, indicating the decrease of dipolar coupling between nanocrystals. The study on MnxFe3-xO4 and CoxFe3-xO4 nanocrystals shows a clear difference in DC and AC magnetic behaviors of soft and hard magnetic nanocrystals. The inductor with zinc ferrite nanocrystal core is embedded into a power converter and its temperature dependent energy efficiency is measured. The energy efficiency of a power converter with the nanocrystal core inductor rises as the temperature increases while that of the power converters with an air core inductor or commercial core inductor decreases. Finally, I describe the hydrodeoxygenation reaction of 5-hydroxymethylfurfural into 2,5-dimethylfuran by metallic nanocrystals such as Pt, PtMn, PtFe, PtCo, and PtNi. Both conversion ratio and selectivity for 2,5-dimethylfuran show clear composition dependent catalytic properties and, in particular, 3.7 nm Pt3Co2 nanocrystals achieve 98 % of selectivity for 2,5-dimethylfuran.

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