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Title: Activation of highly ordered pyrolytic graphite for heterogeneous electron transfer: Relationship between electrochemical performance and carbon microstructure

Technical Report ·
OSTI ID:5314074

The electrochemical and vibrational spectroscopic properties of highly ordered pyrolytic graphite (HOPG) were determined before and after modification by anodization or pulsed laser irradiation. Both treatments greatly accelerated the heterogeneous electron-transfer-rate constants for the Fe(CN)6(3-/4-) and dopamine redox systems on HOPG by approximately six orders of magnitude. At intermediate electrochemical pretreatment (ECP) potentials, a spatially heterogeneous surface resulted, with surface regions exhibiting the 1360/cm band being separated by tens of microns. The results clearly indicate that graphitic edge plane is necessary for fast electron transfer, and that the pretreatment procedures accelerate k0 by generating edge-plane defects in the HOPG lattice. The mechanisms of defect generation for the two procedures appear very different, with ECP appearing to follow a nucleation process leading to a spatially heterogeneous surface, while the laser pulse appears to shatter the HOPG lattice, leading to a more uniform distribution of active sites. The results provide important conclusions about the relationship between carbon electrode microstructure and heterogeneous electron transfer activity. Of particular interest is the heterogeneous electron transfer rate between carbon electrodes and various well-known redox systems such as ascorbic acid, ferri/ferrocyanide, and the catecholamines. Not only are these systems of significant analytical interest, but they serve as benchmarks for comparisons of electrode performance.

Research Organization:
Ohio State Univ., Columbus, OH (USA). Dept. of Chemistry
OSTI ID:
5314074
Report Number(s):
AD-A-211645/7/XAB
Resource Relation:
Other Information: Pub. in Jnl. of the American Chemical Society, Vol. 111, No. 4 p1217-1223(1989)
Country of Publication:
United States
Language:
English