Electrochemical surface rehydrogenation of boron-doped diamond electrodes after electrochemical polishing

Abstract

Non-diamond carbon impurity and surface roughness are features that can affect the response of boron-doped diamond (BDD) electrodes. Herein, we report on the electropolishing of BDD electrodes carried out in the presence of acetic and sulfuric acid for different times (1, 2, and 4 h). The wet electrochemical treatment smooths the polycrystalline diamond surface and reduces the non-diamond sp2 carbon impurity content while increasing the surface oxygen content. Changes in surface texture and microstructure were revealed by atomic force microscopy, Raman spectroscopy, and cyclic voltammetry. Subsequently, the surface oxygen content was reduced by increasingly severe cathodic pretreatments (CPTs). This was revealed by changes in the voltametric response for the [Fe(CN)6]3−/4– and ascorbic acid (AA) redox systems, as both exhibit electron transfer kinetics sensitive to the level of oxidation of the BDD surface. For [Fe(CN)6]3−/4–, greater ∆Ep values were obtained for the electropolished (EP-BDD) electrodes, as compared to the as received (AR-BDD) electrode. However, after CPTs the EP-BDD electrodes exhibited smaller ∆Ep values (∼60 mV), which indicate significantly improved electrochemical reversibility and faster electron-transfer kinetics caused by the decreased level of surface oxidation (greater hydrogenation). The increased surface oxygen content brought on by the electropolishing process had also a significant effect on the AA oxidation peak potential (Eap), making it at least ∼140 mV more positive than that for the AR–BDD electrode. However, after CPTs the Eap values for the EP–BDD electrodes became at least ∼0.1 V less positive than that for the AR–BDD electrode, indicating that the surface of the EP-BDD electrodes possesses less surface carbon‑oxygen functional groups (i.e., it is more hydrogenated). The combination of electropolishing and cathodic pretreatment is a way to process the BDD electrode surface to create a smoother, low oxygen surface in much the same way as a hydrogen plasma treatment does.