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Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules

Nature Materials volume 9, pages 998–1003 (2010)Cite this article

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Abstract

The design of new catalysts for polymer electrolyte membrane fuel cells must be guided by two equally important fundamental principles: optimization of their catalytic behaviour as well as the long-term stability of the metal catalysts and supports in hostile electrochemical environments1,2. The methods used to improve catalytic activity are diverse3,4,5,6,7,8, ranging from the alloying3,4 and de-alloying5 of platinum to the synthesis of platinum core–shell catalysts6. However, methods to improve the stability of the carbon supports and catalyst nanoparticles are limited9,10, especially during shutdown (when hydrogen is purged from the anode by air) and startup (when air is purged from the anode by hydrogen) conditions when the cathode potential can be pushed up to 1.5 V (ref. 11). Under the latter conditions, stability of the cathode materials is strongly affected (carbon oxidation reaction) by the undesired oxygen reduction reaction (ORR) on the anode side. This emphasizes the importance of designing selective anode catalysts that can efficiently suppress the ORR while fully preserving the Pt-like activity for the hydrogen oxidation reaction. Here, we demonstrate that chemically modified platinum with a self-assembled monolayer of calix[4]arene molecules meets this challenging requirement.

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Figure 1: Imaging of Pt(111) and Pt(111)–calix electrodes by STM and corresponding model for adsorbed calix[4]arene molecules on Pt(111).
Figure 2: Relationships between surface coverages by calix[4]arene molecules and Hupd/OHad on Pt(111) in 0.1 M HClO4.
Figure 3: Design of ‘O2-tolerant’ selective anode catalysts for the HOR by controlling Θcalix on Pt(111).
Figure 4: High selectivity of the ORR and HOR is also observed on the calix[4]arene-covered Pt(100) and polycrystalline Pt electrodes, suggesting that the Pt–calix systems are of broad fundamental and technological importance.
Figure 5: Synthesis of calix[4]arene thio derivate 3 used in the present study.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences, US Department of Energy under Contract No. DE-AC03-76SF00098. B.G. acknowledges support from the Center of Excellence Low Carbon Technologies (CO NOT) and the Ministry of Higher Education, Science and Technology of Slovenia (ARRS-3311-04-831034).

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Authors and Affiliations

  1. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva cesta 5, 1000 Ljubljana, Slovenia

    Bostjan Genorio & Stane Pejovnik

  2. National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia

    Bostjan Genorio

  3. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Dusan Strmcnik, Dusan Tripkovic, Goran Karapetrov, Vojislav R. Stamenkovic & Nenad M. Marković

  4. Nuclear Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Ram Subbaraman

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Contributions

B.G., D.S. and N.M. designed the experiments; B.G., R.S., D.S., D.T. and G.K. carried out the experiments. B.G., D.S., V.S., S.P. and N.M. discussed the results and co-wrote the paper.

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Correspondence to Nenad M. Marković.

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Genorio, B., Strmcnik, D., Subbaraman, R. et al. Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules. Nature Mater 9, 998–1003 (2010). https://doi.org/10.1038/nmat2883

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