de.mpg.escidoc.pubman.appbase.FacesBean
English
 
Help Guide Disclaimer Contact us Login
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Quantum-chemical investigation of hydrocarbon oxidative dehydrogenation over spin-active carbon catalyst clusters

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons59349

Khavryuchenko,  Oleksiy
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Chemical Department, Kyiv National Taras Shevchenko University;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21519

Frank,  Benjamin
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22181

Trunschke,  Annette
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21623

Hermann,  Klaus
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22071

Schlögl,  Robert
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

Locator
There are no locators available
Fulltext (public)
There are no public fulltexts available
Supplementary Material (public)
There is no public supplementary material available
Citation

Khavryuchenko, O., Frank, B., Trunschke, A., Hermann, K., & Schlögl, R. (2013). Quantum-chemical investigation of hydrocarbon oxidative dehydrogenation over spin-active carbon catalyst clusters. The Journal of Physical Chemistry C, 117(12), 6225-6234. doi:10.1021/jp312548g.


Cite as: http://hdl.handle.net/11858/00-001M-0000-000E-EE15-C
Abstract
Graphene-like carbon clusters with oxygen-saturated zigzag and armchair edges were used as models for density-functional theory investigations of the oxidative dehydrogenation (ODH) of hydrocarbon molecules over carbon catalysts. The product of the first elementary step of the reaction, which is either a hydrocarbon radical or a surface ether, is found to be strictly dependent on the spin multiplicity of the catalyst, although energies of the initial state are spin-degenerate. The barriers of the first step of the ODH of light hydrocarbons (methane, ethane, and propane) over zigzag-edge carbon clusters are higher (59–104 kJ/mol) than those for ethylbenzene (18–58 kJ/mol), and the barrier of the second H abstraction is generally rate-limiting (82–106 kJ/mol). The armchair edge is passive toward reaction with hydrocarbons, but it reacts almost without a barrier with hydrocarbon radicals. The barrier of reoxidation by O2 was found to decrease from 161 to 69 kJ/mol with an increasing level of saturation with H atoms.