Abstract
Often, trace impurities in a feed stream will cause failures in industrial applications. The efficient removal of such a trace impurity from industrial steams, however, is a daunting challenge due to the extremely small driving force for mass transfer. The issue lies in an activity-stability dilemma, that is, an ultrafine adsorbent that offers a high exposure of active sites is favorable for capturing species of a low concentration, but free-standing adsorptive species are susceptible to rapidly aggregating in working conditions, thus losing their intrinsic high activity. Confining ultrafine adsorbents in a porous matrix is a feasible solution to address this activity-stability dilemma. We herein demonstrate a proof of concept by encapsulating ZnO nanoclusters into a pure-silica MFI zeolite (ZnO@silicalite-1) for the ultradeep removal of H(2)S, a critical need in the purification of hydrogen for fuel cells. The Zn species and their interaction with silicalite-1 were thoroughly investigated by a collection of characterization techniques such as HADDF-STEM, UV-visible spectroscopy, DRIFTS, and (1)H MAS NMR. The results show that the zeolite offers rich silanol defects, which enable the guest nanoclusters to be highly dispersed and anchored in the silicious matrix. The nanoclusters are present in two forms, Zn(OH)(+) and ZnO, depending on the varying degrees of interaction with the silanol defects. The ultrafine nanoclusters exhibit an excellent desulfurization performance in terms of the adsorption rate and utilization. Furthermore, the ZnO@silicalite-1 adsorbents are remarkably stable against sintering at high temperatures, thus maintaining a high activity in multiple adsorption-regeneration cycles. The results demonstrate that the encapsulation of active metal oxide species into zeolite is a promising strategy to develop fast responsive and highly stable adsorbents for the ultradeep removal of trace impurities.