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Title: Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations

Abstract

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 these 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 Brønsted-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.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1001519
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 131; Journal Issue: 16; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 10 SYNTHETIC FUELS; ETHANOL; DECOMPOSITION; CATALYSTS; DENSITY FUNCTIONAL METHOD; MATHEMATICAL MODELS; SURFACE POTENTIAL; POTENTIAL ENERGY; CATALYSIS; TRANSITION ELEMENTS; Environmental Molecular Sciences Laboratory

Citation Formats

Ferrin, Peter A, Simonetti, Dante A, Kandoi, Shampa, Kunkes, Edward L, Dumesic, James A, Norskov, Jens K, and Mavrikakis, Manos. Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations. United States: N. p., 2009. Web. doi:10.1021/ja8099322.
Ferrin, Peter A, Simonetti, Dante A, Kandoi, Shampa, Kunkes, Edward L, Dumesic, James A, Norskov, Jens K, & Mavrikakis, Manos. Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations. United States. doi:10.1021/ja8099322.
Ferrin, Peter A, Simonetti, Dante A, Kandoi, Shampa, Kunkes, Edward L, Dumesic, James A, Norskov, Jens K, and Mavrikakis, Manos. Wed . "Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations". United States. doi:10.1021/ja8099322.
@article{osti_1001519,
title = {Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations},
author = {Ferrin, Peter A and Simonetti, Dante A and Kandoi, Shampa and Kunkes, Edward L and Dumesic, James A and Norskov, Jens K and Mavrikakis, Manos},
abstractNote = {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 these 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 Brønsted-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.},
doi = {10.1021/ja8099322},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 16,
volume = 131,
place = {United States},
year = {2009},
month = {4}
}