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Highly-Dispersed Zinc Species on Zeolites for the Continuous and Selective Dehydrogenation of Ethane with CO <sub>2</sub> as a Soft Oxidant

Jiaxu Liu, Ning He, Zhenmei Zhang, Jinpeng Yang, Xiao Jiang, Zhuolei Zhang, Ji Su, Miao Shu, Rui Si, Xiong Guang, Hong-bin Xie, Gianvito Vilé

2021ACS Catalysis104 citationsDOIOpen Access PDF

Abstract

We report herein the preparation, characterization, and catalytic performance of a series of heterogeneous catalysts featuring highly dispersed zinc sites on zeolitic SSZ-13 and ZSM-5 frameworks. The materials are evaluated in the CO 2 -assisted oxidative ethane dehydrogenation, a very important reaction for the synthesis of platform chemicals. In particular, we find that Zn 2.92 /SSZ-13 exhibits high reactivity in the conversion of C 2 H 6 and CO 2 and high ethene selectivity. In line with the experimental results, we show that the selective character of the catalyst is due to the characteristic compositional structure of the support and its topology that can effectively confine CO 2 molecules. An in-depth molecular analysis via operando studies and DFT calculations shows that the rate-limiting step of the reaction with CO 2 is the second C-H bond dissociation to give C 2 H 4 . The addition of CO 2 effectively reduces the energy barrier of this step, favoring desorption of C 2 H 4 while limiting byproduct formation. Overall, this work demonstrates the breakthrough potential of catalysts made of highly dispersed zinc species on zeolites in relevant transformations.

Topics & Concepts

DehydrogenationCatalysisSelectivityChemistryDissociation (chemistry)ZeoliteZincDesorptionInorganic chemistryMoleculeChemical engineeringPhotochemistryCombinatorial chemistryOrganic chemistryAdsorptionEngineeringCatalysis and Oxidation ReactionsCatalytic Processes in Materials ScienceCarbon dioxide utilization in catalysis