Concerted Bimetallic Nanocluster Synthesis and Encapsulation via Induced Zeolite Framework Demetallation for Shape and Substrate Selective Heterogeneous Catalysis.

Bimetallic nanoparticle encapsulation in microporous zeolite crystals is a promising route for producing catalysts with unprecedented reaction selectivities. Herein, a novel synthetic approach was developed to produce PtZn nanoclusters encapsulated inside zeolite micropores by introducing Pt cations into a zincosilicate framework via ion exchange, and subsequent controlled demetallation and alloying with framework Zn. The resulting zeolites featured nanoclusters with sizes of approximately 1 nm, having an interatomic structure corresponding to a PtZn alloy as confirmed by pair distribution function (PDF) analysis. These materials featured simultaneous shape and substrate specificity demonstrated by the selective production of p-chloroaniline from the competitive hydrogenation of p-chloronitrobenzene and 1,3-dimethyl-5-nitrobenzene.