Redox-State-Regulated Cooperative Hydrogenation in Rh−Co Physically Separated Catalysts

Hydrogenation of aromatic compounds under mild conditions remains challenging because of the high stability of aromatic π systems. Here, we report a physically mixed catalyst comprising rhodium (Rh) and cobalt (Co) nanoparticles embedded in montmorillonite (MMT) that overcomes this limitation. The enhanced activity arises from dynamic interparticle cooperation: Rh nanoparticles selectively dissociate H2, and the resulting hydrogen intermediates are transferred through particle collisions to Co nanoparticles, where aromatic hydrogenation occurs. This cooperative process can be finely regulated by tuning the oxidation states of the individual metal nanoparticles, leading to catalytic performance surpassing that of corresponding Rh−Co alloy catalysts (initial rate: 45 vs 9 μM s-1). Combined experimental and computational investigations reveal that cooperative catalysis can be quantitatively described using linear regression analysis and thereby be predicted through the rate ∼k × (Co2+/Co3+)/(Rh0/Rh3+). Our findings establish a data-driven statistical approach for designing high-performance bimetallic catalysts based on dynamic interparticle interactions.