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Molecular interactions of alcohols with zeolite BEA and MOR frameworks

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Abstract

Zeolites can adsorb small organic molecules such as alcohols from a fermentation broth. Also in the zeolite-catalyzed conversion of alcohols to biofuels, biochemicals, or gasoline, adsorption is the first step. Several studies have investigated the adsorption of alcohols in different zeolites experimentally, but computational investigations in this field have mostly been restricted to zeolite MFI. In this study, the adsorption of C1–C4 alcohols in BEA and MOR was investigated using density functional theory (DFT). Calculated adsorption geometries and the corresponding energies of the designed cluster models were comparable to periodic calculations, and the adsorption energies were in the same range as the corresponding computational and experimental values reported in the literature for zeolite MFI. Thus, BEA and MOR may be good adsorption materials for alcohols in the field of downstream processing and catalysis. Aside from the DFT calculations, adsorption isotherms were determined experimentally in this study from aqueous solutions. For BEA, the adsorption of significant amounts of alcohol from aqueous solution was observed experimentally. In contrast, MOR was loaded with only a very small amount of alcohol. Although differences were found between the affinities obtained from gas-phase DFT calculations and those observed experimentally in aqueous solution, the computational data presented here represent molecular level information on the geometries and energies of C1–C4 alcohols adsorbed in zeolites BEA and MOR. This knowledge should prove very useful in the design of zeolite materials intended for use in adsorption and catalytic processes, as it allows adsorption behavior to be predicted via judiciously designed computational models.

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Acknowledgments

The research leading to these results has received funding from the Ministry of Innovation, Science and Research of North Rhine-Westphalia through the CLIB-Graduate Cluster Industrial Biotechnology initiative, contract no: 314–108 001 08.

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  1. Laboratory of Plant and Process Design, Department of Biochemical and Chemical Engineering, TU Dortmund University, 44227, Dortmund, Germany

    Kai Stückenschneider, Juliane Merz & Gerhard Schembecker

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Correspondence to Juliane Merz.

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The online version of this article contains supplementary material, which is available to authorized users. Additional information on experiments and theoretical data, such as the optimized geometries of the alcohols adsorbed in BEA and MOR, is listed. (PDF 1.15 mb)

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Stückenschneider, K., Merz, J. & Schembecker, G. Molecular interactions of alcohols with zeolite BEA and MOR frameworks. J Mol Model 19, 5611–5624 (2013). https://doi.org/10.1007/s00894-013-2048-9

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