TY - JOUR
T1 - Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Bronsted-Evans-Polanyi Relations
AU - Ferrin, P.
AU - Simonetti, D.
AU - Kandoi, S.
AU - Kunkes, E.
AU - Dumesic, J.A.
AU - Nørskov, Jens Kehlet
AU - Mavrikakis, M.
PY - 2009
Y1 - 2009
N2 - Applying density functional theory (DFT) calculations to the rational design of catalysts for complex reaction networks has been an ongoing challenge, primarily because of the high computational cost of there calculations. Certain correlations can be used to reduce the number and complexity of DFT calculations necessary to describe trends in activity and selectivity across metal and alloy surfaces, thus extending the reach of DFT to more complex systems. In-this work, the well-known family of Bronsted-Evans-Polanyi (BEP) correlations, connecting minima with maxima in the potential energy surface of elementary steps, in tandem with a scaling relation, connecting binding energies of complex adsorbates with those of simpler ones (e.g., C, O), is used to develop a potential-energy surface for ethanol decomposition on 10 transition metal surfaces. Using a simple kinetic model, the selectivity and activity on a subset of these surfaces are calculated. Experiments on supported catalysts verify that this simple model is reasonably accurate in describing reactivity trends across metals, suggesting that the combination of BEP and scaling relations may substantially reduce the cost of DFT calculations required for identifying reactivity descriptors of more complex reactions.
AB - Applying density functional theory (DFT) calculations to the rational design of catalysts for complex reaction networks has been an ongoing challenge, primarily because of the high computational cost of there calculations. Certain correlations can be used to reduce the number and complexity of DFT calculations necessary to describe trends in activity and selectivity across metal and alloy surfaces, thus extending the reach of DFT to more complex systems. In-this work, the well-known family of Bronsted-Evans-Polanyi (BEP) correlations, connecting minima with maxima in the potential energy surface of elementary steps, in tandem with a scaling relation, connecting binding energies of complex adsorbates with those of simpler ones (e.g., C, O), is used to develop a potential-energy surface for ethanol decomposition on 10 transition metal surfaces. Using a simple kinetic model, the selectivity and activity on a subset of these surfaces are calculated. Experiments on supported catalysts verify that this simple model is reasonably accurate in describing reactivity trends across metals, suggesting that the combination of BEP and scaling relations may substantially reduce the cost of DFT calculations required for identifying reactivity descriptors of more complex reactions.
U2 - 10.1021/ja8099322
DO - 10.1021/ja8099322
M3 - Journal article
VL - 131
SP - 5809
EP - 5815
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 16
ER -