Identifying the roles of acid–base sites in formation pathways of tolualdehydes from acetaldehyde over MgO-based catalysts. Issue 2 (2nd January 2020)

• Record Type: Journal Article
• Authors: Lusardi, Marcella; Struble, Thomas; Teixeira, Andrew R.; Jensen, Klavs F.
• Is Part Of: Catalysis science & technology. Volume 10:Issue 2(2020)
• Page Start: 536
• Page End: 548
• Publication Date: 2020-01-02
• Subjects: Catalysis -- Periodicals; 541.395
• DOI: 10.1039/c9cy01927h
• Languages: English
• ISSNs: 2044-4753

Abstract

Abstract : Basic (M–O)-type centers convert C4 intermediates to renewable xylene analogs and proximal acid sites tune isomeric selectivity. 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, 27 Al 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 (Al 3+ /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.