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Mechanistic Investigation on Ethanol to Butadiene Conversion Reaction over Metal Oxide Clusters: A Computational Study
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  • Valeria Butera,
  • Yusuke Tanabe,
  • Yu Shinke,
  • Tomohisa Miyazawa,
  • Tadahiro Fujitani,
  • Megumi Kayanuma,
  • Yoong-Kee Choe
Valeria Butera
Sangyo Gijutsu Sogo Kenkyujo Tsukuba
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Yusuke Tanabe
Research Association of High-Throughput Design and Development for Advanced Functional Materials
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Yu Shinke
Research Association of High-Throughput Design and Development for Advanced Functional Materials
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Tomohisa Miyazawa
Sangyo Gijutsu Sogo Kenkyujo Tsukuba
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Tadahiro Fujitani
Sangyo Gijutsu Sogo Kenkyujo Tsukuba
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Megumi Kayanuma
Sangyo Gijutsu Sogo Kenkyujo Tsukuba
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Yoong-Kee Choe
Sangyo Gijutsu Sogo Kenkyujo Tsukuba
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Abstract

Density functional theory (DFT) calculations were conducted to investigate mechanistic details of ethanol-to-butadiene conversion reaction over MgO or ZnO catalyst. We evaluated the Lewis acidity and basicity of MgO and ZnO and found that ZnO had the stronger Lewis acidity and basicity compared with those of MgO. Potential energy surfaces (PESs) of ethanol-to-butadiene conversion, which included relevant transition states (TSs) and intermediates, were computed in detail following the generally accepted mechanism reported in the literature, where such mechanism included ethanol dehydrogenation, aldol condensation, Meerwein-Pondorf-Verley (MPV) reduction and crotyl alcohol dehydration. DFT results showed that ethanol dehydrogenation was the rate limiting step of overall reaction when the reaction was catalyzed by MgO. Also, DFT results showed that ethanol dehydrogenation occurred more easily on ZnO compared with MgO where such a result correlated with the stronger Lewis acidity of ZnO. In addition, we computed ethanol dehydration which generates ethylene, one of the major undesired side reaction products for butadiene formation. DFT results showed that ZnO favored dehydrogenation over dehydration while MgO favored dehydration.

Peer review status:ACCEPTED

11 Aug 2020Submitted to International Journal of Quantum Chemistry
11 Aug 2020Submission Checks Completed
11 Aug 2020Assigned to Editor
27 Aug 2020Reviewer(s) Assigned
07 Sep 2020Review(s) Completed, Editorial Evaluation Pending
07 Sep 2020Editorial Decision: Revise Minor
08 Sep 20201st Revision Received
09 Sep 2020Submission Checks Completed
09 Sep 2020Assigned to Editor
17 Sep 2020Reviewer(s) Assigned
17 Sep 2020Review(s) Completed, Editorial Evaluation Pending
17 Sep 2020Editorial Decision: Accept