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Mobility of Stable π-Complexes of Ethylene with Ag+ Cations in Ag/H-ZSM-5 Zeolite : A 2H Solid-State NMR Study. / Kolokolov, Daniil I.; Arzumanov, Sergei S.; Freude, Dieter и др.
в: Journal of Physical Chemistry C, Том 120, № 9, 17.03.2016, стр. 4993-5000.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Mobility of Stable π-Complexes of Ethylene with Ag+ Cations in Ag/H-ZSM-5 Zeolite
T2 - A 2H Solid-State NMR Study
AU - Kolokolov, Daniil I.
AU - Arzumanov, Sergei S.
AU - Freude, Dieter
AU - Haase, Jürgen
AU - Stepanov, Alexander G.
PY - 2016/3/17
Y1 - 2016/3/17
N2 - Ethylene has been established to form stable π-complexes with Ag+ cations in Ag-modified zeolite H-ZSM-5 (Ag/H-ZSM-5), which strongly affect the reactivity of ethylene on this catalyst. With the aim of revealing the catalytic and adsorptive properties of Ag+ cations in Ag/H-ZSM-5, a characterization of the mobility of ethylene π-complex, located in the zeolite pores, has been performed with 2H solid-state NMR spectroscopy. Ethylene molecules were established to remain bound to the Ag+ cations at temperatures up to 556 K. In the bound state, ethylene exhibits a 2H NMR line shape typical for anisotropic motions. It is inferred that being adsorbed on Ag+ cation, ethylene molecule is involved in two internal rotations about its symmetry axes: along the C2 axis aligned with the C=C bond and about the second C′2 axis orthogonal to the molecule plane. The first rotation occurs with the rate k1 of 10-40 kHz and activation barrier E1 = 2.3 kJ mol-1, while the second motion occurs with the rate k2 of 10-400 kHz and E2 = 4.7 kJ mol-1. The latter motion is faster than the former one. Both motions occur by four-site jump exchange mechanism. When methane is coadsorbed on the zeolite, the dynamical picture becomes different within two different temperature regions, with T ≤ 392 K and T > 392 K. Below 392 K, the rotation mechanism is similar to that without methane coadsortion. However, the barrier for the rotation about the C′2 axis increases (E2II = 7.4 kJ mol-1), which is evidence for the methane interaction with the ethylene π-complex. At temperatures as high as 392 K, the 2H NMR line shape of adsorbed ethylene becomes typical for isotropic-like motion. The barrier of the motion, E = 25 kJ mol-1, is accounted for by involvement of ethylene in the presence of methane in some isotropic or translational motions. At T ≥ 491 K, the line shape analysis reveals an H/D exchange between C2D4 and CH4.
AB - Ethylene has been established to form stable π-complexes with Ag+ cations in Ag-modified zeolite H-ZSM-5 (Ag/H-ZSM-5), which strongly affect the reactivity of ethylene on this catalyst. With the aim of revealing the catalytic and adsorptive properties of Ag+ cations in Ag/H-ZSM-5, a characterization of the mobility of ethylene π-complex, located in the zeolite pores, has been performed with 2H solid-state NMR spectroscopy. Ethylene molecules were established to remain bound to the Ag+ cations at temperatures up to 556 K. In the bound state, ethylene exhibits a 2H NMR line shape typical for anisotropic motions. It is inferred that being adsorbed on Ag+ cation, ethylene molecule is involved in two internal rotations about its symmetry axes: along the C2 axis aligned with the C=C bond and about the second C′2 axis orthogonal to the molecule plane. The first rotation occurs with the rate k1 of 10-40 kHz and activation barrier E1 = 2.3 kJ mol-1, while the second motion occurs with the rate k2 of 10-400 kHz and E2 = 4.7 kJ mol-1. The latter motion is faster than the former one. Both motions occur by four-site jump exchange mechanism. When methane is coadsorbed on the zeolite, the dynamical picture becomes different within two different temperature regions, with T ≤ 392 K and T > 392 K. Below 392 K, the rotation mechanism is similar to that without methane coadsortion. However, the barrier for the rotation about the C′2 axis increases (E2II = 7.4 kJ mol-1), which is evidence for the methane interaction with the ethylene π-complex. At temperatures as high as 392 K, the 2H NMR line shape of adsorbed ethylene becomes typical for isotropic-like motion. The barrier of the motion, E = 25 kJ mol-1, is accounted for by involvement of ethylene in the presence of methane in some isotropic or translational motions. At T ≥ 491 K, the line shape analysis reveals an H/D exchange between C2D4 and CH4.
UR - http://www.scopus.com/inward/record.url?scp=84961118098&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.5b12687
DO - 10.1021/acs.jpcc.5b12687
M3 - Article
AN - SCOPUS:84961118098
VL - 120
SP - 4993
EP - 5000
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 9
ER -
ID: 23331487