Construction of Metal/Zeolite Hybrid Nanoframe Reactors via in-Situ-Kinetics Transformations

Abstract

Metal/zeolite hybrid nanoframes featuring highly accessible compartmental environments, abundant heterogeneous interfaces, and diverse chemical compositions are expected to possess significant potential for heterogeneous catalysis, yet their general synthetic methodology has not yet been established. In this study, we developed a two-step in-situ-kinetics transformation approach to prepare metal/ZSM-5 hybrid nanoframes with exceptionally open nanostructures, tunable metal compositions, and abundant accessible active sites. Initially, the process involved the formation of single-crystalline ZSM-5 nanoframes through an anisotropic etching and recrystallization kinetic transformation process. Subsequently, through an in situ reaction of the Ni2+ ions and the silica species etched from ZSM-5 nanoframes, layered nickel silicate emerged on both the inner and outer surfaces of the zeolite nanoframes. Upon reduction under a hydrogen atmosphere, well-dispersed Ni nanoparticles were produced and immobilized onto the ZSM-5 nanoframes. Strikingly, this strategy can be extended to immobilize a variety of ultrasmall monometallic and bimetallic alloy nanoparticles on zeolite nanoframes. Benefiting from the structural and compositional advantages, the resultant hybrid nanoframes with a high loading of discrete Ni nanoparticles exhibited enhanced performance in the hydrodeoxygenation of stearic acid into liquid fuels. Overall, the methodology shares fresh insights into the rational construction of intricate frame-like metal/zeolite hybrid nanoreactors for many potential catalytic applications.