TY - JOUR
T1 - Effects of zeolite structural confinement on adsorption thermodynamics and reaction kinetics for monomolecular cracking and dehydrogenation of n-butane
AU - Janda, Amber
AU - Vlaisavljevich, Bess
AU - Lin, Li Chiang
AU - Smit, Berend
AU - Bell, Alexis T.
PY - 2016
Y1 - 2016
N2 - The effects of zeolite structure on the kinetics of n-butane monomolecular cracking and dehydrogenation are investigated for eight zeolites differing in the topology of channels and cages. Monte Carlo simulations are used to calculate enthalpy and entropy changes for adsorption (ΔHads-H+ and ΔSads-H+) of gas-phase alkanes onto Brønsted protons. These parameters are used to extract intrinsic activation enthalpies (ΔHint ‡), entropies (ΔSint ‡), and rate coefficients (kint) from measured data. As ΔSads-H+ decreases (i.e., as confinement increases), ΔHint ‡ and ΔSint ‡ for terminal cracking and dehydrogenation decrease for a given channel topology. These results, together with positive values observed for ΔSint ‡, indicate that the transition states for these reactions resemble products. For central cracking (an earlier transition state), ΔHint ‡ is relatively constant, while ΔSint ‡ increases as ΔSads-H+ decreases because less entropy is lost upon protonation of the alkane. Concurrently, selectivities to terminal cracking and dehydrogenation decrease relative to central cracking because ΔSint ‡ decreases for the former reactions. Depending on channel topology, changes in the measured rate coefficients (kapp) with confinement are driven by changes in kint or by changes in the adsorption equilibrium constant (Kads-H+). Values of ΔSint ‡ and ΔHint ‡ are positively correlated, consistent with weaker interactions between the zeolite and transition state and with the greater freedom of movement of product fragments within more spacious pores. These results differ from earlier reports that ΔHint ‡ and ΔSint ‡ are structure-insensitive and that kapp is dominated by Kads-H+. They also suggest that ΔSads-H+ is a meaningful descriptor of confinement for zeolites having similar channel topologies.
AB - The effects of zeolite structure on the kinetics of n-butane monomolecular cracking and dehydrogenation are investigated for eight zeolites differing in the topology of channels and cages. Monte Carlo simulations are used to calculate enthalpy and entropy changes for adsorption (ΔHads-H+ and ΔSads-H+) of gas-phase alkanes onto Brønsted protons. These parameters are used to extract intrinsic activation enthalpies (ΔHint ‡), entropies (ΔSint ‡), and rate coefficients (kint) from measured data. As ΔSads-H+ decreases (i.e., as confinement increases), ΔHint ‡ and ΔSint ‡ for terminal cracking and dehydrogenation decrease for a given channel topology. These results, together with positive values observed for ΔSint ‡, indicate that the transition states for these reactions resemble products. For central cracking (an earlier transition state), ΔHint ‡ is relatively constant, while ΔSint ‡ increases as ΔSads-H+ decreases because less entropy is lost upon protonation of the alkane. Concurrently, selectivities to terminal cracking and dehydrogenation decrease relative to central cracking because ΔSint ‡ decreases for the former reactions. Depending on channel topology, changes in the measured rate coefficients (kapp) with confinement are driven by changes in kint or by changes in the adsorption equilibrium constant (Kads-H+). Values of ΔSint ‡ and ΔHint ‡ are positively correlated, consistent with weaker interactions between the zeolite and transition state and with the greater freedom of movement of product fragments within more spacious pores. These results differ from earlier reports that ΔHint ‡ and ΔSint ‡ are structure-insensitive and that kapp is dominated by Kads-H+. They also suggest that ΔSads-H+ is a meaningful descriptor of confinement for zeolites having similar channel topologies.
UR - http://www.scopus.com/inward/record.url?scp=84964670716&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b11355
DO - 10.1021/jacs.5b11355
M3 - Article
C2 - 26909765
SN - 0002-7863
VL - 138
SP - 4739
EP - 4756
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 14
ER -