First-Principles Study of n-Butane Monomolecular Cracking and Dehydrogenation on Two-Dimensional-Zeolite Model Systems: Reaction Mechanisms and Effects of Spatial Confinement

Wang, Mengen; Boscoboinik, Jorge Anibal; Lu, Deyu

doi:10.1021/acs.jpcc.3c01403

First-Principles Study of n-Butane Monomolecular Cracking and Dehydrogenation on Two-Dimensional-Zeolite Model Systems: Reaction Mechanisms and Effects of Spatial Confinement

Journal Article · Fri Jul 07 04:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c01403· OSTI ID:1992874

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Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Two-dimensional (2D) ultrathin (~0.5 nm) aluminosilicate bilayer films, consisting of hexagonal prisms (a.k.a. double 6-membered rings D6R) with acidic bridging hydroxyl groups exposed on the surface, have been previously synthesized on a Ru(0001) surface as a zeolite model system. These structures are helpful for mimicking zeolite catalysts with D6R building blocks, such as chabazite. We performed density functional theory calculations to investigate the monomolecular cracking and dehydrogenation of n-butane molecules over the acidic hydroxyl groups of the 2D model system and compared the reaction energetics with that in bulk chabazite. The intrinsic activation energy barrier is the highest for dehydrogenation and lowest for central C–C bond cracking in bulk chabazite. The trend of intrinsic energy barriers for dehydrogenation and terminal and central C–C bond cracking is reproduced on the 2D aluminosilicate film. Overall, the activation barriers are higher on the 2D film than in bulk chabazite due to the lack of confinement in the former. We further explored the effects of the zeolite channel size on the n-butane adsorption and monomolecular cracking using different bulk nanoporous zeolite frameworks (TON, MEL, MEI, and VFI). We found that as the confinement of channels decreases, n-butane adsorption becomes weaker, and the intrinsic energy barrier of terminal C–C cracking increases. The activation energy barriers (dehydrogenation and terminal and central C–C cracking) on the 2D bilayer film surface, which may be considered as zeolite cages at the infinite cage size limit, are close to that in VFI with a relatively large channel size. Comparing the reaction pathway of n-butane terminal C–C cracking in 3D nanocages and on the surface of the 2D aluminosilicate film revealed that stabilizing the transition states in the 3D nanocages is responsible for the decrease in the intrinsic energy barriers for bulk zeolites.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC02-05CH11231

OSTI ID:: 1992874

Report Number(s):: BNL-224614-2023-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 28 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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