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A density functional theory study of hydrocarbon combustion and synthesis on Ni surfaces

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Abstract

Combustion and synthesis of hydrocarbons may occur directly (CH → C + H and CO → C + O) or via a formyl (CHO) intermediate. Density functional theory (DFT) calculations were performed to calculate the activation and reaction energies of these reactions on Ni(111), Ni(110), and Ni(100) surfaces. The results show that the energies are sensitive to the surface structure. The dissociation barrier for methylidyne (CH → C + H: catalytic hydrocarbon combustion) is lower than that for its oxidation reaction (CH + O → CHO) on the Ni(110) and Ni(100) surfaces. However the oxidation barrier is lower than that for dissociation on the Ni(111) surface. The dissociation barrier for methylidyne dissociation decreases in the order Ni(111) > Ni(100) > Ni(110). The barrier of formyl dissociation to CO and H is almost the same on the Ni(111) and Ni(110) surfaces and is lower compared to the Ni(100) surface. The energy barrier for carbon monoxide dissociation (CO → C + O: catalytic hydrocarbon synthesis) is higher than that of for its hydrogenation reaction (CO + H → CHO) on all three surfaces. This means that the hydrogenation to CHO is favored on these nickel surfaces. The energy barrier for both reactions decreases in the order Ni(111) > Ni(100) > Ni(110). The barrier for formyl dissociation to CH + O decreases in the order Ni(100) > Ni(111) > Ni(110). Based on these DFT calculations, the Ni(110) surface shows a better catalytic activity for hydrocarbon combustion compared to the other surfaces, and Ni is a better catalyst for the combustion reaction than for hydrocarbon synthesis, where the reaction rate constants are small. The reactions studied here support the BEP principles with R2 values equal to 0.85 for C-H bond breaking/forming and 0.72 for C-O bond breaking /forming reactions.

A density functional theory study of hydrocarbon combustion and synthesis on Ni surfaces

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Acknowledgments

This research is funded by Stiftelsen Föreningssparbanken Sjuhärad. The computations and simulations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at PDC Centre for High Performance Computing (PDC-HPC) and the Uppsala Multidisciplinary Centre for Advanced Computational Science (UPPMAX). We also acknowledge that the results of this research have been achieved using the PRACE-2IP project (FP7 RI-283493) resource Abel based in Norway at UiO.

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  1. Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden

    Abas Mohsenzadeh, Tobias Richards & Kim Bolton

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  1. Abas Mohsenzadeh
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Correspondence to Abas Mohsenzadeh.

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Mohsenzadeh, A., Richards, T. & Bolton, K. A density functional theory study of hydrocarbon combustion and synthesis on Ni surfaces. J Mol Model 21, 46 (2015). https://doi.org/10.1007/s00894-015-2590-8

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