Highly Dispersed Nickel Particles Encapsulated in Multi‐hollow Silicalite‐1 Single Crystal Nanoboxes: Effects of Siliceous Deposits and Phosphorous Species on the Catalytic Performances

Abstract

AbstractMulti‐hollow silicalite‐1 single crystals (MH) were prepared for the first time by an original synthesis pathway by using tetrabutylphosphonium hydroxide (TBPOH) as a mild desilicating agent. This new generation of hierarchical zeolite allowed the encapsulation of nanoparticles (NPs) featuring an enhanced confinement of the metallic guest and a thin wall thickness. The MH catalyst exhibited a better stability for methane steam reforming at 700 °C than a single‐hollow counterpart (SH). Ni average particle size could be kept lower than 4 nm after 20 h on stream for the MH sample. However, a detailed analysis of kinetic data of the structure‐insensitive CO methanation used as a model reaction revealed that the sample activity was adversely affected by two main factors deriving from the preparation steps. First, a siliceous over‐layer derived from the decomposition of intermediate Ni phyllosilicates, which partly covered the resulting Ni nanoparticles. Second, phosphorus from the templates remained in the samples, probably forming a Ni–P compound upon reduction. The overall catalytic activities observed here were therefore a complex interplay of improved dispersion and poisonous effects.