Date Available


Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation




Chemical and Materials Engineering

First Advisor

Dr. Bruce J Hinds


A novel electrochemical method to generate nm-scale bubbles at the tips of CNTs can temporarily block the membrane. A 92% blocking efficiency is achieved when the bubbles are stabilized in 30-60 nm diameter „wells‟ at the tips of CNTs. This well is formed by the electrochemical oxidation of the conductive CNTs partially into the polymer matrix of the membrane. Meanwhile, the nanoscale bubbles can be removed with 0.004 atm pressure to recover the transport through the CNT membrane. The CNT membrane with nanoscale bubble valve system was used to demonstrate electrochemical energy storage.

Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazonium benzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CH3OH/0.5 M H2SO4. A novel programmed pulse potential at 0 V was also seen to nearly eliminate the effects of carbon monoxide poisoning on catalyst Pt. Furthermore, the Pt monolayer was deposited on buckypaper by replacing the precursor Cu monolayer coated on CNTs by the underpotential deposition. The electrochemical surface modification of graphite CNTs by fluorinated benzoic acid was critical to coordinate Cu ions for monolayer formation. The mass activity of the monolayer can be improved to the record value of 2711 A/g. This is about 13 times higher than that of the ~10 nm thick Pt film coated on MWCNTs. Besides the high mass activity, the Pt monolayer coated on buckypaper can be used as catalyst for fuel cells with several advantages such as low cost, high surface area, flexibility, mechanical robustness and enhanced pressure flow.

Finally, a new strategy has been developed toward electrochemical water oxidation with Ir complexes catalyst, which was grafted on buckypaper by direct binding to enhance catalyst activity. The TOF (turn over frequency) of the Ir catalyst for water splitting was 7.9 s-1 at the constant potential of 1.4 V vs Ag/AgCl.