Effect of Surface Oxygen on the Wettability and Electrochemical Properties of Boron-Doped Nanocrystalline Diamond Electrodes in Room-Temperature Ionic Liquids

摘要

This paper reports on how the surface chemistry of boron-doped nanocrystalline diamond (BDD) thin-film electrodes (H vs O) affects the wettability and electrochemical properties in two room-temperature ionic liquids (RTILs): [BMIM][PF6] and [HMLM][PF6]. Comparative measurements were made in 0.5 mol L-1 H2SO4. The BDD electrodes were modified by microwave or radio-frequency (RF) plasma treatment in H-2 (H-BDD), Ar BDD), or O-2 (O-BDD). These modifications produced low-, medium-, and high-oxygen surface coverages. Atomic O/C ratios, as determined by X-ray photoelectron spectroscopy (XPS), were 0.01 for H-BDD, 0.08 for Ar-BDD, and 0.17 for O-BDD. The static contact angle of ultrapure water on the modified electrodes decreased from 110 degrees (H-BDD) to 41 degrees (O-BDD) with increasing surface oxygen coverage, as expected as the surface becomes more hydrophilic. Interestingly, the opposite trend was seen for both RTILs as the contact angle increased from 20 degrees (H-BDD) to 50 degrees (O-BDD) with increasing surface oxygen coverage. The cyclic voltammetric background current and potential-dependent capacitance in both RTILs were largest for BDD electrodes with the lowest O/C ratio (H-BDD) and smallest contact angle. Slightly larger voltammetric background currents and capacitance were observed in [HMIM][PF6] than in [BMIM][PF6]. Capacitance values ranged from 8 to 16 mu F cm(-2) over the potential range for H-BDD and from 4 to 6 mu F cm(-2) for O-BDD. The opposite trend was observed in H2SO4 as the voltammetric background current and capacitance were largest for BDD electrodes with the highest O/C ratio (O-BDD) and smallest contact angle. In summary, reducing the surface oxygen on BDD electrodes increases the wettability to two RTILs and this increases the voltammetric background current and capacitance.