Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts
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c9cy01927h.pdf
Description
Published version
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2.14 MB
Format
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Checksum (MD5)
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Author(s)
Lusardi, Marcella R. (Marcella Rose)
Struble, Thomas J
Teixeira, Andrew R.
Jensen, Klavs F
Date Issued
December 2019
Journal
Catalysis Science & Techonology
Publisher
Royal Society of Chemistry (RSC)
Citation
Lusardi, Marcella et al. "Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts." Catalysis Science & Techonology 10, 2 (January 2020): 536-548 © 2020 Royal Society of Chemistry
Version
Final published version
Abstract
Pure and Al-substituted MgO catalysts are studied to identify the contributions of acid-base sites in the formation of two valuable xylene analogs, ortho- and para-tolualdehydes, from an ethanol derivative, acetaldehyde. The catalyst properties are characterized through XRD, ²⁷Al MAS NMR, ICP-AES, N₂ physisorption, TPD-MS, and DRIFTS experiments. Reactivity comparisons of untreated and CO₂-titrated catalysts at 250 °C, coupled with CO₂ DRIFTS studies on fresh and spent samples, indicate the formation of tolualdehydes from intermediates is initiated through deprotonation by a medium-strength basic site in a specific, metal-oxygen (M-O)-type coordination environment. Analyses of the catalytic surface properties and reactivity, pathways of formation, and natural bond orbital (NBO) charge distribution suggest C₄ + C₄ (rather than C₂ + C₆) mechanistic steps dominate tolualdehyde production over these catalysts under the investigated reaction conditions. Isomeric selectivity to ortho-tolualdehyde is 92 and 81 mol% over pure and Al-substituted MgO catalysts, respectively. We propose that the shift in isomeric selectivity towards para- upon introduction of a proximal Lewis acidic functionality (Al³⁺/MgO) to the catalyst is caused by electron redistribution in the conjugated enolate from the γ-C (forming ortho-) towards the α-C (forming para-) due to the carbonyl-O/Lewis acid coordination. This insight provides a framework for the development of next generation catalysts that give improved reactivity in cascade reactions of C₂ feedstocks to aromatics.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Chemical Engineering
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Creative Commons Attribution 3.0 unported license
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DOI of Published Version
https://doi.org/10.1039/c9cy01927h
