The development of efficient technologies for light olefin
production
is crucial to the petrochemical industry. In particular, isobutene
synthesis via n-butane dehydroisomerization, catalyzed
by a bifunctional catalyst containing Pt nanoparticles supported on
acidic zeolites, is one of the most significant catalytic pathways.
However, it often suffers from low catalyst stability due to sintering
and coke deposition, eventually hindering their catalytic performance.
In this contribution, we report the rational design of ultrasmall
PtZn nanoparticles supported on diverse zeolite composites containing
different parent zeolites [e.g., ferrierite (FER), mordenite, and
Zeolite Socony Mobil-5] as cores and hierarchical silicalite-1 (SN1)
as shells via a two-step hydrothermal process. The synthesized composites
revealed that the SN1 nanocrystals were fully covered on the outermost
surfaces of core zeolites with highly dispersed PtZn nanoparticles
on the SN1 phase. The synergistic effect of the additional zinc species
in Pt, preventing sintering and altering electronic properties of
metals, along with weakened Brønsted acidity at the outermost
surface of a parent zeolite due to covered SN1 shells, enhanced the
catalytic performance and stability in n-butane dehydroisomerization.
Among several designer composites, FER/SN1 achieved the highest isobutene
yield (16.2%) by suppressing side reactions through modified acid
and shape-selective properties. These findings demonstrate the feasibility
of the rational design of alloy nanoparticles supported on zeolite
composites with modified acid and shape-selective properties for isobutene
production.