First‐Principles Design of Highly Active and Selective Catalysts for Phosgene‐Free Synthesis of Aromatic Polyurethanes

Catalyst design: First principles calculations predict that phosgene can be substituted by dimethyl carbonate (DMC) in the carbamoylation of aromatic amines when using a CeO2 catalyst preferentially exposing the low energy {111} facet. Experimental results confirm the theoretical predictions, and CeO2 nano-octahedra terminated by low energy {111} facets show high activity and selectivity toward the desired dicarbamoylated product.