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

Sang Ho Chung; Teng Li; Tuiana Shoinkhorova; Sarah Komaty; Adrian Ramirez; Ildar Mukhambetov; Edy Abou-Hamad; Genrikh Shterk; Selvedin Telalovic; Alla Dikhtiarenko; Bart Sirks; Polina Lavrik; Xinqi Tang; Bert M. Weckhuysen; Pieter C.A. Bruijnicx; Jorge Gascon; Javier Ruiz-Martínez

doi:10.1038/s41929-023-00945-0

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

Sang Ho Chung^*, Teng Li, Tuiana Shoinkhorova, Sarah Komaty, Adrian Ramirez, Ildar Mukhambetov, Edy Abou-Hamad, Genrikh Shterk, Selvedin Telalovic, Alla Dikhtiarenko, Bart Sirks, Polina Lavrik, Xinqi Tang, Bert M. Weckhuysen, Pieter C.A. Bruijnicx, Jorge Gascon, Javier Ruiz-Martínez^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

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. [Figure not available: see fulltext.].

Original language	English (US)
Pages (from-to)	363-376
Number of pages	14
Journal	Nature Catalysis
Volume	6
Issue number	4
DOIs	https://doi.org/10.1038/s41929-023-00945-0
State	Published - Apr 2023

Bibliographical note

Funding Information:
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).

Funding Information:
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).

Publisher Copyright:
© 2023, The Author(s), under exclusive licence to Springer Nature Limited.

ASJC Scopus subject areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

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10.1038/s41929-023-00945-0

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Chung, S. H., Li, T., Shoinkhorova, T., Komaty, S., Ramirez, A., Mukhambetov, I., Abou-Hamad, E., Shterk, G., Telalovic, S., Dikhtiarenko, A., Sirks, B., Lavrik, P., Tang, X., Weckhuysen, B. M., Bruijnicx, P. C. A., Gascon, J., & Ruiz-Martínez, J. (2023). Origin of active sites on silica–magnesia catalysts and control of reactive environment in the one-step ethanol-to-butadiene process. Nature Catalysis, 6(4), 363-376. https://doi.org/10.1038/s41929-023-00945-0

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

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 {\AA}) promote butadiene formation. [Figure not available: see fulltext.].",

author = "Chung, {Sang Ho} and Teng Li and Tuiana Shoinkhorova and Sarah Komaty and Adrian Ramirez and Ildar Mukhambetov and Edy Abou-Hamad and Genrikh Shterk and Selvedin Telalovic and Alla Dikhtiarenko and Bart Sirks and Polina Lavrik and Xinqi Tang and Weckhuysen, {Bert M.} and Bruijnicx, {Pieter C.A.} and Jorge Gascon and Javier Ruiz-Mart{\'i}nez",

note = "Funding Information: 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 (Universit{\"a}t T{\"u}bingen) 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). Funding Information: 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 (Universit{\"a}t T{\"u}bingen) 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). Publisher Copyright: {\textcopyright} 2023, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2023",

month = apr,

doi = "10.1038/s41929-023-00945-0",

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Chung, SH , Li, T, Shoinkhorova, T, Komaty, S, Ramirez, A, Mukhambetov, I , Abou-Hamad, E , Shterk, G , Telalovic, S , Dikhtiarenko, A, Sirks, B, Lavrik, P , Tang, X, Weckhuysen, BM, Bruijnicx, PCA, Gascon, J & Ruiz-Martínez, J 2023, 'Origin of active sites on silica–magnesia catalysts and control of reactive environment in the one-step ethanol-to-butadiene process', Nature Catalysis, vol. 6, no. 4, pp. 363-376. https://doi.org/10.1038/s41929-023-00945-0

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T1 - Origin of active sites on silica–magnesia catalysts and control of reactive environment in the one-step ethanol-to-butadiene process

AU - Chung, Sang Ho

AU - Li, Teng

AU - Shoinkhorova, Tuiana

AU - Komaty, Sarah

AU - Ramirez, Adrian

AU - Mukhambetov, Ildar

AU - Abou-Hamad, Edy

AU - Shterk, Genrikh

AU - Telalovic, Selvedin

AU - Dikhtiarenko, Alla

AU - Sirks, Bart

AU - Lavrik, Polina

AU - Tang, Xinqi

AU - Weckhuysen, Bert M.

AU - Bruijnicx, Pieter C.A.

AU - Gascon, Jorge

AU - Ruiz-Martínez, Javier

N1 - Funding Information: 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). Funding Information: 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). Publisher Copyright: © 2023, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2023/4

Y1 - 2023/4

N2 - 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. [Figure not available: see fulltext.].

AB - 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. [Figure not available: see fulltext.].

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DO - 10.1038/s41929-023-00945-0

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ER -

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

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