Ab-Initio Simulation Laboratory

Citation:

Chou, J. P., Pai W. W., Kuo C. C., Lee J. D., Lin C. H., & Wei C. M. (2009).  Promotion of CO Oxidation on Bimetallic Au-Ag(110) Surfaces: A Combined Microscopic and Theoretical Study. Journal of Physical Chemistry C. 113, 13151-13159., Jul, Number 30

Abstract:

The clean-off reaction of AgO added rows by CO on Ag(110) and Au/Ag(110) bimetallic surfaces was studied by scanning tunneling microscopy (STM) and compared with density functional theory (DFT). This combined study of a model system illustrated the complexity of catalytic enhancement in bimetallic systems. By analyzing in situ time-lapsed STM image series, we found that CO oxidation on a Au-enriched Ag(110) surface leads to an exponential depletion of oxygen with time and a reaction rate that is synergistically enhanced by the presence of Au. First principles calculations indicate that the local atomic configuration around the active reaction sites at the chain ends and the preference of An atom substitution into the subsurface second Ag layer are of critical importance. By calculating CO adsorption energies and reaction barriers for plausible reaction pathways, a detailed description of the CO oxidation reaction emerges, For the optimal reaction pathway, a large (similar to 0.09 eV) barrier reduction and a small barrier of similar to 0.01 eV were found for the Eley-Rideal (ER) mechanism. In contrast, a small (similar to 0.03 eV) barrier reduction and a moderate barrier of similar to 0.23 eV were obtained for the Langmuir-Hinshelwood (LH) mechanism. The ER transitional state was also found to be lower in energy. We conclude that, irrespective of whether the ER mechanism is actually rate dominating, it is definitively enhanced.

Notes:

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