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Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation

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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Figure 1: Crystal structure and catalytic properties of Al13Fe4.
Figure 2: XPS investigation of Al13Fe4.
Figure 3: In situ X-ray diffraction of Al13Fe4.

References

  1. Piringer, O. G. & Baner, A. L. Plastic Packaging: Interactions with Food and Pharmaceuticals 2nd edn (Wiley, 2008).

    Book  Google Scholar 

  2. Borodzinski, A. & Bond, G. C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts. Part 1. Effect of changes to the catalyst during reaction. Catal. Rev. Sci. Engin. 48, 91–144 (2006).

    CAS  Article  Google Scholar 

  3. Borodzinski, A. & Bond, G. C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts, Part 2: Steady-state kinetics and effects of palladium particle size, carbon monoxide, and promoters. Catal. Rev. Sci. Eng. 50, 379–469 (2008).

    CAS  Article  Google Scholar 

  4. Ahn, I. Y., Lee, J. H., Kim, S. K. & Moon, S. H. Three-stage deactivation of Pd/SiO2 and Pd–Ag/SiO2 catalysts during the selective hydrogenation of acetylene. Appl. Catal. A 360, 38–42 (2009).

    CAS  Article  Google Scholar 

  5. Khan, N. A., Shaikhutdinov, S. & Freund, H-J. Acetylene and ethylene hydrogenation on alumina supported Pd–Ag model catalysts. Catal. Lett. 108, 159–164 (2006).

    CAS  Article  Google Scholar 

  6. Derouane, E. G. Second European Symposium on Catalysis by Metals. Multimetallic catalysts in synthesis and transformation of hydrocarbons: Concluding remarks, critical issues and perspectives. J. Mol. Catal. 25, 51–58 (1984).

    CAS  Article  Google Scholar 

  7. Paul, R. & Hilly, G. Preparation of an active iron and its application to the semihydrogenation of acetylene derivatives. Bull. Soc. Chim. Fr. 6, 218–223 (1939).

    CAS  Google Scholar 

  8. Thompson, A. F. & Wyatt, S. B. Partial reduction of acetylenes to olefins using an iron catalyst. J. Am. Chem. Soc. 62, 2555–2556 (1940).

    CAS  Article  Google Scholar 

  9. Reppe, W. Ethynylation. IV. Reactions of α-alkynols and γ-alkynediols. Justus Liebigs Ann. Chem. 596, 38–79 (1955).

    CAS  Article  Google Scholar 

  10. Taira, S-I. The Urusibara catalysts. I. Some structural features revealed by X-ray diffraction. Bull. Chem. Soc. Jpn 35, 844–851 (1962).

    CAS  Article  Google Scholar 

  11. Nitta, Y., Matsugi, S. & Imanaka, T. Partial hydrogenation of phenylacetylene on copper-promoted iron catalyst. Catal. Lett. 5, 67–72 (1990).

    CAS  Article  Google Scholar 

  12. Phua, P-H., Lefort, L., Boogers, J. A. F., Tristany, M. & de Vries, J. G. Soluble iron nanoparticles as cheap and environmentally benign alkene and alkyne hydrogenation catalysts. Chem. Commun. 3747–3749 (2009).

  13. Sabatier, P. & Senderens, J. B. Nouvelles méthodes générales d’hydrogénation et de dédoublement moléculaire basées sur l’emploi des métaux divisés. Ann. Chim. Phys. 4, 319–432 (1905).

    Google Scholar 

  14. Studt, F. et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene. Science 320, 1320–1322 (2008).

    CAS  Article  Google Scholar 

  15. Armbrüster, M. et al. Pd–Ga intermetallic compounds as highly selective semi-hydrogenation catalysts. J. Am. Chem. Soc. 132, 14745–14747 (2010).

    Article  Google Scholar 

  16. Armbrüster, M., Wowsnick, G., Friedrich, M., Heggen, M. & Cardoso-Gil, R. Synthesis and catalytic properties of nanoparticulate intermetallic Ga–Pd compounds. J. Am. Chem. Soc. 133, 9112–9118 (2011).

    Article  Google Scholar 

  17. Kovnir, K. et al. In situ surface characterization of the intermetallic compound PdGa. A highly selective hydrogenation catalyst. Surf. Sci. 603, 1784–1792 (2009).

    CAS  Article  Google Scholar 

  18. Osswald, J. et al. Palladium–gallium intermetallic compounds for the selective hydrogenation of acetylene Part II: Surface characterization and catalytic performance. J. Catal. 258, 219–227 (2008).

    CAS  Article  Google Scholar 

  19. Osswald, J. et al. Palladium–gallium intermetallic compounds for the selective hydrogenation of acetylene Part I: Preparation and structural investigation under reaction conditions. J. Catal. 258, 210–218 (2008).

    CAS  Article  Google Scholar 

  20. Kovnir, K. et al. PdGa and Pd3Ga7: Highly-selective catalysts for the acetylene partial hydrogenation. Stud. Surf. Sci. Catal. 162, 481–488 (2006).

    CAS  Article  Google Scholar 

  21. Kovnir, K. et al. A new approach to well-defined, stable and site-isolated catalysts. Sci. Technol. Adv. Mater. 8, 420–427 (2007).

    CAS  Article  Google Scholar 

  22. Grin, J., Burkhardt, U., Ellner, M. & Peters, K. Refinement of the Fe4Al13 structure and its relationship to the quasihomological homeotypical structures. Z. Kristallogr. 209, 479–487 (1994).

    CAS  Google Scholar 

  23. Gille, P. & Bauer, B. Single crystal growth of Al13Co4 and Al13Fe4 from Al-rich solutions by the Czochralski method. Cryst. Res. Technol. 43, 1161–1167 (2008).

    CAS  Article  Google Scholar 

  24. Stampfl, C., Ganduglia-Pirovano, M. V., Reuter, K. & Scheffler, M. Catalysis and corrosion: The theoretical surface-science context. Surf. Sci. 500, 368–394 (2002).

    CAS  Article  Google Scholar 

  25. Seah, M. P. et al. Ultra-thin SiO2 on Si IX: Absolute measurements of the amount of silicon oxide as a thickness of SiO2 on Si. Surf. Interface Anal. 41, 430–439 (2009).

    CAS  Article  Google Scholar 

  26. Teschner, D. et al. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science 320, 86–89 (2008).

    CAS  Article  Google Scholar 

  27. Popv, P. et al. Anisotropic physical properties of the Al13Fe4 complex intermetallic and its ternary derivative Al13(Fe,Ni)4 . Phys. Rev. B 81, 184203 (2010).

    Article  Google Scholar 

  28. De Smit, E. & Weckhuysen, B. M. The renaissance of iron-based Fischer–Tropsch synthesis: On the multifaceted catalyst deactivation behaviour. Chem. Soc. Rev. 37, 2758–2781 (2008).

    CAS  Article  Google Scholar 

  29. Danafara, F., Fakhru’l-Razi, A., Salleh, M. A. M. & Biak, D. R. A. Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—a review. Chem. Eng. J. 155, 37–48 (2009).

    Article  Google Scholar 

  30. Powell, C. J. & Jablonski, A. Evaluation of electron inelastic mean free paths for selected elements and compounds. Surf. Interf. Anal. 29, 108–114 (2000).

    CAS  Article  Google Scholar 

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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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Correspondence to M. Armbrüster.

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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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