Core-shell and egg-shell zeolite catalysts for enhanced hydrocarbon processing

Le, Thuy T.; Shilpa, Kumari; Lee, Choongsze; Han, Sungmin; Weiland, Conan; Bare, Simon R.; Dauenhauer, Paul J.; Rimer, Jeffrey D.

doi:10.1016/j.jcat.2021.11.004

Core-shell and egg-shell zeolite catalysts for enhanced hydrocarbon processing

Journal Article · Fri Nov 12 00:00:00 EST 2021 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2021.11.004· OSTI ID:1869904

^[1]; Shilpa, Kumari ^[1]; ^[2]; Han, Sungmin ^[1]; Weiland, Conan ^[3]; ^[4]; Dauenhauer, Paul J. ^[2]; ^[1]

Univ. of Houston, TX (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Lab.
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Developing structure-performance relationships with the underlying goal of optimizing known zeolite catalysts involves the manipulation of their physicochemical properties. Here, we systematically assessed the impact of mesoscopic gradients in acid site concentration, which has generally received little attention in the design of zeolite catalysts for hydrocarbon upgrading. A series of core–shell MEL-type zeolites were synthesized with catalytically active ZSM-11 cores and passivated silicalite-2 shells of varying thickness. Our findings revealed that ZSM-11@silicalite-2 particles with ultrathin shells (<10 nm) have enhanced mass transport, characteristic of relatively smaller particles, compared to the corresponding ZSM-11 core. Additionally, catalytic testing using the methanol-to-hydrocarbon (MTH) reaction showed that core–shell zeolites exhibit longer lifetimes, higher total turnovers, and an unexpected promotion of the aromatic cycle in the hydrocarbon pool mechanism. Time-resolved acid titration of core and core–shell catalysts confirmed that the siliceous shell introduces a hydrophobic exterior that impacts molecular diffusion. In comparison, prepared MFI core-shells (ZSM-5@silicalite-1) showed similar enhancement in catalyst performance. Moreover, we prepared egg-shell configurations of each zeolite, silicalite-2@ZSM-11 and silicalite-1@ZSM-5, comprised of an inert core and catalytically active shell. This inverse design of the egg-shell created pseudo nanosheets with total turnovers that were markedly higher than their homogeneous counterparts. Collectively, this study demonstrated that mesoscopic gradients in acid concentration via the design of core–shell and egg-shell zeolites significantly improve catalyst performance over conventional analogues for hydrocarbon upgrading.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Natural Science Foundation of Henan Province; USDOE; University Key Research Projects of Henan Province

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1869904

Alternate ID(s):: OSTI ID: 1844464

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 405; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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