Electrochemical Toluene Hydrogenation Using Binary Platinum-Based Alloy Nanoparticle-Loaded Carbon Catalysts

A couple of toluene (TL) and its hydrogenation product, methylcyclohexane (MCH), are promising high-density hydrogen carriers to store and transport large amounts of hydrogen. Electrochemical hydrogenation of TL to MCH can achieve energy savings compared with hydrogenation using molecular hydrogen generated separately, and development of highly active catalysts for electrochemical TL hydrogenation is indispensable. In this study, binary Pt₃M (M = Rh, Au, Pd, Ir, Cu and Ni) alloy nanoparticle-loaded carbon catalysts were prepared by a colloidal method, and their activity for electrochemical TL hydrogenation was evaluated by linear sweep voltammetry. Each Pt₃M electrode was initially activated by 100 cycles of potential sweep over a potential range of 0–1.2 or 0.8 V vs. reversible hydrogen electrode (RHE). For all activated Pt₃M electrodes, the cathodic current density for electrochemical TL hydrogenation was observed above 0 V, that is the standard potential of hydrogen evolution reaction. Both specific activity, cathodic current density per electrochemical surface area, and mass activity, cathodic current density per mass of Pt₃M, at 0 V for the Pt₃Rh/C electrode were the highest, and about 8- and 1.2-times as high as those of the commercial Pt/C electrode, respectively, which could mainly be attributed to electronic modification of Pt by alloying with Rh. The Tafel slope for each activated Pt₃M/C electrode exhibited the alloying of Pt with the second metals did not change the electrochemical TL hydrogenation mechanism.