Harnessing Synergistic Cooperation of Neighboring Active Motifs in Heterogeneous Catalysts for Enhanced Catalytic Performance.

Understanding the intricate interplay between catalytically active motifs in heterogeneous catalysts has long posed a significant challenge in the design of highly active and selective reactions. Drawing inspiration from biological enzymes and homogeneous catalysts, the synergistic cooperation between neighboring active motifs has emerged as a crucial factor in achieving effective catalysis. This synergistic control is often observed in natural enzymes and homogeneous systems through ligand coordination. The synergistic interaction is especially vital in reactions involving tandem or cascade steps, where distinct active motifs provide different functionalities to enable the co-activation of the reaction substrate(s). Situated within a 3D spatial domain, these catalytically active motifs can shape favorable catalytic landscapes by modulating electronic and geometric characteristics, thereby stabilizing specific intermediate or transition state species in a specific catalytic reaction. In this review, we aim to explore a diverse array of the latest heterogeneous catalytic systems that capitalize on the synergistic cooperativity between neighboring active motifs. We will delve into how such synergistic interactions can be utilized to engineer more favorable catalytic landscapes, ultimately resulting in the modulation of catalytic reactivities.