caa a22 4500 605511969 CHVBK 20210128100653.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00894-015-2590-8 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2590-8 A density functional theory study of hydrocarbon combustion and synthesis on Ni surfaces [Elektronische Daten] [Abas Mohsenzadeh, Tobias Richards, Kim Bolton] 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. Graphical Abstract A density functional theory study of hydrocarbon combustion and synthesis on Ni surfaces Springer-Verlag Berlin Heidelberg, 2015 DFT nationallicence Hydrocarbon combustion nationallicence Hydrocarbon synthesis nationallicence Nickel nationallicence Mohsenzadeh Abas Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut Richards Tobias Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut Bolton Kim Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-11 1610-2940 21:3<1 2015 21 894 https://doi.org/10.1007/s00894-015-2590-8 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2590-8 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Mohsenzadeh Abas Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut NATIONALLICENCE 700 1- Richards Tobias Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut NATIONALLICENCE 700 1- Bolton Kim Swedish Centre for Resource Recovery, University of Borås, SE 501-90, Borås, Sweden aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-11 1610-2940 21:3<1 2015 21 894