Understanding anodic wear at boron doped diamond film electrodes

Abstract

This research investigated the mechanisms associated with anodic wear of boron-doped diamond (BDD) film electrodes. Cyclic voltammetry (CV), x-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS) were used to measure changes in electrode response and surface chemistry as a function of the charge passed and applied current density. Density functional theory (DFT) modeling was used to evaluate possible reaction mechanisms. The initial hydrogen-terminated surface was electrochemically oxidized at lower potentials than water oxidation (≤ 1.83V/SHE), and was not catalyzed by the hydrogen-terminated surface. In the region where water oxidation produces hydroxyl radicals (OH), the hydrogen-terminated surface may also be oxidized by chemical reaction with OH. Oxygen atoms became incorporated into the surface via reaction of carbon atoms with OH, forming both CO and C-OH functional groups, that were also detected by XPS measurements. Experimental and DFT modeling results indicate that the oxygenated diamond surface lowers the potential for activationless water oxidation from 2.74V/SHE for the hydrogen terminated surface to 2.29V/SHE for the oxygenated surface. Electrode wear was accelerated at high current densities (i.e., 500mAcm−2), where SEM results indicated oxidation of the BDD film resulted in significant surface roughening. These results are supported by EIS measurements that document an increase in the double-layer capacitance as a function of the charge passed. DFT simulations provide a possible mechanism that explains the observed diamond oxidation. DFT simulation results indicate that BDD edge sites (=CH2) can be converted to COOH functional groups, which are further oxidized via reactions with OH to form H2CO3(aq.) with an activation energy of 58.9kJmol−1.