Zeolite-Encaged Isolated Platinum Ions Enable Heterolytic Dihydrogen Activation and Selective Hydrogenations

Understanding the unique behaviors of atomically dispersed catalysts and the origin thereof is a challenging topic. Herein, we demonstrate a facile strategy to encapsulate Ptd(+) species within Y zeolite and reveal the nature of selective hydrogenation over a Pt@Y model catalyst. The unique configuration of Pt@Y, namely atomically dispersed Pt delta+ stabilized by the surrounding oxygen atoms of six-membered rings shared by sodalite cages and supercages, enables the exclusive heterolytic activation of dihydrogen over Ptd(+)center dot center dot center dot O-2(-) units, resembling the well-known classical Lewis pairs. The charged hydrogen species, i.e., H+ and H delta-, are active reagents for selective hydrogenations, and therefore, the Pt@Y catalyst exhibits remarkable performance in the selective hydrogenation of alpha,beta-unsaturated aldehydes to unsaturated alcohols and of nitroarenes to arylamines.