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1.
Angew Chem Int Ed Engl ; 61(16): e202117742, 2022 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-35138688

RESUMEN

Tailoring processes of nucleation and growth to achieve desired material properties is a pervasive challenge in synthetic crystallization. In systems where crystals form via nonclassical pathways, engineering materials often requires the controlled assembly and structural evolution of colloidal precursors. In this study, we examine zeolite SSZ-13 crystallization and show that several polyquaternary amines function as efficient accelerants of nucleation, and, in selected cases, tune crystal size by orders of magnitude. Among the additives tested, polydiallyldimethylammonium (PDDA) was found to have the most pronounced impact on the kinetics of SSZ-13 formation, leading to a 4-fold reduction in crystallization time. Our findings also reveal that enhanced nucleation occurs at an optimal PDDA concentration where a combination of light-scattering techniques demonstrate these conditions lead to polymer-induced aggregation of amorphous precursors and the promotion of (alumino)silicate precipitation from the growth solution. Here, we show that relatively low concentrations of polymer additives can be used in unique ways to dramatically enhance SSZ-13 crystallization rates, thereby improving the overall efficiency of zeolite synthesis.

2.
Angew Chem Int Ed Engl ; 61(8): e202113077, 2022 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-34877748

RESUMEN

Designing zeolite catalysts with improved mass transport properties is crucial for restrictive networks of either one- or two-dimensional pore topologies. Here, we demonstrate the synthesis of finned ferrierite (FER), a commercial zeolite with two-dimensional pores, where protrusions on crystal surfaces behave as pseudo nanoparticles. Catalytic tests of 1-butene isomerization reveal a 3-fold enhancement of catalyst lifetime and an increase of 12 % selectivity to isobutene for finned samples compared to corresponding seeds. Electron tomography was used to confirm the identical crystallographic registry of fins and seeds. Time-resolved titration of Brønsted acid sites confirmed the improved mass transport properties of finned ferrierite compared to conventional analogues. These findings highlight the advantages of introducing fins through facile and tunable post-synthesis modification to impart material properties that are otherwise unattainable by conventional synthesis methods.

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