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  • Perspective
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The kinetics of elementary thermal reactions in heterogeneous catalysis

Nature Reviews Chemistry volume 3, pages 723–732 (2019)Cite this article

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Abstract

The kinetics of elementary reactions is fundamental to our understanding of catalysis. Just as microkinetic models of atmospheric chemistry provided the predictive power that led to the Montreal Protocol reversing loss of stratospheric ozone, pursuing a microkinetic approach to heterogeneous catalysis has tremendous potential for societal impact. However, the development of this approach for catalysis faces great challenges. Methods for measuring rate constants are quite limited, and the present predictive theoretical methods remain largely unvalidated. Here, we present a short Perspective on recent experimental advances in the measurement of rates of elementary reactions at surfaces that rely on a stroboscopic pump–probe concept for neutral matter. We present the principles behind successful measurement methods and discuss a recent implementation of those principles. The topic is discussed within the context of a specific but highly typical surface reaction, CO oxidation on Pt, which, despite more than 40 years of study, was only clarified after experiments with velocity-resolved kinetics became possible. This deceptively simple reaction illustrates fundamental lessons concerning the coverage dependence of activation energies, the nature of reaction mechanisms involving multiple reaction sites, the validity of transition-state theory to describe reaction rates at surfaces and the dramatic changes in reaction mechanism that are possible when studying reactions at low temperatures.

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Fig. 1: Hyperthermal CO2 from CO oxidation on Pt(111).
Fig. 2: CO2 product angular distribution from the CO oxidation on Pt(111).
Fig. 3: An instrument for velocity-resolved surface-reaction kinetics.
Fig. 4: Ion imaging of chemical reaction products from CO oxidation on Pt(111).
Fig. 5: Comparison of the density versus time trace with the velocity-resolved CO2 flux trace.
Fig. 6: Temperature and coverage dependence of effective activation energies.
Fig. 7: The role of steps in a surface reaction.
Fig. 8: Measured and calculated rate constants for CO oxidation reactions occurring on steps or terraces.
Fig. 9: Angular and translational-energy distributions from ab initio molecular dynamics trajectories.

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Acknowledgements

A.M.W. gratefully acknowledges support from the Alexander von Humboldt Foundation. The authors acknowledge support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation), the Ministerium für Wissenschaft und Kultur (MWK) Niedersachsen and the VolkswagenStiftung under grant no. INST 186/952-1. C.T.C. acknowledges support for this work by the US National Science Foundation under grant no. CHE-1665077. T.N.K. acknowledges the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. [833404]). D.B. thanks the BENCh graduate school, funded by the DFG — (389479699/GRK2455).

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Authors and Affiliations

  1. Institute for Physical Chemistry, Georg-August University of Göttingen, Göttingen, Germany

    G. Barratt Park, Dmitriy Borodin, Jannis Neugebohren & Alec M. Wodtke

  2. Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Göttingen, Germany

    G. Barratt Park, Theofanis N. Kitsopoulos, Kai Golibrzuch, Daniel J. Auerbach & Alec M. Wodtke

  3. Department of Chemistry, University of Crete, Heraklion, Greece

    Theofanis N. Kitsopoulos

  4. Institute of Electronic Structure and Laser – FORTH, Heraklion, Greece

    Theofanis N. Kitsopoulos

  5. Department of Chemistry, University of Washington, Seattle, WA, USA

    Charles T. Campbell

  6. International Center for Advanced Studies of Energy Conversion, Georg-August University of Göttingen, Göttingen, Germany

    Alec M. Wodtke

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Contributions

A.M.W. conceived and wrote the Perspective together with C.T.C. G.B.P., T.N.K., D.B. and J.N. researched data for the Perspective. G.B.P., D.B. and C.T.C. contributed to the revisions and editing of the article. All authors contributed to the discussion of the Perspective.

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Correspondence to Alec M. Wodtke.

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Glossary

Langmuir–Hinshelwood mechanism

A common reaction mechanism in heterogeneous catalysis comprising four steps: adsorption of reactants to the catalyst including possibly dissociation of reactant(s), followed by diffusion bringing reactants together and reaction, followed by product desorption.

Lean NOx traps

Devices that use adsorption to reduce NOx emissions in lean-burn combustion engines, which operate with high levels of O2. Such traps must be periodically purged when they become saturated with NOx. The traps are typically regenerated by the injection of fuel, leading to a reduction in fuel efficiency.

Selective catalytic reduction systems

An alternative to NOx traps that involves the catalytic reduction of NOx by a stoichiometric amount of reductant (such as urea or ammonia) that must be continuously injected into the flue or exhaust gas.

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Park, G.B., Kitsopoulos, T.N., Borodin, D. et al. The kinetics of elementary thermal reactions in heterogeneous catalysis. Nat Rev Chem 3, 723–732 (2019). https://doi.org/10.1038/s41570-019-0138-7

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