Elucidating the Cooperative Roles of Water and Lewis Acid–Base Pairs in Cascade C–C Coupling and Self-Deoxygenation Reactions

Li, Houqian; Guo, Dezhou; Ulumuddin, Nisa; Jaegers, Nicholas R.; Sun, Junming; Peng, Bo; McEwen, Jean-Sabin; Hu, Jianzhi; Wang, Yong

doi:10.1021/jacsau.1c00218

Title: Elucidating the Cooperative Roles of Water and Lewis Acid–Base Pairs in Cascade C–C Coupling and Self-Deoxygenation Reactions

Journal Article · Tue Aug 17 00:00:00 EDT 2021 · JACS Au

DOI:https://doi.org/10.1021/jacsau.1c00218· OSTI ID:1813882

Li, Houqian ^[1]; Guo, Dezhou ^[1]; Ulumuddin, Nisa ^[1]; Jaegers, Nicholas R. ^[2];

^[1]; Peng, Bo ^[3];

^[4];

^[2]; Wang, Yong ^[1]

The Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States
The Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
The Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States, Department of Physics and Astronomy, Washington State University, Pullman, Washington 99164, United States, Department of Chemistry, Washington State University, Pullman, Washington 99164, United States, Department of Biological Systems Engineering, Washington State University, Pullman, Washington 99164, United States

Water plays pivotal roles in tailoring reaction pathways in many important reactions, including cascade C-C bond formation and oxygen elimination. Herein, a kinetic study combined with complementary analyses (DRIFTS, isotopic study, 1H solid-state magic angle spinning nuclear magnetic resonance) and density functional theory (DFT) calculations are performed to elucidate the roles of water in cascade acetone-to-isobutene reactions on a ZnxZryOz mixed metal oxide with balanced Lewis acid-base pairs. Our results reveal that the reaction follows the acetone-diacetone alcohol-isobutene pathway. Isobutene is produced through an intramolecular rearrangment of the eight-membered ring intermediate formed via the adsorption of diacetone alcohol on the Lewis acid-base pairs in the presence of cofed water. OH adspecies, formed by the dissociative adsorption of water on the catalyst surface, were found to distort diacetone alcohol’s hydroxyl functional group toward its carbonyl functional group and facilitate the intramolecular rearrangement of diacetone alcohol to form isobutene. In the absence of water, diacetone alcohol binds strongly to the Lewis acid site, e.g., at a Zr4+ site, via its carbonyl functional group, leading to its dramatic structural distortion and further dehydration reaction to form mesityl oxide as well as subsequent polymerization reactions and the formation of coke. The present results provide insights into the cooperative roles of water and Lewis acid-base pairs in catalytic upgrading of biomass to fuels and chemicals.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-RL01830; FW-47319; FWP-47319; AC05-76RL01830; AC02-05CH11231

OSTI ID:: 1813882

Alternate ID(s):: OSTI ID: 1822417; OSTI ID: 1837656

Report Number(s):: PNNL-SA-164561

Journal Information:: JACS Au, Journal Name: JACS Au Vol. 1 Journal Issue: 9; ISSN 2691-3704

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
water
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aldolization
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metal oxide
catalysts
hydroxyls
chemical reactions
oxides
ketones
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aldolization
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metal oxide

Title: Elucidating the Cooperative Roles of Water and Lewis Acid–Base Pairs in Cascade C–C Coupling and Self-Deoxygenation Reactions

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