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Decarboxylation of Lactones over Zn/ZSM‐5: Elucidation of the Structure of the Active Site and Molecular Interactions
Author(s) -
Ye Lin,
Song Qi,
Lo Benedict T. W.,
Zheng Junlin,
Kong Dejing,
Murray Claire A.,
Tang Chiu C.,
Tsang S. C. Edman
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704347
Subject(s) - decarboxylation , aromatization , chemistry , catalysis , active site , hydrolysis , nucleophile , molecule , butene , organic chemistry , ethylene
Herein, we report the catalytic decarboxylation of γ‐valerolactone (GVL) over Zn/ZSM‐5 to butene, followed by aromatization at high yield with co‐feeding of water. An evaluation of the catalytic performance after prolonged periods of time showed that a water molecule is essential to maintain the decarboxylation and aromatization activities and avoid rapid catalyst deactivation. Synchrotron X‐ray powder diffraction and Rietveld refinement were then used to elucidate the structures of adsorbed GVL and immobilized Zn species in combination with EXAFS and NMR spectroscopy. A new route for the cooperative hydrolysis of GVL by framework Zn−OH and Brønsted acidic sites to butene and then to aromatic compounds has thus been demonstrated. The structures and fundamental pathways for the nucleophilic attack of terminal Zn−OH sites are comparable to those of Zn‐containing enzymes in biological systems.