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

Nature Chemistry

Volumn 4, Issue 9, 2012, Pages 739-745

  Teschner, Detre ^a,b   Novell Leruth, Gerard ^c   Farra, Ramzi ^a   Knop Gericke, Axel ^a   SchlÖgl, Robert ^a   Szentmiklósi, László ^b   Hevia, Miguel González ^c   Soerijanto, Hary ^d   Schomäcker, Reinhard ^d   Pérez Ramírez, Javier ^e   López, Núria ^c  

^a FRITZ HABER INSTITUT DER MAX PLANCK GESELLSCHAFT   (Germany)

^b INSTITUTE OF EXPERIMENTAL MEDICINE   (Hungary)

^c INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^d TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

^e ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84866879044     PISSN: 17554330     EISSN: 17554349     Source Type: Journal    
DOI: 10.1038/nchem.1411     Document Type: Article

References (36)

1. Ertl, G., Knotzinger, H., Schuth, F. & Weitkamp J. (eds) Handbook of Heterogeneous Catalysis (Wiley-VCH, 2008).
2. Constable, F. H. The mechanism of catalytic decomposition. Proc. R. Soc. Lond. A 108, 355-378 (1925).
3. Cremer, E. The compensation effect in heterogeneous catalysis. Adv. Catal. 7, 75-91 (1955).
4. Wilson, M. C. & Galwey, A. K. Compensation effect in heterogeneous catalytic reactions including hydrocarbon formation on clays. Nature 243, 402-404 (1973).
5. Bond, G. C., Keane, M. A., Kral, H. & Lercher, J. A. Compensation phenomena in heterogeneous catalysis: general principles and a possible explanation. Catal. Rev. Sci. Eng. 42, 323-383 (2000).
6. Hibi, T., Nishida, H. & Abekawa, H. Process for producing chlorine. US patent 5,871,707 (1999).
7. Hibi, T. et al. Process for producing chlorine. European patent EP936184 (1999).
8. Wolf, A., Mleczko, L., Schluter, O. F. & Schubert, S. Method for producing chlorine by gas phase oxidation. European patent EP2026905 (2006).
9. Wolf, A., Mleczko, L., Schubert, S. & Schluter, O. F. Method for producing chlorine by gas phase oxidation. European patent EP2027063 (2006).
10. Seki, K. Development of RuO2/rutile-TiO2 catalyst for industrial HCl oxidation process. Catal. Surv. Asia 14, 168-175 (2010).
11. Mondelli, C., Amrute, A. P., Schmidt, T. & Perez-Ramrez, J. Shaped RuO2/SnO2-Al2O3 catalyst for large-scale stable Cl2 production by HCl oxidation. ChemCatChem. 3, 657-660 (2011).
12. Liu, L. & Guo, Q. X. Isokinetic relationship, isoequilibrium relationship, and enthalpy-entropy compensation. Chem. Rev. 101, 673-695 (2001).
13. Bligaard, T. et al. On the compensation effect in heterogeneous catalysis. J. Phys. Chem. B 107, 9325-9331 (2003).
14. Lynggaard, H., Andreasen, A., Stegelmann, C. & Soltze, P. Analysis of simple kinetic models in heterogeneous catalysis. Prog. Surf. Sci. 77, 71-137 (2004).
15. Kang, H. C., Jachimowski, T. A. & Weinberg, W. H. Role of local configurations in a Langmuir-Hinshelwood surface reaction: kinetics and compensation. J. Chem. Phys. 93, 1418-1429 (1990).
16. Chorkendorff, I. & Niemansverdriet, J. W. in Concepts of Modern Catalysis and Kinetics Ch. 2 (Wiley-VCH, 2003).
17. Temel, B., Meskine, H., Reuter, K., Scheffler, M. & Metiu, H. Does phenomenological kinetics provide an adequate description of heterogeneous catalytic reactions. J. Chem. Phys. 126, 204711 (2007).
18. Atkins, P. & de Paula, J. Atkins' Physical Chemistry 8th edn (Oxford Univ. Press, New York, 2006).
19. Laidler, K. J. Chemical Kinetics 3rd edn (Prentice Hall, 1987).
20. Bond, G. C. Rosa, F. C. & Short, E. L. Kinetics of hydrolysis of carbon tetrachloride by acidic solids. Appl. Catal. A. Gen. 329, 46-57 (2007).
21. Temkin, M. Relation between the apparent and the true activation energy of heterogeneous reactions. Acta Physicochim. URSS 2, 313-316 (1935).
22. Yelon, A., Movaghar, B. & Crandall, R. S. Multi-excitation entropy: its role in thermodynamics and kinetics. Rep. Prog. Phys. 69, 1156-1194 (2006) and references therein.
23. Estrup, P. J., Greene, E. F., Cardillo, M. J. & Tully, J. C. Influence of surface phase transitions on desorption kinetics: the compensation effect. J. Phys. Chem. 90, 4099-4104 (1986).
24. Crihan, D. et al. Stable Deacon process for HCl oxidation over RuO2. Angew. Chem. Int. Ed. 47, 2131-2134 (2008).
25. Zweidinger, S. et al. Reaction mechanism of the oxidation of HCl over RuO2(110). J. Phys Chem. C 112, 9966-9969 (2008).
26. Lopez, N., Gomez-Segura, J., Marn, R. P. & Perez-Ramrez, J. Mechanism of HCl oxidation (Deacon process) over RuO2. J. Catal. 255, 29-39 (2008).
27. Studt, F. et al. Volcano relation for the Deacon process over transition-metal oxides. ChemCatChem 2, 98-102 (2010).
28. Hevia, M. A. G., Amrute, A. P., Schmidt, T. & Perez-Ramrez, J. Transient mechanistic study of the gas-phase HCl oxidation to Cl2 on bulk and supported RuO2 catalysts. J. Catal. 276, 141-151 (2010).
29. Teschner, D. et al. An integrated approach to Deacon chemistry on RuO2-based catalysts. J. Catal. 285, 273-284 (2012).
30. Perez-Ramrez, J. & Kondratenko, E. V. Evolution, achievements, and perspectives of the TAP technique. Catal. Today 121, 160-169 (2007).
31. Gleaves, J. T., Yablonsky, G., Zheng, X. L., Fushimi, R. & Mills, P. L. Temporal analysis of products (TAP) - recent advances in technology for kinetic analysis of multi-component catalysts. J. Mol. Catal. A 315, 108-134 (2010).
32. Revay, Z. et al. In situ determination of hydrogen inside a catalytic reactor using prompt g activation analysis. Anal. Chem. 80, 6066-6071 (2008).
33. Teschner, D. et al. The roles of subsurface carbon and hydrogen in palladiumcatalyzed alkyne hydrogenation. Science 320, 86-89 (2008).
34. Hammer, B., Hansen, L. B. & Nskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys. Rev. B 59, 7413-7421 (1999).
35. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758-1775 (1999).
36. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integration. Phys. Rev. B 13, 5188-5192 (1976).