Slowing the Kinetics of Alumina Sol-Gel Chemistry for Controlled Catalyst Overcoating and Improved Catalyst Stability and Selectivity

Catalyst overcoating is an emerging approach to engineer surface functionalities on supported metal catalyst and improve catalyst selectivity and durability. Alumina deposition on high surface area material by sol–gel chemistry is traditionally difficult to control due to the fast hydrolysis kinetics of aluminum‐alkoxide precursors. Here, sol–gel chemistry methods are adapted to slow down these kinetics and deposit nanometer‐scale alumina overcoats. The alumina overcoats are comparable in conformality and thickness control to overcoats prepared by atomic layer deposition even on high surface area substrates. The strategy relies on regulating the hydrolysis/condensation kinetics of Al(sBuO)3 by either adding a chelating agent or using nonhydrolytic sol–gel chemistry. These two approaches produce overcoats with similar chemical properties but distinct physical textures. With chelation chemistry, a mild method compatible with supported base metal catalysts, a conformal yet porous overcoat leads to a highly sintering‐resistant Cu catalyst for liquid‐phase furfural hydrogenation. With the nonhydrolytic sol–gel route, a denser Al2O3 overcoat can be deposited to create a high density of Lewis acid–metal interface sites over Pt on mesoporous silica. The resulting material has a substantially increased hydrodeoxygenation activity for the conversion of lignin‐derived 4‐propylguaiacol into propylcyclohexane with up to 87% selectivity.