Effect of Zn–Brønsted acid in zeolites on ethane dehydrogenation with tandem reverse water gas shift reaction

The abundant hydroxyl groups and tunable Brønsted acid sites (BAS) of MWW zeolites were used to introduce and anchor zinc active sites, preventing the volatilization and deactivation of ZnOx due to its reduction to Zn0. Fabricated Zn/MWW catalysts effectively promoted ethane dehydrogenation (EDH) and tandem complex reaction of dehydroaromatization and CO2 oxidative dehydrogenation at high temperatures. Brønsted Zn/MWW catalysts containing [ZnOH]+ were prepared via incipient wetness impregnation using liquid ion exchange whereas those containing [ZnOx]2+ were prepared via atom planting using the gas dechlorination reaction. Additionally, the different acidic sites in MWW zeolites effectively affected the interaction between ZnCl2 and hydroxyl groups during the dechlorination reaction. The catalytic EDH performance of [ZnOx]2+ active sites generated using stronger BASs was higher than that of [ZnOx]2+ active sites generated via weaker BASs and silanol. The synergetic effect of Zn and BASs in zeolites catalyzed dehydroaromatization can be suppress by control the [ZnOH]+ location in the external surface of zeolite or by homogenous consumption of the BAS by [ZnOx]2+. Furthermore, [ZnOH]+ and [ZnOx]2+ catalyzed the reverse water gas shift reaction, accelerated the rate-limiting step of EDH via the CO2 oxidative EDH reaction, inhibited the selectivity of aromatics, and consumed coke via the Boudouard reaction.