Developing silicalite-1 encapsulated Ni nanoparticles as sintering-/coking-resistant catalysts for dry reforming of methane

Abstract

The stability of catalysts in dry reforming of methane (DRM) is a known issue. In this paper an encapsulation strategy has been employed to improve the stability compared with conventional impregnation methods. Herein, nickel nanoparticles encapsulated in silicalite-1 were prepared using a range of methods including post treatment, direct hydrothermal and seed-directed methods to investigate the effect of synthesis protocol on the properties of catalysts, such as degree of encapsulation and Ni dispersion, and anti-coking/-sintering performance in DRM. The Ni@SiO2-S1 catalysts obtained by the seed-directed synthesis presented the full encapsulation of Ni NPs by the zeolite framework with small particle sizes (∼2.9 nm) and strong metal-support interaction, which could sterically hinder the migration/aggregation of Ni NPs and carbon deposition. Therefore, Ni@SiO2-S1 showed stable CO2/CH4 conversions of 80% and 73%, respectively, with negligible metal sintering and coking deposition (∼0.5 wt%) over 28 h, which outperformed the other catalysts prepared. In contrast, the catalysts developed by the post-treatment and ethylenediamine-protected hydrothermal methods showed the co-existence of Ni phase on the internal and external surfaces, i.e. incomplete encapsulation, with large Ni particles, contributing to Ni sintering and coking. The correlation of the synthesis-structure-performance in this study sheds light on the design of coking-/sintering-resistant encapsulated catalysts for DRM.