Surface-Modified Pd/CeO₂ Single-Atom Catalyst Shows Increased Activity for Suzuki Cross-Coupling

Single-atom catalysts (SACs) comprise catalytically active atoms dispersed on supports; they combine the high activity and site uniformity of homogeneous catalysts with the ease of separability of heterogeneous catalysts. However, SACs lack fine control over the active site, provided by ligands in homogeneous catalysts. In this work, we demonstrate that modification of the support with an organic monolayer is a viable approach to improving the catalytic performance. The addition of catechol-type monolayers to a Pd/CeO₂ SAC increases its catalytic activity for Suzuki cross-coupling, a central reaction in the synthesis of fine chemicals and pharmaceuticals. Kinetic trials reveal that the coating reduces the activation energy from 49 ± 9 to 22 ± 5 kJ/mol and produces a 4-fold rate enhancement at 25 °C, an effect we attribute to π-π interactions between the reactant and the catechol coating. Further development of this approach could vastly increase the utility of SACs in organic synthesis.