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On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets

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Abstract

We present a study of the dissociative chemisorption of NO, O2, and N2 over close-packed, stepped, kinked, and open (fcc {111}, {211}, {311}, {532}, {100}, and {110}) transition metal facets using density functional theory (DFT). The offset of the Brønsted–Evans–Polanyi (BEP) relations suggest that the {111} surface is the least reactive, and that the {110} surface is the most reactive. This observation is verified by establishing volcano-relations based on mean-field microkinetic models for each facet, showing that the maximum rate over {110} is 4 orders of magnitude larger than the maximum {111} rate. The ordering of the maximum activity over the facets is: {110} > {100} ~ {532} > {311} ~ {211} > {111}, which is in general agreement with the offset in the BEP relations. We show that the top-point location and shape of the volcano relations are approximately independent of facet. This observation lends credibility to the approach of analyzing trends in catalytic reactivity over a single low-index facet, and assuming the experimentally observed activity trends are qualitatively well-described by such a single-facet analysis. Our study suggests that a key element for generally obtaining quantitative agreement between theory and experiments is for the simulations to address in detail the propensities of the various types of active sites. Finally, we show that the ordering of NO decomposition rates among metals and facets is essentially unaltered when using BEP- and scaling relations in the microkinetics instead of explicit DFT calculations for each elementary reaction step, and that using a “universal” BEP relation introduces no significant additional qualitative error in trend prediction.

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Acknowledgments

The authors wish to thank Professor J.K. Nørskov, both for helpful discussions on the present study, and also more generally for the great privilege it has been to have him as mentor during the early stages of our research careers. Financial support from the U.S. Department of Energy, Office of Basic Energy Sciences to the SUNCAT Center for Interface Science and Catalysis, and from the Strategic Research Council of Denmark to the Technical University of Denmark, is gratefully acknowledged.

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Authors and Affiliations

  1. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA

    Hanne Falsig, Tuhin Suvra Khan & Thomas Bligaard

  2. Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, Building 307, 2800, Lyngby, Denmark

    Hanne Falsig, Juan Shen, Tuhin Suvra Khan, Wei Guo & Glenn Jones

  3. Center for Individual Nanoparticle Functionality (CINF), Department of Physics, Nano DTU, Technical University of Denmark, Building 307, 2800, Lyngby, Denmark

    Søren Dahl

  4. Department of Chemical Engineering, Stanford University, Stanford, CA, 94305, USA

    Thomas Bligaard

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  1. Hanne Falsig
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  2. Juan Shen
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  3. Tuhin Suvra Khan
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  4. Wei Guo
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  5. Glenn Jones
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  7. Thomas Bligaard
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Correspondence to Thomas Bligaard.

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Falsig, H., Shen, J., Khan, T.S. et al. On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets. Top Catal 57, 80–88 (2014). https://doi.org/10.1007/s11244-013-0164-5

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