Thermally‐stable single‐site Pd on CeO2 catalyst for selective amination of phenols to aromatic amines without external hydrogen

Abstract Developing a new route to produce aromatic amines as key chemicals from renewable phenols is a benign alternative to current fossil‐based routes like nitroaromatic hydrogenation, but is challenging because of the high dissociation energy of the Ar−OH bond and difficulty in controlling side reactions. Herein, an aerosolizing‐pyrolysis strategy was developed to prepare high‐density single‐site cationic Pd species immobilized on CeO 2 (Pd 1 /CeO 2 ) with excellent sintering resistance. The obtained Pd 1 /CeO 2 catalysts achieved remarkable selectivity of important aromatic amines (yield up to 76.2 %) in the phenols amination with amines without external hydrogen sources, while Pd nano‐catalysts mainly afforded phenyl‐ring‐saturation products. The excellent catalytic properties of the Pd 1 /CeO 2 are closely related to high‐loading Pd single‐site catalysts with abundant surface defect sites and suitable acid‐base properties. This report provides a sustainable route for producing aromatic amines from renewable feedstocks.