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Mechanistic Insights into the Catalytic Condensation of Methyl Ketones on MgO Surfaces

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Abstract

Ketone coupling via aldol condensation is one of the promising routes to produce cyclic and value-added precursors for renewable hydrocarbon biofuels. A first-principles-based microkinetic modeling is performed to evaluate the surface-mediated reaction mechanisms and the role of water molecules in the observed activities for 2-pentanone and 3-pentanone aldol condensation on dehydroxylated MgO(111) surface and hydroxylated terminated surface[OH-MgO(111)]. We have identified the enhancement of the surface OH group to MgO(111) surface catalytic activity by destabilizing the binding strength of reaction intermediates and reducing the energy barriers of rate-determining steps(proton transfer and dehydration steps). The 2-pentanone has one elementary step less in the complete reaction mechanism of aldol condensation and preferable energy barrier for proton transfer and dehydration steps, revealing 2-pentanone as terminal ketone is more reactive than 3-pentanone as central ketone. The water molecules dominated the OH-MgO(111) surface after further addition of water, leading to the reduction of turnover frequency of the aldol condensation dimer product as the loss of aldol condensation reaction intermediates in competitive adsorption with water molecules.

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Acknowledgements

This work was supported by the Science Foundation of China University of Petroleum, Beijing, China(No.2462022YJRC010).

We would like to thank Derek R. VARDON at National Renewable Energy Laboratory of USA for his contributions and helpful discussion. This work was conducted as part of the Computational Chemistry Physics Consortium(CCPC), which is supported by the Bioenergy Technologies Office(BETO) of Energy Efficiency and Renewable Energy(EERE). We also gratefully acknowledge the computing resources provided on “BEBOP”, a computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory of USA(ANL).

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Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, 102249, P. R. China

    Mingxia Zhou

  2. Materials Science Division, Argonne National Laboratory, Lemont, Illinois, 60439, USA

    Larry A. Curtiss & Rajeev S. Assary

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  1. Mingxia Zhou
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  2. Larry A. Curtiss
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  3. Rajeev S. Assary
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Correspondence to Mingxia Zhou or Rajeev S. Assary.

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Zhou, M., Curtiss, L.A. & Assary, R.S. Mechanistic Insights into the Catalytic Condensation of Methyl Ketones on MgO Surfaces. Chem. Res. Chin. Univ. 39, 1010–1016 (2023). https://doi.org/10.1007/s40242-023-3074-5

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