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Tuning the Mechanism of H/D Exchange for Isobutane on H-BEA by Loading Zn Species in Zeolite
Sergei S Arzumanov1, Anton A Gabrienko1, Dieter Freude2
1Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk, 630090, Russia.
Abstract:
Kinetics of H/D hydrogen exchange between deuterated isobutane-d10 and Brønsted acid sites (BAS) of three zeolite samples (H-BEA, ZnO/H-BEA, Zn2+ /H-BEA) were monitored with 1 H MAS NMR in situ at 343-468 K. The regioselective H/D exchange in the methyl groups detected on H-BEA can be rationalized in terms of the mechanism of indirect exchange, which involves protonation of the intermediate olefin and further hydride abstraction from the other alkane molecule by the formed carbenium ion. Loading of Zn species in the zeolite results in a decrease of the rate and an increase of the activation energy of the exchange. The loaded Zn species provide the tuning effect on the reaction occurrence, changing the mechanism from the indirect one to the mechanism of the direct exchange.
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