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Applying Dynamic and Synchronous DRIFTS/EXAFS to the Structural Reactive Behaviour of Dilute (≤1 wt%) Supported Rh/Al2O3 Catalysts using Quick and Energy Dispersive EXAFS

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Abstract

Examples of the application of a synchronous DRIFTS/EXAFS/mass spectrometry (MS) methodology to the study of dilute (≤ 1wt%) Rh/Al2O3 catalysts are discussed. These are used to explore the potential of this approach for understanding of the behaviour of supported metal catalysts “in a single shot”, and in the often preferred regime of low (<1 wt%) loadings of active precious metals. Firstly, the sequential interaction of NO (323 K) and then CO (373 K) with reduced, 0.5 wt% Rh/Al2O3 catalysts is studied. Infrared spectroscopy indicates that two surface species (a bent Rh(NO−) and Rh(CO)2 species) can be created using this sequential gas absorption/reaction method with minimal interference from other carbonyl or nitrosyl species. As such the potential for a reliable structural characterisation of the local structure of these species by EXAFS becomes possible. However, in contrast to the infrared spectroscopy, analysis of the EXAFS data also indicates that, even for such low loaded Rh systems, oxidative disruption of the Rh by the NO and CO is not complete and that bonding typical of small Rh clusters persists in both cases. The possible sources of this apparent spectroscopic difference of opinion are discussed. Secondly, 1wt% Rh/Al2O3 catalysts are studied using dispersive EXAFS at 573 K with 100 ms time resolution, during a redox switching event involving a reducing feedstock comprising just 3000 ppm of CO and 3000 ppm of NO. It is shown that highly useful and insightful time resolved and synchronously obtained XANES/EXAFS/IR data can be obtained even in this dilute Rh and more “realistic” case. Additional data, regarding the overall performance of the experiment, as currently implemented at the ESRF, along with a discussion of where enhanced performance might be yet still be gained, are also given.

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Notes

  1. Manufacturers specification for unmodified DRIFTS Cell. To date this system has been regularly and successfully used at 673 K [11, 12] and occasionally at higher temperatures (to 773 K). At the time or writing, however, extended and reliable use at temperatures significantly greater than 673 K has yet to be demonstrated for the system after modification for the combined X-ray/DRIFTS experiment.

  2. Since the compilation and submission of this paper a fast (<<1 secs/scan) Quick scanning EXAFS resource of the sort identified as being sorely needed has indeed become available (at the Swiss Light Source) to a wider user community. The author is given to understand (and sincerely hopes) that other resources of this nature are planned elsewhere, and will pass into the realm of accessible user facilities in the relatively near future. Further information regarding this new type of QUEXAFS resource can be found in [58, 59] or (http://sls.web.psi.ch/view.php/beamlines/superxas/).

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Acknowledgments

The ESRF is thanked for access to facilities and for the funding to develop this experiment and the offline facilities wherein it is housed. Florian Perrin, Trevor Mairs, Pascal Dideron, Gemma Guilera, Olivier Mathon, Sakura Pascarelli and Anna Kroner at ID24 are thanked for their support and the various contributions they have made to the development of the experiment. Anna Kroner is especially thanked for the synthesis and EXAFS spectrum of the supported Rh(CO)2Cl/Al2O3 reference sample. Wim Bras and Sergei Nikitenko at DUBBLE are acknowledged for the provision of the beamtime and the support given during the experiment. Andy Beale and Fouad Soulimani (University of Utrecht) are also thanked for sharing of the DUBBLE beamtime used to collect the scanning EXAFS/infrared data reported here. The author is extremely grateful to Masahide Miura, Toyota Motor Corporation, Naoyuki Hara, Toyota Motor Europe, and Yasutaka Nagai, Toyota Central Research and Development Laboratories, for their longstanding commitment to research and development at ID24 and for the permission to use the Energy dispersive/DRIFTS data shown in this paper. Lastly the author would like to thank Augusto Marcelli, INFN-Laboratori Nazionali di Frascati, Italy, for discussions and information regarding new possibilities for exploitation of synchrotron based infra red light.

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  1. The European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, BP-220, Grenoble, 38043, France

    Mark A. Newton

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Newton, M.A. Applying Dynamic and Synchronous DRIFTS/EXAFS to the Structural Reactive Behaviour of Dilute (≤1 wt%) Supported Rh/Al2O3 Catalysts using Quick and Energy Dispersive EXAFS. Top Catal 52, 1410–1424 (2009). https://doi.org/10.1007/s11244-009-9321-2

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