Growth of Phthalocyanine Doped and Undoped Nanotubes Using Mild Synthesis Conditions for Development of Novel Oxygen Reduction Catalysts
co-authored with Shelley D. Minteer from Saint Louis University
Precious metal alloys have been the predominant electrocatalyst used for oxygen reduction in fuel cells since the... more
Precious metal alloys have been the predominant electrocatalyst used for oxygen reduction in fuel cells since the 1960s.
Although performance of these catalysts is high, they do have drawbacks. The two main problems with precious metal alloys are catalyst passivation and cost. This is why new novel catalysts are being developed and employed for oxygen reduction. This paper details the low temperature solvothermal synthesis and characterization of carbon nanotubes that have been doped with both iron and cobalt centered phthalocyanine. The synthesis is a novel low-temperature, supercritical solvent synthesis that reduces halocarbons to form a metal chloride byproduct and carbon nanotubes. Perchlorinated phthalocyanine was added to the nanotube synthesis to incorporate the phthalocyanine structure into the graphene sheets of the nanotubes to produce doped nanotubes that have the catalytic
oxygen reduction capabilities of the metallo-phthalocyanine and the advantageous material qualities of carbon nanotubes. The cobalt phthalocyanine doped carbon nanotubes showed a half wave oxygen reduction potential of -0.050 ( 0.005 V vs Hg\HgO, in comparison to platinum’s half wave oxygen reduction potential of -0.197 ( 0.002 V vs Hg\HgO).
Chemical polymerization and electrochemical characterization of thiazines for NADH electrocatalysis applications
Co-authored with Shelley D. Minteer from Saint Louis University
Electrochemically polymerized azines have been employed frequently as ... more
Electrochemically polymerized azines have been employed frequently as NADH electrocatalysts in biosensors and biofuel cells. However, some applications of these electrocatalysts do not lend themselves to electropolymerization. Therefore, this research investigates the chemical synthesis and application
of poly(methylene blue) (PMB) and poly(methylene green) (PMG) in electrocatalysis. In an attempt to develop a simple synthesis for polymerized thiazines that could be immobilized on any surface, we investigated several polymerization protocols that are described in this paper. Structural analyses imply that the chemically synthesized polymers are chemically unique in comparison to the electropolymerized polymers. Amperometric investigations were used to compare the catalytic activity of chemically and electrochemically synthesized polymers as electrocatalysts for the oxidation of NADH and the chemically
synthesized polymers were employed at the bioanode of a methanol/air biofuel cell to show their utility for this application.
Cyanamide-derived non-precious metal catalyst for oxygen reduction
co-authored with Piotr Zelenay from LANL and Deborah J . Myers from ANL
Cyanamide was used in the preparation series of ... more Cyanamide was used in the preparation series of metal–nitrogen–carbon (M–N–C) oxygen reduction catalysts. The best catalyst, treated at 1050 °C, shows good performance versus previously reported nonprecious metal catalysts with an OCV ~1.0 V and a current density of 105 mA/cm 2 (iR-corrected) at 0.80 V in H 2 /O 2 fuel cell testing (catalyst loading: 4 mg cm− 2 ). Although nitrogen content has been previously correlated positively with ORR activity, no such trend is observed here for any nitrogen type. The combined effects of nitrogen and sulfur incorporation into the carbon may account for the high activity of the 1050 °C catalyst.
Functionalized Graphene as a Catalytic Counter Electrode in Dye Sensitized Solar Cells
J. D. Roy-Mayhew, D. J. Bozym, C. Punckt, I. A. Aksay
ACS Nano 4 (2010) 6203
When applied on the counter electrode of a dye-sensitized solar cell, functionalized graphene sheets with... more When applied on the counter electrode of a dye-sensitized solar cell, functionalized graphene sheets with oxygen-containing sites perform comparably to platinum (conversion efficiencies of 5.0 and 5.5%, respectively, at 100 mW/cm² AM1.5G simulated light). To interpret the catalytic activity of functionalized graphene sheets toward the reduction of triiodide, we propose a new electrochemical impedance spectroscopy equivalent circuit that matches the observed spectra features to the appropriate phenomena. Using cyclic voltammetry, we also show that tuning our material by increasing the amount of oxygen-containing functional groups can improve its apparent catalytic activity. Furthermore, we demonstrate that a functionalized graphene sheet based ink can serve as a catalytic, flexible, electrically conductive counter electrode material.
Electrochemical Performance of Graphene as Effected by Electrode Porosity and Graphene Functionalization
C. Punckt, M. A. Pope, J. Liu, Y. Lin, I. A. Aksay
Electroanalysis 22 (2010) 2834
Graphene-based electrodes have recently gained popularity due to their superior electrochemical properties. However,... more Graphene-based electrodes have recently gained popularity due to their superior electrochemical properties. However, the exact mechanisms of electrochemical activity are not yet understood. Here, we present data from NADH oxidation and ferri/ferrocyanide redox probe experiments to demonstrate that both (i) the porosity of the graphene electrodes, as effected by the packing morphology, and (ii) the functional group and the lattice defect concentration play a significant role on their electrochemical performance.

