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CO Dissociation at Vacancy Sites on Hägg Iron Carbide: Direct Versus Hydrogen-Assisted Routes Investigated with DFT

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Abstract

The mechanism of activation of CO remains under debate in Fe-catalysed Fischer–Tropsch synthesis, in which iron carbides form under reaction conditions. Direct and H-assisted paths for CO activation and dissociation are investigated at carbon vacancy and non-vacancy sites on the Fe5C2(010) surface of Hägg iron carbide using density functional theory. The calculated overall energy barrier for direct and for H-assisted dissociation of CO via formation of an HCO intermediate is the same, 1.42 and 1.41 eV, respectively, but the lowest energy paths are facilitated by different vacancy sites. Furthermore, dissociation at a non-vacancy site is only marginally higher in energy by 0.1 eV. Dissociation through formation of a hydroxymethylidyne (COH) intermediate is less competitive kinetically.

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Notes

  1. Note that in ref. 54 a left-handed axis system was used for the monoclinic unit cell of bulk Hägg iron carbide. The surface termination labelled Fe5C2(001)−0.05 in ref. 54 is equivalent to Fe5C2(100)−0.098 relative to the orientation of the bulk unit cell used in the current work.

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Acknowledgments

We thank members of the Sasol Fischer–Tropsch Molecular Modelling study team for useful discussions during the course of this work, and we thank Ivan Bester (Information Management, Sasol) for infrastructure support.

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  1. Werner Janse van Rensburg

    Present address: Centre for High Performance Computing, 15 Lower Hope Road, Rosebank, Cape Town, 7700, South Africa

Authors and Affiliations

  1. Sasol Technology (Pty) Ltd., R&D Division, 1 Klasie Havenga Road, Sasolburg, 1947, South Africa

    Melissa A. Petersen & Werner Janse van Rensburg

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  1. Melissa A. Petersen
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Correspondence to Melissa A. Petersen.

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Petersen, M.A., van Rensburg, W.J. CO Dissociation at Vacancy Sites on Hägg Iron Carbide: Direct Versus Hydrogen-Assisted Routes Investigated with DFT. Top Catal 58, 665–674 (2015). https://doi.org/10.1007/s11244-015-0405-x

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