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Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction

Nature Materials volume 11, pages 970–977 (2012)Cite this article

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Abstract

A careful choice of the surface coverage of iron phthalocyanine (FePc) on Ag (110) around the single monolayer allows us to drive with high precision both the long-range supramolecular arrangement and the local adsorption geometry of FePc molecules on the given surface. We show that this opens up the possibility of sharply switching the catalytic activity of FePc in the oxygen reduction reaction and contextual surface oxidation in a reproducible way. A comprehensive and detailed picture built on diverse experimental evidence from scanning tunnelling microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy, coupled with density functional theory calculations, sheds new light on the nature of the catalytically active molecule–surface coordination and on the boundary conditions for its occurrence. The results are of relevance for the improvement of the catalytic efficiency of metallo-macrocycles as viable substitutes for platinum in the cathodic compartment of low-temperature fuel cells.

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Figure 1: Monolayer phases of FePc on Ag (110): STM images and ball models20.
Figure 2: The effect of oxygen dosage and annealing on FePc/Ag(110) phases: STM evidence.
Figure 3: The effect of oxygen dosage and annealing on FePc/Ag(110) phases: XPS evidence.
Figure 4: The effect of oxygen dosage and annealing on low density FePc/Ag(110) phases: XAS evidence.
Figure 5: The effect of oxygen dosage on the R1-LD FePc/Ag(110) phase: DFT results.
Figure 6: Removing oxygen from the surface by ionized hydrogen: STM and XPS data.

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Acknowledgements

This work has been partially funded by MIUR (PRIN 2008, Project n. 2008MXZEAS: ‘Molecular SPACE’) and by the University of Padova (Progetto Strategico STPD08RCX5_003 ‘HELIOS’ and Progetti di Ricerca di Ateneo - CPDA118475/11).

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Authors and Affiliations

  1. Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131 Padova, Italy

    F. Sedona, M. Di Marino, D. Forrer, A. Vittadini, M. Casarin & M. Sambi

  2. CR-INSTM ‘Village’, Via Marzolo 1, 35131 Padova, Italy

    D. Forrer, A. Vittadini & M. Casarin

  3. CNR-ISTM, Via Marzolo 1, 35131 Padova, Italy

    A. Vittadini & M. Casarin

  4. CNR-IOM, Laboratorio Nazionale TASC, Area Science Park, Basovizza S. S. 14, 34149 Trieste, km 163.5, Italy

    A. Cossaro, L. Floreano & A. Verdini

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F.S., M.D.M. and D.F. contributed equally to this work.

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Sedona, F., Di Marino, M., Forrer, D. et al. Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction. Nature Mater 11, 970–977 (2012). https://doi.org/10.1038/nmat3453

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