Document Type


Date of Degree


Degree Name

PhD (Doctor of Philosophy)

Degree In


First Advisor

Johna Leddy


The majority of power generated worldwide is from combustion of fossil fuels. The sustainability and environmental impacts of this non renewable process are severe. Alternative fuels and power generation systems are needed, however, to cope with increasing energy demands. Ammonia shows promise for use in power generation, however it is costly to produce and very few methods of using it as a fuel are developed. To address the need for alternative methods of ammonia synthesis, this research designed and tested a bioelectrochemical device that generates NH3 through electrode induced enzyme catalysis. The ammonia generating device consists of an electrode modified with a polymer that contains whole cell Anabaena variabilis, a photosynthetic cyanobacterium. A. variabilis contains nitrogenase and nitrate/nitrite reductase, catalysts for the production of ammonia. In this system, the electrode supplies driving force and generates a reductive microenvironment near cells to facilitate enzymatic production of NH3 at ambient temperatures and pressures.

Farm animal wastes contain significant amounts of NO2- and NO3-, which can leech into groundwater sources and contaminate them. The system described here recycles NO2- and NO3- to NH4sup+ by the nitrate/nitrite reductase enzyme. Unlike nitrogen fixation by the nitrogenase enzyme whose substrate is atmospheric N2, the substrates for nitrate/nitrite reductase are NO2- and NO3-. The ammonia produced by this system shows great potential as a crop fertilizer.

While the substrates and enzymatic basis for ammonia production by nitrogenase and nitrate/nitrite reductase are very different, there is utility in the comparison of commercially produced ammonia by the Haber Bosch synthesis and by the bioelectrocatalytic device described here. In one day, the Haber Bosch process produces 1800 tons of NH3 at an energetic cost of $500/ton. Per ton of ammonia, the Haber Bosch process consumes 28 GJ of energy. The bioelectrocatalytic device produces 1 ton of NH3 for $10/ton, consuming only 0.04 GJ energy, which can be obtained by sunlight via installation of a photovoltaic device. Thus, the system presented here demonstrates ammonia production with significant impact to the economy.

NH3 production by the bioelectrocatalytic is dependent upon A. var. cell density and electrode polarization. The faradaic current response from cyclic voltammetry is linearly related to cell density and ammonia production. Without electrode polarization, immobilized A. var. do not produce ammonia above the basal level of 2.8 ± 0.4 ΜM. Ten minutes after cycled potential is applied across the electrode, average ammonia output increases to 22 ± 8 ΜM depending on the mediator and substrate chemicals present. Ammonia is produced by this system at 25 °℃ and 1 atm. The electrochemical basis for enhanced NH3 by immobilized cyanobacteria is complex with multiple levels of feedback.


Ammonia, Anabaena variabilis, Cyclic Voltammetry, Enzyme catalysis, Model


xii, 208 pages


Includes bibliographical references (pages 202-208).


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Copyright 2012 Timothy M. Paschkewitz

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