Dual Optimization Approach to Bimetallic Nanoparticle Catalysis: Impact of M1/M2 Ratio and Supporting Polymer Structure on Reactivity

A dual optimization approach to nanoparticle catalysis is reported in which both the composition of a bimetallic nanoparticle and the electronic properties of the supporting polystyrene-based polymer can be varied to optimize reactivity and chemoselectivity in nitroarene reductions. Ruthenium-cobalt nanoparticles supported on polystyrene are shown to catalyze nitroarene reductions at room temperature with exceptional activity, as compared with monometallic ruthenium catalysts. Both the identity of the second metal and the M-1/M-2 ratio show a profound effect on the chemoselectivity of nitroarene reductions. These polymer-supported bimetallic catalysts are shown to react with nearly complete chemoselectivity for nitro group reduction over a variety of easily reducible functional groups. The electronic properties of the supporting polymer also have a significant impact on catalysis, in which electron-deficient polystyrenes enable 100% conversion to the aniline product in just 20 min at room temperature. Polymer effects are also shown to influence the mechanism of the reduction reaction, in addition to accelerating the rate, confirming the impact of the polymer structure on catalytic efficiency. These catalysts are easily prepared in a single step from commercial materials and can be readily recycled without loss of activity.