Effect of the chemical termination of conductive diamond substrate on the resistance to carbon monoxide-poisoning during methanol oxidation of platinum particles

Boron-doped diamond (BDD) films were annealed in hydrogen or oxygen streams and were further used as substrates for Pt electrochemical deposition. SEM and AFM measurements have shown that, from the point of view of the efficiency of noble metal utilization, a hydrogen-terminated diamond (HT-BDD) support is more convenient because it enables better dispersion and smaller size of the deposited particles. An enhancement of ca. 23% of the electrocatalyst specific surface area was observed for Pt/HT-BDD, compared to the case of Pt deposited at oxygen-terminated diamond (OT-BDD). Nevertheless, it was found that when deposited on oxidized BDD, Pt particles are more resistant to fouling during methanol oxidation. Electrochemical oxidation of adsorbed carbon monoxide was investigated by anodic stripping voltammetry and it was demonstrated that the use of OT-BDD substrate facilitates oxidative desorption of CO from the platinum active sites. This behavior was tentatively ascribed to the high surface concentration of oxygenated carbon species, evidenced by XPS, which may act as oxygen donors and/or could partially weaken Pt-CO bonds, thus enabling easier CO eviction from the electrocatalyst surface.