Spatial Coordination of Cooperativity in Silica-Supported Cu/TEMPO/Imidazole Catalytic Triad

Multifunctional catalysts obtained by the covalent immobilization of discrete molecular species on porous supports represent a unique approach to emulate some of the design principle and performances of enzymes. However, it is decisive in such systems to control the stoichiometry, spatial distribution, and proximity between the grafted catalytic centers to satisfy the chemical and geometrical requirements for cooperativity. Here, we present strategies to optimize the activity of a catalytic triad on mesoporous silica particles in the representative aerobic oxidation of benzyl alcohol and show that, in contrast with the more-traditional mixed-monolayer approach, activity can be amplified by tuning the spatial distribution of the co-catalysts to maximize the probability of full synergistic pairings.