Peter A. Ferrin1, Dante Simonetti1, Shampa Kandoi1, James A. Dumesic1, Jens K. Norskov2, and Manos Mavrikakis1. (1) Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI 53706, (2) Center for Atomic-scale Materials Physics, Dept. of Physics, Technical University of Denmark, Lyngby, Denmark
Two major challenges exist in the first-principles evaluation of even relatively simple catalytic reactions, such as the decomposition of ethanol. The first is obtaining all the necessary data, which requires large amounts of computing power. The second is using this data to develop a coherent model that captures the experimental behavior. In this study, we combine first-principles methods with Bronsted-Evans-Polanyi correlations
1-3 and the approach formulated by Abild-Pedersen, et al.
4 to derive essential data for ethanol decomposition on several transition metals, using a relatively small amount of DFT data for the binding energies of key reaction intermediates. We then apply transition state theory to the produced large data set to develop a simple model that predicts the activity and selectivity of different metal surfaces toward C-C and C-O bond cleavage. Synthesis and experimental reaction studies on multiple supported transition metal catalysts validate the proposed model and illustrate the power of this approach for modeling trends in activity across transition metal catalysts.
1R. Alcala, M. Mavrikakis, J. A. Dumesic. Journal of Catalysis 218 (2003) 178.
2J. K. Nørskov, et al. Journal of Catalysis 209 (2002) 275.
3Y. Xu, A. Ruban, M. Mavrikakis. Journal of the American Chemical Society 126 (2004) 4717
4F. Abild-Pedersen, et al. Physical Review Letters 99 (2007) 016105.