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In situ surface coverage analysis of RuO2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis

Nature Chemistry volume 4, pages 739–745 (2012)Cite this article

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Abstract

In heterogeneous catalysis, rates with Arrhenius-like temperature dependence are ubiquitous. Compensation phenomena, which arise from the linear correlation between the apparent activation energy and the logarithm of the apparent pre-exponential factor, are also common. Here, we study the origin of compensation and find a similar dependence on the rate-limiting surface coverage term for each Arrhenius parameter. This result is derived from an experimental determination of the surface coverage of oxygen and chlorine species using temporal analysis of products and prompt gamma activation analysis during HCl oxidation to Cl2 on a RuO2 catalyst. It is also substantiated by theory. We find that compensation phenomena appear when the effect on the apparent activation energy caused by changes in surface coverage is balanced out by the entropic configuration contributions of the surface. This result sets a new paradigm in understanding the interplay of compensation effects with the kinetics of heterogeneously catalysed processes.

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Figure 1: Constable–Cremer relation for HCl oxidation over RuO2/SnO2-Al2O3.
Figure 2: Schematic representation of the RuO2(110) surface.
Figure 3: TAP experiments identifying the role of surface oxygen.
Figure 4: In situ PGAA experiments evaluating the role of surface Cl.
Figure 5: DFT-based microkinetic modelling of the Deacon reaction over RuO2(110) validates the effect of coverage in the compensation.

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Acknowledgements

The authors acknowledge support from ETH Zurich, BMBF Project 033R018A, Bayer MaterialScience, the ICIQ Foundation, MICINN (CTQ2009-07753/BQU), BSC-RES, the EU FP7 NMI3 Access Programme, a NAP VENEUS grant (OMFB-00184/2006) and the cooperation project between the Fritz-Haber Institute and the former Institute of Isotopes founded by the MPG. K. Honkala is thanked for valuable suggestions.

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Authors and Affiliations

  1. Fritz-Haber Institute of the Max Planck Society, Berlin, D-14195, Germany

    Detre Teschner, Ramzi Farra, Axel Knop-Gericke & Robert Schlögl

  2. Centre for Energy Research, Hungarian Academy of Sciences, Budapest, H-1525, Hungary

    Detre Teschner & László Szentmiklósi

  3. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, Tarragona, 43007, Spain

    Gerard Novell-Leruth, Miguel González Hevia & Núria López

  4. Department of Chemistry, Technical University of Berlin, Berlin, D-10623, Germany

    Hary Soerijanto & Reinhard Schomäcker

  5. Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, Zurich, CH-8093, Switzerland

    Javier Pérez-Ramírez

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  1. Detre Teschner
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Contributions

H.S and R.S. carried out and evaluated catalytic experiments to derive the Constable–Cremer relation. M.G.H. and J.P.R. performed and evaluated the TAP measurements. G.N.L. and N.L. carried out DFT calculations, microkinetic simulations and model system analysis. D.T., R.F., A.K.G. and L.Sz. performed and evaluated PGAA measurements. R.S. provided valuable suggestions for interpreting the results. D.T., J.P.R. and N.L. contributed to writing the manuscript.

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Correspondence to Detre Teschner or Núria López.

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Teschner, D., Novell-Leruth, G., Farra, R. et al. In situ surface coverage analysis of RuO2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis. Nature Chem 4, 739–745 (2012). https://doi.org/10.1038/nchem.1411

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