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Issue 2, 2020
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Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts

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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.

Graphical abstract: Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts

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Supplementary files

Article information


Submitted
24 Sep 2019
Accepted
15 Dec 2019
First published
16 Dec 2019

This article is Open Access

Catal. Sci. Technol., 2020,10, 536-548
Article type
Paper

Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts

M. Lusardi, T. Struble, A. R. Teixeira and K. F. Jensen, Catal. Sci. Technol., 2020, 10, 536
DOI: 10.1039/C9CY01927H

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