The electrocatalytic hydrogenation (ECH) of phenanthrene, anthracene, and naphthalene has been investigated under constant current at Raney nickel electrodes in a mixed aqueous organic medium. The influence of various parameters on the efficiency of the process determined by the current efficiency (a measure of the competition between hydrogenation and hydrogen evolution, the only two electrochemical processes occurring), the extent of hydrogenation (yield of octahydro-derivatives), and the conversion rate was studied with phenanthrene. The best conditions were ethylene glycol or propylene glycol as cosolvent containing between 1.5 to 5% of water, a neutral or slightly acidic medium containing boric acid (0.1 M) as buffer (initial pH of 2.6, final pH of 6.0–6.2), sodium chloride or tetrabutylammonium chloride as supporting electrolyte, a temperature of 80° C, and a current density of 42 to 84 mA/cm2. The most active electrodes (consisting of Raney Ni particles dispersed in a nickel matrix and surrounded by a layer of porous nickel) were obtained by leaching the dispersed alloy particles at 75 °C for 7 h in 30% aqueous sodium hydroxide. The electrohydrogenation stopped at derivatives with a single aromatic ring, namely the octahydrophenanthrenes, octahydroanthracenes, and tetralin. In a non-buffered medium, tetrahydrophenanthrene could be obtained with selectivities of 80% or better. Keywords: electrocatalytic hydrogenation, Raney nickel electrodes, phenanthrene, anthracene, naphthalene.
