Effects of pore surface oxidation on electrochemical and mass-transport properties of nanoporous carbon

A new nanoporous (NP) carbon material with a high surface area and a narrow pore size distribution, around 8 A, has been used to investigate the effects that electrochemical oxidation at positive potentials exerts on the capacitance values and effective diffusion coefficients of ions inside the nanopores. An electroanalytical method, based on the single-particle microelectrode technique with micromanipulator, was applied to calculate the diffusion coefficients of 6 M KOH ions in NP carbon. The results were analyzed for short times using the Cottrell model and for long times using the spherical diffusion model. Using cyclic voltammetry, was found that different stages of oxidation took place between 0 and 0.5 V vs. Hg\HgO. After repeated cycling in the first region of oxidation (0-0.3 V), an activation leading to higher capacitance was observed, but the diffusion coefficients decreased from approximately 2 x 10(-9) to 0.5 x 10(-10) cm(2) s(-1). In the second region of oxidation (0.3-0.5 V), where CO2 and 02 evolution can occur, both the capacitance and the diffusion coefficients decreased more dramatically. The effective diffusion coefficients of ions of an activated carbon particle were dependent on the operation potential; decreasing by an order of magnitude when going from -0.3 to +0.3 V. The results are discussed in terms of chemisorption of small oxygen functional groups (-OH or C=O) and ionic interaction with the pore wall. (C) 2004 The Electrochemical Society. All rights reserved.