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Origin of active sites on silica–magnesia catalysts and control of reactive environment in the one-step ethanol-to-butadiene process

Nature Catalysis volume 6, pages 363–376 (2023)Cite this article

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An Author Correction to this article was published on 11 September 2023

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Abstract

Wet-kneaded silica–magnesia is a benchmark catalyst for the one-step ethanol-to-butadiene Lebedev process. Magnesium silicates, formed during wet kneading, have been proposed as the active sites for butadiene formation, and their properties are mainly explained in terms of the ratio of acid and base sites. However, their mechanism of formation and reactivity have not yet been fully established. Here we show that magnesium silicates are formed by the dissolution of Si and Mg subunits from their precursors, initiated by the alkaline pH of the wet-kneading medium, followed by cross-deposition on the precursor surfaces. Using two individual model systems (Mg/SiO2 and Si/MgO), we demonstrate that the location of the magnesium silicates (that is, Mg on SiO2 or Si on MgO) governs not only their chemical nature, but also the configuration of adsorbed ethanol and resulting selectivity. By using an NMR approach together with probe molecules, we demonstrate that acid and basic sites in close atomic proximity (~5 Å) promote butadiene formation.

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Fig. 1: Wet-kneading approach and time-resolved characterization of the silica–magnesia catalyst during wet kneading.
Fig. 2: Location and type of magnesium silicates on a wet-kneaded, dried catalyst.
Fig. 3: Characterization of wet-kneaded silica–magnesia catalysts before and after calcination.
Fig. 4: Catalytic performances of wet-kneaded silica–magnesia catalysts at different wet-kneading times.
Fig. 5: Identification of the key surface magnesium silicates responsible for the one-step Lebedev process.
Fig. 6: Characterization of acid–base site proximity and formation of reaction intermediates.

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The data supporting the findings of this article are available in the paper and its Supplementary Information or from the corresponding author on reasonable request.

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Acknowledgements

The authors are grateful for financial support from King Abdullah University of Science and Technology. We thank J. Vittenet and E. Kaliyamoorthy for ICP-OES analysis, S. Lopatin for TEM–EDX measurements, C. Canlas for technical support in recording solid-state NMR spectra, Y. Yuan for in situ PXRD measurements and K. Eichele (Universität Tübingen) for WSolids1 software support. The preliminary experiments in this research were performed within the framework of the CatchBio programme. B.M.W. and P.C.A.B. acknowledge the support of the Smart Mix Program of the Netherlands Ministry of Economic Affairs, the Netherlands Ministry of Education, Culture and Science, and NWO (Middelgroot programme, grant no. 700.58.102).

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  1. KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Sang-Ho Chung, Teng Li, Tuiana Shoinkhorova, Sarah Komaty, Adrian Ramirez, Ildar Mukhambetov, Genrikh Shterk, Selvedin Telalovic, Alla Dikhtiarenko, Polina Lavrik, Jorge Gascon & Javier Ruiz-Martínez

  2. Core Labs, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Edy Abou-Hamad & Xinqi Tang

  3. Inorganic Chemistry and Catalysis Group, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, the Netherlands

    Bart Sirks, Bert M. Weckhuysen & Pieter C. A. Bruijnincx

  4. Organic Chemistry and Catalysis Group, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, the Netherlands

    Pieter C. A. Bruijnincx

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Contributions

S.-H.C. and J.R.-M. conceived the research and directed the project. S.-H.C. designed the experiments and analysed the data. T.L. and A.R. collected and processed the DRIFTS–MS spectra and catalytic activity test results, respectively. T.S., S.K., I.M., G.S., S.T., A.D., E.A.-H., X.T. and P.L. characterized the prepared catalysts under the guidance of S.-H.C., J.G. and J.R.-M. B.S. conducted preliminary experiments for the catalyst synthesis under the supervision of B.M.W. and P.C.A.B. S.-H.C. and J.R.-M. co-wrote the paper. All authors discussed the results and commented on different versions of the manuscript.

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Correspondence to Sang-Ho Chung or Javier Ruiz-Martínez.

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Supplementary Figs. 1–27, Tables 1–4, Notes 1–6 and references.

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Chung, SH., Li, T., Shoinkhorova, T. et al. Origin of active sites on silica–magnesia catalysts and control of reactive environment in the one-step ethanol-to-butadiene process. Nat Catal 6, 363–376 (2023). https://doi.org/10.1038/s41929-023-00945-0

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