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Effect of the cerium modification on acid–base properties of Mg–Al hydrotalcite-derived oxide system and catalytic performance in ethanol conversion

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Abstract

The prospects of using cerium as a modifying additive of Mg–Al hydrotalcite-derived oxide system have been estimated by low-temperature nitrogen ad(de)sorption, X-ray diffraction, scanning electron microscopy, 1H and 27Al solid-state nuclear magnetic resonance (NMR), X-ray photoelectron and UV–Vis diffuse reflectance spectroscopy techniques. The effect of such tuning of structural-textural characteristics and acid–base properties of the surface on its catalytic performance in ethanol conversion has been studied. Solid-state NMR spectroscopic study of the probe molecule adsorption and temperature-programmed desorption of NH3 and CO2 with mass-spectrometry control are used to determine the nature and strength distribution of acidic and basic sites of Mg–Al(–Ce) oxide systems. It has been found that the selectivity towards 1-butanol up to 68.1% (548 K) is achieved in ethanol conversion over Mg–Al–Ce sample at time-on-stream ≤ 2 h. At higher time-on-stream, the specific rates of the target product (1-butanol) formation are comparable for both modified and un-modified catalysts, but the products distribution differs. Cerium modification of Mg–Al oxide catalyst leads to increase in specific rate of acetaldehyde formation due to increase in the number of basic sites and their surface density. Wherein, the rate of ethanol dehydration products (ethylene and diethyl ether) is reduced, apparently, due to decrease in a number of Lewis acidic sites formed by Al3+ cations octahedrally coordinated to oxygen.

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Acknowledgements

This work was financially supported by the National Academy of Sciences of Ukraine, program KPKVK 6541230 “Support for the development of priority areas of scientific research” (0120U101212), grant of National Academy of Sciences of Ukraine for implementation of research projects of young scientist groups (0120U100182). The authors also acknowledge CERIC-ERIC Consortium for access to experimental facilities at Nuclear Magnetic Resonance Spectrometer “Magic” at Slovenian NMR Centre (Proposal Number: 20182046) and financial support.

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  1. Department of Catalytic Oxidative-Reductive Processes, L.V. Pisarzhevskii Institute of Physical Chemistry, The National Academy of Sciences of Ukraine, 31 Prosp. Nauky, Kyiv, 03028, Ukraine

    Olga V. Larina & Karina V. Valihura

  2. Department of Inorganic Chemistry and Technology, National Institute of Chemistry, Hajdrihova 19, 1001, Ljubljana, Slovenia

    Tomaž Čendak

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Larina, O.V., Valihura, K.V. & Čendak, T. Effect of the cerium modification on acid–base properties of Mg–Al hydrotalcite-derived oxide system and catalytic performance in ethanol conversion. Reac Kinet Mech Cat 132, 359–378 (2021). https://doi.org/10.1007/s11144-020-01907-4

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