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The Challenge of CO Hydrogenation to Methanol: Fundamental Limitations Imposed by Linear Scaling Relations

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Abstract

Recent developments in computational catalysis have allowed the routine reduction of the dimensionality of complex reaction networks to a few descriptors based on linear scaling relations. Despite this convenient benefit, linear scaling relations fundamentally limit the activity and selectivity of a given class of materials towards a given reaction. Here, we show an example by offering a novel description of the fundamental limits on the activity of CO hydrogenation to methanol; a reaction that offers a sustainable route to obtaining value-added chemicals from syngas. First, we show that there is a strong linear correlation between the formation energy of CO* (where * denotes an adsorbed species) and those of the transition states of a number of elementary steps along the methanol synthesis pathway on these surfaces. Using microkinetic modeling, we cast this information into activity volcano plots with the formation energies of a given transition state and CO* as independent descriptors. This analysis reveals the fundamental limits on activity imposed by the aforementioned linear scaling relations, and invites a vigorous search for novel materials that escape these linear scaling relations as a necessary condition for achieving improved activity towards methanol from CO hydrogenation. Specifically, we point out the transition states H–CO* and CH3O–H* as key transition states to be stabilized independently of CO* for improved activity and selectivity towards methanol synthesis.

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Acknowledgements

The authors acknowledge support through V-Sustain: The VILLUM Centre for the Science of Sustainable Fuels and Chemicals (#20886) from VILLUM FONDEN.

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  1. Julia Schumann

    Present address: Department of Physics and Astronomy, University College London, London, UK

  2. Pallavi Bothra

    Present address: Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, CA, 90024, USA

  3. Julia Schumann

    Present address: Department of Chemical Engineering, University College London, London, UK

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  1. Department of Physics, Technical University of Denmark, 2800, Lyngby, Denmark

    Ahmed O. Elnabawy, Ang Cao & Jens K. Nørskov

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Elnabawy, A.O., Schumann, J., Bothra, P. et al. The Challenge of CO Hydrogenation to Methanol: Fundamental Limitations Imposed by Linear Scaling Relations. Top Catal 63, 635–648 (2020). https://doi.org/10.1007/s11244-020-01283-2

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