Transition-metal nanoparticles (Co,
Ni, and Cu) encapsulated in
hollow zeolite single crystals were prepared by recrystallization
of impregnated bulk MFI crystals in the presence of tetrapropylammonium
(TPAOH) solutions. The size and number of particles in hollow MFI
depended mainly on the aluminum content. The encapsulation of the
nanoparticles prevented them from growing, thus enabling the control
of particle size even after high temperature treatments. For low metal
loadings (<3 wt %), the mean particle sizes for Co, Ni, and Cu
in hollow silicalite-1 were 3.5 ± 0.3, 3.1 ± 0.5, and 1.5
± 0.2 nm, respectively. In the case of hollow ZSM-5, higher loadings
(∼8 wt %) could be obtained with mean particle sizes of 17
± 2 nm, 13 ± 2 nm, and 15 ± 2 nm for Co, Ni, and Cu
systems. The mechanism of transition metal nanoparticle formation
was markedly different from that of noble metals. At high pH values,
transition-metal cations first reacted with dissolved silica species
yielding fibrous metal phyllosilicates that were located inside the
crystal cavities. The metal phyllosilicates were then converted into
nanoparticles upon reduction under H2 at high temperature
(500–750 °C). Silicalite-1 encapsulated Ni particles were
used in the catalytic hydrogenation of substituted benzenes and showed
an outstanding size-selectivity effect. Ni particles were accessible
to toluene but not to mesitylene, confirming that the activity is
directly related to the diffusion properties of molecules through
the zeolite membrane.