Abstract
Replacing noble metals in heterogeneous catalysts by low-cost substitutes has driven scientific and industrial research for more than 100 years. Cheap and ubiquitous iron is especially desirable, because it does not bear potential health risks like, for example, nickel. To purify the ethylene feed for the production of polyethylene, the semi-hydrogenation of acetylene is applied (80 × 106 tons per annum; refs 1, 2, 3). The presence of small and separated transition-metal atom ensembles (so-called site-isolation), and the suppression of hydride formation are beneficial for the catalytic performance4,5,6. Iron catalysts necessitate at least 50 bar and 100 °C for the hydrogenation of unsaturated C–C bonds, showing only limited selectivity towards semi-hydrogenation7,8,9,10,11,12,13. Recent innovation in catalytic semi-hydrogenation is based on computational screening of substitutional alloys to identify promising metal combinations using scaling functions14 and the experimental realization of the site-isolation concept employing structurally well-ordered and in situ stable intermetallic compounds of Ga with Pd (refs 15, 16, 17, 18, 19). The stability enables a knowledge-based development by assigning the observed catalytic properties to the crystal and electronic structures of the intermetallic compounds20,21. Following this approach, we identified the low-cost and environmentally benign intermetallic compound Al13Fe4 as an active and selective semi-hydrogenation catalyst. This knowledge-based development might prove applicable to a wide range of heterogeneously catalysed reactions.
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Acknowledgements
We thank G. Auffermann for chemical analysis, R. Wagner for the UHV preparation of the single crystals and S. Hoffmann as well as E. Kitzelmann for in situ differential thermal analysis and thermal gravimetric measurements. The European Network of Excellence on ‘Complex Metallic Alloys’, contract No. NMP3-CT-2005-500140, the EU FP7 NMI3 Access Programme and the NAP VENEUS grant (OMFB-00184/2006) are acknowledged for supporting this work in part and the in situ PGAA measurements, respectively. Beam time for in situ XPS measurements was provided by the Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (ID 2010_1_90734) and we thank the team of the ISIS-PGM beamline for continuous support. The European Centre for Development of Alloys and Compounds (C-MAC) nurtured this publication by providing a networking platform.
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P.G., M. Hahne, M. Heggen and M. Feuerbacher provided the samples that were characterized by M.A. Catalytic measurements were performed by M.A., K.K. and M. Friedrich, and D.T., G.W., M. Friedrich and M.A. conducted the XPS studies after D.R. prepared the samples. In situ PGAA and XRD experiments were conducted by L.S. and F.G., respectively. R.S. and Y.G. gave conceptual advice and M.A., M. Feuerbacher and D.T. wrote the paper.
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Armbrüster, M., Kovnir, K., Friedrich, M. et al. Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation. Nature Mater 11, 690–693 (2012). https://doi.org/10.1038/nmat3347
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DOI: https://doi.org/10.1038/nmat3347
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