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 -