Modeling of Crytical Steps of Conversion of Syntesis Gas into Alcohols on Modified Molybdenum Disulfide Catalysts Using DFT in Plane Wave Basis Set

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Abstract

The work discusses mechanistic aspects of higher alcohol syntesys on KCoMoS catalysts. A model of the active site is constructed and used in DFT calculations of surface species involved in highter alcohol synthesis. The activation energy of the key steps is found using NEB approach. Two main paths of C-O bond scissions are considered: the one involving formation of methyl and methylene intermidiates. Mechanism of the folloup chain growth is considered. The role of potassium is studied by comparing energy profiles of higher alcohol synthesis on active sites modified and not-modified by on pristine and potassium modified active sites. The most obvious effect of introduction of potassium into the model is stabilization of methilene intermidiate.

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About the authors

E. A. Permyakov

N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: permeakra@ioc.ac.ru
Russian Federation, Moscow

V. M. Kogan

N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences

Email: permeakra@ioc.ac.ru
Russian Federation, Moscow

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2. Fig. 1. Schematic of the computational model, projection onto the z = 0 plane. Dotted lines show the boundaries of the repeating section of the ribbon; coloured font highlights the atoms of the active centre; blue circles show the positions of potassium atoms for the model: solid - those closer to the observer and obscuring molybdenum atoms behind them, dashed - the model ribbon obscured by a molybdenum atom

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3. Fig. 2. Schematic of the computational model, projection on the plane x = 0, blue circles show the positions of potassium atoms

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4. Fig. 3. Schematic representation of the model active centre and adsorption energy (Ef) of CO and [H] at some positions

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5. Fig. 4. Simplified scheme of the reaction network in ethanol synthesis. The energy of the structure relative to the reference structure 1 and CO and H2 molecules is given under the structures. Activation energies (ΔE#) are given for key stages. Energy values (eV) are given for structures with potassium (3K) and without potassium (0K)

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6. Fig. 5. Energy profile of key steps of alcohol synthesis in the model without potassium

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7. Fig. 6. Energy profile of key steps of alcohol synthesis in the model with three potassium atoms

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