Ferrin P, Simonetti D, Kandoi S, Kunkes E, Dumesic J A, Nørskov J K, Mavrikakis M
Department of Chemical and Biological Engineering, University of Wisconsin Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2009 Apr 29;131(16):5809-15. doi: 10.1021/ja8099322.
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.
将密度泛函理论（DFT）计算应用于复杂反应网络催化剂的合理设计一直是一项持续的挑战，主要是因为这些计算的计算成本很高。某些关联关系可用于减少描述金属和合金表面活性和选择性趋势所需的DFT计算的数量和复杂性，从而将DFT的适用范围扩展到更复杂的体系。在这项工作中，著名的布朗斯特-埃文斯-波拉尼（BEP）关联关系族，将基元步骤势能面上的最小值与最大值联系起来，与一种标度关系相结合，将复杂吸附质的结合能与较简单吸附质（如C、O）的结合能联系起来，用于开发乙醇在10种过渡金属表面分解的势能面。使用一个简单的动力学模型，计算了这些表面子集中的选择性和活性。负载型催化剂的实验证实，这个简单模型在描述金属间的反应性趋势方面相当准确，这表明BEP和标度关系的结合可能会大幅降低识别更复杂反应的反应性描述符所需的DFT计算成本。
