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A Comparative Discussion of the Catalytic Activity and CO2-Selectivity of Cu-Zr and Pd-Zr (Intermetallic) Compounds in Methanol Steam Reforming

Institute of Physical Chemistry, University of Innsbruck, Innrain 80‐82, A‐6020 Innsbruck, Austria
Institute of Mineralogy and Petrography, University of Innsbruck, Innrain 52d, A‐6020 Innsbruck, Austria
University Service Facility for Transmission Electron Microscopy (USTEM), Technische Universität Wien, Wiedner Hauptstrasse 8‐10/057B, A‐1040 Wien, Österreich
Department of Inorganic Chemistry, Fritz‐Haber‐Institute of the Max‐Planck‐Society, Faradayweg 4‐6, D‐14195 Berlin, Germany
Author to whom correspondence should be addressed.
Catalysts 2017, 7(2), 53;
Received: 10 January 2017 / Accepted: 7 February 2017 / Published: 9 February 2017
(This article belongs to the Special Issue Reforming Catalysts)
PDF [6052 KB, uploaded 15 February 2017]


The activation and catalytic performance of two representative Zr-containing intermetallic systems, namely Cu-Zr and Pd-Zr, have been comparatively studied operando using methanol steam reforming (MSR) as test reaction. Using an inverse surface science and bulk model catalyst approach, we monitored the transition of the initial metal/intermetallic compound structures into the eventual active and CO2-selective states upon contact to the methanol steam reforming mixture. For Cu-Zr, selected nominal stoichiometries ranging from Cu:Zr = 9:2 over 2:1 to 1:2 have been prepared by mixing the respective amounts of metallic Cu and Zr to yield different Cu-Zr bulk phases as initial catalyst structures. In addition, the methanol steam reforming performance of two Pd-Zr systems, that is, a bulk system with a nominal Pd:Zr = 2:1 stoichiometry and an inverse model system consisting of CVD-grown ZrOxHy layers on a polycrystalline Pd foil, has been comparatively assessed. While the CO2-selectivity and the overall catalytic performance of the Cu-Zr system is promising due to operando formation of a catalytically beneficial Cu-ZrO2 interface, the case for Pd-Zr is different. For both Pd-Zr systems, the low-temperature coking tendency, the high water-activation temperature and the CO2-selectivity spoiling inverse WGS reaction limit the use of the Pd-Zr systems for selective MSR applications, although alloying of Pd with Zr opens water activation channels to increase the CO2 selectivity. View Full-Text
Keywords: Zirconium-tert.-butoxide; Palladium; Zr reduction; methanol steam reforming; copper Zirconium-tert.-butoxide; Palladium; Zr reduction; methanol steam reforming; copper

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Köpfle, N.; Mayr, L.; Schmidmair, D.; Bernardi, J.; Knop‐Gericke, A.; Hävecker, M.; Klötzer, B.; Penner, S. A Comparative Discussion of the Catalytic Activity and CO2-Selectivity of Cu-Zr and Pd-Zr (Intermetallic) Compounds in Methanol Steam Reforming. Catalysts 2017, 7, 53.

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