Using solid-state 1H and 13C MAS NMR spectroscopy, the performance of H-BEA zeolite, modified with either Zn2+ cations (Zn2+/H-BEA) or ZnO clusters (ZnO/H-BEA), has been investigated with respect to n-butane transformation by aromatization and hydrogenolysis pathways. 13C-labeled n-butane has been used to follow the main stages of n-butane transformation on both Zn2+/H-BEA and ZnO/H-BEA with 13C MAS NMR at 298–623 K. Similar surface species, including n-butylzinc, n-butene, allyl-like oligomers, are formed as the intermediates on both zeolites. The kinetics of n-butane transformation has been monitored with 1H MAS NMR in situ at 543–573 K. Kinetics modeling reveals that Zn2+/H-BEA is more active for n-butane transformation than ZnO/H-BEA. A remarkable difference in the rates and the pathways of hydrogenolysis for Zn2+/H-BEA and ZnO/H-BEA has also been established. Propane and methane are hydrogenolysis products on ZnO/H-BEA whereas ethane is produced by the reaction on Zn2+/H-BEA. 13C NMR data and the kinetics analysis provide an insight on the occurrence of joint methane and n-butane conversion on Zn-modified zeolites under non-oxidative conditions.
|Журнал||Journal of Catalysis|
|Состояние||Опубликовано - 1 нояб. 2020|