On the changing electrochemical behaviour of boron-doped diamond surfaces with time after cathodic pre-treatments

The electrochemical response of the Fe(CN)(6)(4-/3-) redox couple on boron-doped diamond (BDD) electrodes immediately after a cathodic pretreatment and as a function of time exposed to atmospheric conditions is reported here. After this pre-treatment the electrode exhibits a changing electrochemical behaviour, i.e., a loss of the reversibility, for the Fe(CN)(6)(4-/3-) redox couple as a function of time. Raman spectra showed that neither important bulk structural differences nor significant changes in the sp(2)/sp(3) content are introduced into the BDD film by the cathodic pre-treatment indicating that H-terminated sites play an important role in the electrochemical response of the electrodes. Thus, the changing behaviour reflected by a progressive decrease of the electron transfer rate with time must be associated to a loss of superficial hydrogen due to oxidation by oxygen from the air, as confirmed by X-ray photoelectron spectroscopy (XPS) analysis. Moreover, it was also found that this changing electrochemical behaviour is inversely proportional to the doping level, suggesting that the boron content has a stabilizing effect on the H-terminated surface. These results point out the necessity of doing the cathodic pre-treatment just before the electrochemical experiments are carried out in order to ensure reliable and reproducible results. (c) 2006 Elsevier Ltd. All rights reserved.