Nanoscience and Microsystems ETDs

Publication Date



Although they were first discovered more than a century ago, modern enzymatic electrodes used in enzymatic fuel cells and enzymatic amperometric sensors are a rapidly diversifying field, the applications of which have yet to be fully realized. The design parameters that guide the research and industry are also changing as the fundamental mechanisms at the core of the technology become clearer. One of the key design parameters is concerned with how the enzyme catalyst engages the underlying electrode current collector. This one design consideration has led to considerable branching of the field into different fundamental endeavors such as development of enzyme immobilization techniques, research in to the different interfacial electron transfer mechanisms, electrode material characteristics, enzyme orientation in relation to the electrode, and modifications to the electrode to mediate or promote the charge transfer. This work attempts to look at the overall picture of enzyme engagement of the electrode and the subsequent impact of these different characteristics on the overall performance of the electrode. The goal of this work is to develop immobilization, orientation, and electrode modification techniques and to characterize the impact on the electrode. To accomplish this, different bi-functional tethering agents are compared with covalent bonding of the enzyme to the electrode. Two different enzyme orientation techniques are developed, one involving the interaction between an enzyme and its natural substrate and the other involving the interaction of an electric field with the enzyme dipole moment. The internal electron transport chain of a specific group of redox enzymes is explored and then mimicked on the surface of the electrode to aid in the interfacial electron transfer. The mechanisms and techniques elucidated from the previous studies are then applied towards the development of an enhanced enzymatic fuel cell. Finally, the interaction of monochromatic electromagnetic radiation with immobilized metalloporphyrins and the subsequent promotion effect through photo-induced electron transfer is explored.


Enzymatic Fuel Cell, Enzyme Orientation, Photoelectrochemical Biofuel Cell


National Science Foundation Army Research Office

Document Type




Degree Name

Nanoscience and Microsystems

Level of Degree


Department Name

Nanoscience and Microsystems

First Advisor

Atanassov, Plamen

First Committee Member (Chair)

Artyushkova, Kateryna

Second Committee Member

Shreve, Andrew

Third Committee Member

Babanova, Sofia