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SLAC Publication: SLAC-PUB-14660
SLAC Release Date: February 16, 2012
Elementary Steps of Syngas Reactions on Mo2C(001): Adsorption Thermochemistry and Bond Dissociation
Medford, Andrew.
Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo2C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorbtion energy scaling relations and Bronsted-Evans-Polanyi relationships are established and used to p... Show Full Abstract
Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo2C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorbtion energy scaling relations and Bronsted-Evans-Polanyi relationships are established and used to place Mo2C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C2H2 or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo2C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen. Show Partial Abstract
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