Date of Award

Fall 12-2009

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

Committee Chair

Steven Stevenson

Committee Chair Department

Chemistry and Biochemistry

Committee Member 2

Paige Buchanan

Committee Member 2 Department

Chemistry and Biochemistry

Abstract

Metallic nitride fullerenes (MNFs) were discovered in 1999. This class of endohedral fullerenes show promise in a new diverse range of useful applications. Since then, focus has shifted to the selective synthesis of these molecules with yields that would accommodate adequate sample distribution. Using the electric arc method, the traditional yield of these molecules has been very low (i.e. < 5 mg), and only a small percentage of the fullerene products (i.e. < 5%). This dissertation introduces the novel CAPTEAR (Chemically Adjusting Plasma Temperature, Energy, And Reactivity) method that allows the targeted synthesis of MNFs in high purity and yield. This method utilizes a nontraditional oxidizing method for fullerene synthesis that has not only provided optimization of MNFs, but also resulted in the discovery of two new classes of fullerenes: metallic nitride azafullerenes (MNAFs) and oxo-metallic fullerenes (OMFs). Evidence suggests that the nitrogen of the MNAF cage provides stability for the trimetallic nitride clusters, while the OMFs are the first fullerenes to encapsulate oxygen and incorporate a seven atom cluster inside a Cgo cage.

Other efforts to increase yields resulted from scaling up production of fullerenes by using larger quantities of starting materials. These larger quantities required energy (electrical current) beyond the capacity of the traditional electric arc generator. Therefore, a new electric arc generator was designed and fabricated to accommodate these demands. This scale-up process resulted in yield increases by an average of 400%. However, to reduce the waste of scaling up as well as costs, our lab developed a recycling method for the expensive metal oxide starting materials. This method has greatly improved cost effectiveness and waste reduction.

Included in

Chemistry Commons

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