In situ surface coverage analysis of RuO 2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis

Detre Teschner, Gerard Novell-Leruth, Ramzi Farra, Axel Knop-Gericke, Robert SchlÖgl, L. Szentmiklósi, Miguel González Hevia, Hary Soerijanto, Reinhard Schomäcker, Javier Pérez-Ramírez, Núria López

Research output: Contribution to journalArticle

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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 Cl 2 on a RuO 2 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.

Original languageEnglish
Pages (from-to)739-745
Number of pages7
JournalNature Chemistry
Volume4
Issue number9
DOIs
Publication statusPublished - Sep 2012

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Surface analysis
Catalysis
Oxidation
Activation energy
Activation analysis
Chlorine
Oxygen
Catalysts
Kinetics
Compensation and Redress
Temperature

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

In situ surface coverage analysis of RuO 2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis. / Teschner, Detre; Novell-Leruth, Gerard; Farra, Ramzi; Knop-Gericke, Axel; SchlÖgl, Robert; Szentmiklósi, L.; Hevia, Miguel González; Soerijanto, Hary; Schomäcker, Reinhard; Pérez-Ramírez, Javier; López, Núria.

In: Nature Chemistry, Vol. 4, No. 9, 09.2012, p. 739-745.

Research output: Contribution to journalArticle

Teschner, D, Novell-Leruth, G, Farra, R, Knop-Gericke, A, SchlÖgl, R, Szentmiklósi, L, Hevia, MG, Soerijanto, H, Schomäcker, R, Pérez-Ramírez, J & López, N 2012, 'In situ surface coverage analysis of RuO 2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis', Nature Chemistry, vol. 4, no. 9, pp. 739-745. https://doi.org/10.1038/nchem.1411
Teschner, Detre ; Novell-Leruth, Gerard ; Farra, Ramzi ; Knop-Gericke, Axel ; SchlÖgl, Robert ; Szentmiklósi, L. ; Hevia, Miguel González ; Soerijanto, Hary ; Schomäcker, Reinhard ; Pérez-Ramírez, Javier ; López, Núria. / In situ surface coverage analysis of RuO 2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis. In: Nature Chemistry. 2012 ; Vol. 4, No. 9. pp. 739-745.
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