A comparison of nickel boride and Raney nickel electrode activity in the electrocatalytic Hydrogenation of Phenanthrene

Abstract

The electrocatalytic activity of nickel boride in the electrocatalytic hydrogenation (ECH) of phenanthrene in ethylene glycol–water at 80 °C has been compared to that of Raney nickel and fractal nickel. The intrinsic activity of the electrode material (real electrode activity) is the same for nickel boride and Raney nickel electrodes and is lower for fractal nickel electrodes. The apparent electrode activity of nickel boride pressed powder electrodes (Ni2B electrodes) is less than that of codeposited Raney nickel (RaNi) electrodes and pressed powder fractal nickel/Raney nickel (Ni/RaNi = 50/50 to 0/100) electrodes. The apparent activity of Ni2B electrodes is improved by adding sodium chloride to the powder and dissolving it after pressing (Ni2B–NaCl electrodes). The Ni2B–NaCl electrodes have the same apparent activity as codeposited RaNi and pressed powder Ni/RaNi (20/80 to 0/100) electrodes. The apparent and real electrode activity of Ni/RaNi electrodes increases with the RaNi content up to a 20/80 ratio. The Tafel and alternating current (ac) impedance parameters were determined for the hydrogen evolution reaction (HER) in 1 M aqueous sodium hydroxide at 25 °C at nickel boride and at codeposited RaNi electrodes. The intrinsic electrocatalytic activity for HER, expressed by the ratio of the exchange current density over the roughness factor (I0/R), is similar for Ni2B, Ni2–NaCl, and codeposited RaNi electrodes. Surface characterization of Ni2B and Ni2B–NaCl electrodes was carried out by BET, ac impedance, scanning electron microscopy, and mercury porosimetry. No direct relation between the apparent electrode activity in ECH and the surface measured by BET and ac impedance was found. The ac impedance measurements were also carried out in the presence of sodium trans-cinnamate.