Preparation and characterization of nitrogen doped carbon nanotube electrode materials

This dissertation describes the preparation and characterization of nitrogen doped carbon nanotube films by a chemical vapor deposition (CVD) process. Thorough description of the preparation method is given. A variety of techniques are used to demonstrate the relationship between the physicochemical properties and electrochemical properties of nitrogen doped carbon nanotubes, shedding insight to the influence of nitrogen doping on observed electrocatalysis phenomena. Chapter 1 comprises a general overview of the presented material and scope of the work. Chapter 2 details the CVD preparation of nitrogen doped carbon nanotubes. Scanning electron microscopy, thermal gravimetric analysis, and x-ray photoelectron spectroscopy are used to demonstrate the degree of control afforded by the CVD process over the resultant properties of the prepared carbon nanotubes. The direct preparation of carbon nanotube films on a current collector is shown. Chapter 3 consists of a thorough characterization and comparison of nitrogen doped carbon nanotubes and non-doped carbon nanotubes. Transmission electron microscopy, thermal gravimetric analysis, and Raman spectroscopy demonstrate the increased disorder caused by nitrogen doping into the graphitic lattice structure of carbon nanotubes. X-ray photoelectron spectroscopy highlights the existence of multiple carbon-nitrogen surface functionalities that change in relative abundance as the nitrogen content is varied. Titration analyses indicate that nitrogen doped carbon nanotubes are basic and acquire a cationic surface charge in solutions of neutral pH. Chapter 4 presents a collection of voltammetric responses of several outer-sphere and innersphere redox probes. The similarities and differences between the responses at non-doped carbon nanotube electrodes and nitrogen doped carbon nanotube electrodes are noted and discussed in the context of the conclusions of the physical characterizations. A detailed mechanistic analysis of the O2 reduction process at nitrogen doped carbon nanotube electrodes is presented. Chapter 5 details continuing work with carbon nanotube materials for fundamental and applied studies.