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Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst

Nature Nanotechnology volume 6, pages 302–307 (2011)Cite this article

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Abstract

Formic acid (HCOOH) has great potential as an in situ source of hydrogen for fuel cells, because it offers high energy density, is non-toxic and can be safely handled in aqueous solution. So far, there has been a lack of solid catalysts that are sufficiently active and/or selective for hydrogen production from formic acid at room temperature. Here, we report that Ag nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H2 from formic acid at ambient temperature. Atom probe tomography confirmed that the nanoparticles have a core–shell configuration, with the shell containing between 1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically promoted by the Ag core, leading to significantly enhanced catalytic properties. Our nanocatalysts could be used in the development of micro polymer electrolyte membrane fuel cells for portable devices and could also be applied in the promotion of other catalytic reactions under mild conditions.

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Figure 1: Plot of rates of formic acid decomposition monitored by 13C NMR over different metal colloid catalysts (2 × 10−4 mol in 600 µl in D2O versus d-band centre; size, ∼2–4 nm, except Ag, 8 nm) and M-core Pd shell (1:1) catalysts.
Figure 2: Catalytic formic acid decomposition shows a strong dependence on the surface structure of the metal particle28,29.
Figure 3: Correlation of rate of formic acid decomposition and core–shell geometry.
Figure 4: Correlation of hydrogen production activity with electronic promotion from the Ag core to the Pd shell using a CO probe combined with a Fourier transform infrared (FTIR) technique.
Figure 5: APT data from Ag@Pd nanoparticles.

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Acknowledgements

The authors acknowledge the Engineering and Physical Sciences Research Council (EPSRC) of the UK Research Council for financial support. The authors are grateful to Johnson Matthey PLC for the donation of precious metal salts. K.T. thanks the Thai Government for providing a PhD scholarship to Oxford.

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Authors and Affiliations

  1. Department of Chemistry, Wolfson Catalysis Centre, University of Oxford, Oxford, OX1 3QR, UK

    Karaked Tedsree, Simon Jones, Chun Wong Aaron Chan, Kai Man Kerry Yu & Shik Chi Edman Tsang

  2. Department of Materials, University of Oxford, Oxford, OX1 3PH, UK

    Tong Li, Paul A. J. Bagot, Emmanuelle A. Marquis & George D. W. Smith

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  1. Karaked Tedsree
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  3. Simon Jones
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Contributions

K.T., S.J., C.W.A.C. and K.M.K.Y. contributed to material synthesis, testing and characterization. T.L., P.A.J.B., E.A.M. and G.D.W.S. contributed to atom probe tomography. S.C.E.T. initiated, supervised and coordinated the research. All authors discussed the results and commented on the manuscript.

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Correspondence to Shik Chi Edman Tsang.

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Tedsree, K., Li, T., Jones, S. et al. Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst. Nature Nanotech 6, 302–307 (2011). https://doi.org/10.1038/nnano.2011.42

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