A Ru/RuO₂ heterostructure boosting electrochemistry-assisted selective benzoic acid hydrogenation

Electrocatalytic hydrogenation of benzoic acid (BA) to cyclohexanecarboxylic acid (CCA) at ambient temperature and pressure has been recognized as a promising alternative to thermal hydrogenation since water is required as the hydrogen source. So far, only a few Pt-based electrocatalysts have been developed in acidic electrolyte. To overcome the limitations of reactant solubility and catalyst corrosion, herein, carbon fiber-supported Ru electrocatalysts with abundant Ru/RuO₂ heterojunctions were fabricated via cyclic electrodeposition between -0.8 and 1.1 V vs. Ag/AgCl. In an alkaline environment, a Ru/RuO₂ catalyst achieves an excellent ECH reactivity in terms of high BA conversion (100%) and selectivity towards CCA (100%) within 180 min at a current density of 200/3 mA cm^-2, showing exceptional reusability and long-term stability. 1-Cyclohexenecarboxylic acid (CEA) was identified as the reaction intermediate, whose the selectivity is governed by the applied potential. Kinetic studies demonstrate that ECH of BA over Ru/RuO₂ follows a Langmuir-Hinshelwood (L-H) mechanism. In situ Raman spectroscopy and theoretical calculations reveal that the Ru/RuO₂ interface enhances the adsorption strength of CEA, thereby facilitating the production of fully hydrogenated CCA. This work provides a deep understanding of the ECH pathway of BA in alkaline media, and gives a new methodology to fabricate heterostructure electrocatalysts.