Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of <i>m</i>‑Cresol

In this work, a series of Pd/Fe₂O₃ catalysts were synthesized, characterized, and evaluated for the hydrodeoxygenation (HDO) of <i>m</i>-cresol. It was found that the addition of Pd remarkably promotes the catalytic activity of Fe while the product distributions resemble that of monometallic Fe catalyst, showing high selectivity toward the production of toluene (C–O cleavage without saturation of aromatic ring and C–C cleavage). Reduced catalysts featured with Pd patches on the top of reduced Fe nanoparticle surface, and the interaction between Pd and Fe, was further confirmed using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray absorption near edge fine structure (XANES). A possible mechanism, including Pd assisted H₂ dissociation and Pd facilitated stabilization of the metallic Fe surface as well as Pd enhanced product desorption, is proposed to be responsible for the high activity and HDO selectivity in Pd–Fe catalysts. The synergic catalysis derived from Pd–Fe interaction found in this work was proved to be applicable to other precious metal promoted Fe catalysts, providing a promising strategy for future design of highly active and selective HDO catalysts