Enabling direct H2O2 production through rational electrocatalyst design

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  • A Corrigendum to this article was published on 17 December 2013
  • An Erratum to this article was published on 23 January 2014

Abstract

Future generations require more efficient and localized processes for energy conversion and chemical synthesis. The continuous on-site production of hydrogen peroxide would provide an attractive alternative to the present state-of-the-art, which is based on the complex anthraquinone process. The electrochemical reduction of oxygen to hydrogen peroxide is a particularly promising means of achieving this aim. However, it would require active, selective and stable materials to catalyse the reaction. Although progress has been made in this respect, further improvements through the development of new electrocatalysts are needed. Using density functional theory calculations, we identify Pt–Hg as a promising candidate. Electrochemical measurements on Pt–Hg nanoparticles show more than an order of magnitude improvement in mass activity, that is, A g−1 precious metal, for H2O2 production, over the best performing catalysts in the literature.

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Figure 1: Overview of different electrocatalysts for H2O2 production from the literature and from the present work.
Figure 2: Theoretical modelling of oxygen reduction to H2O and H2O2.
Figure 3: Experimental characterization of Pt–Hg on extended surfaces.
Figure 4: Experimental characterization of Pt–Hg/C nanoparticles.

Change history

  • 21 November 2013

    In the version of this Article originally published, the middle initials of the penultimate author were missing; the name should have read Ifan E. L. Stephens. In the Author contributions and Additional information sections 'I.S.' should have read 'I.E.L.S.' These errors have now been corrected in the online versions of the Article.

  • 23 December 2013

    In the version of this Article originally published, in Fig. 1, the top two values on the y axis were switched. This error has now been corrected in the online versions of the Article.

References

  1. 1

    Perlo, P. et al. Catalysis for Sustainable Energy Production 89–105 (Wiley, 2009).

  2. 2

    Armaroli, N. & Balzani, V. The future of energy supply: challenges and opportunities. Angew. Chem. Int. Ed. 46, 52–66 (2007).

  3. 3

    Kotrel, S. & Brauninger, S. in Handbook of Heterogeneous Catalysis 2nd edn (eds Ertl, G., Knoezinger, H., Schueth, F. & Weitkamp, J.) 1963 (Wiley, 2008).

  4. 4

    Ullmann’s Encyclopedia of Industrial Chemistry (Wiley, 1999–2013).

  5. 5

    Samanta, C. Direct synthesis of hydrogen peroxide from hydrogen and oxygen: An overview of recent developments in the process. Appl. Catal. A 350, 133–149 (2008).

  6. 6

    Campos-Martin, J. M., Blanco-Brieva, G. & Fierro, J. L. G. Hydrogen peroxide synthesis: An outlook beyond the anthraquinone process. Angew. Chem. Int. Ed. 45, 6962–6984 (2006).

  7. 7

    Fukuzumi, S., Yamada, Y. & Karlin, K. D. Hydrogen peroxide as a sustainable energy carrier: Electrocatalytic production of hydrogen peroxide and the fuel cell. Electrochim. Acta 82, 493–511 (2012).

  8. 8

    Hâncu, D., Green, J. & Beckman, E. J. H2O2 in CO2/H2O biphasic systems: Green synthesis and epoxidation reactions. Ind. Eng. Chem. Res. 41, 4466–4474 (2002).

  9. 9

    Edwards, J. K. et al. Switching off hydrogen peroxide hydrogenation in the direct synthesis process. Science 323, 1037–1041 (2009).

  10. 10

    Ford, D. C., Nilekar, A. U., Xu, Y. & Mavrikakis, M. Partial and complete reduction of O2 by hydrogen on transition metal surfaces. Surf. Sci. 604, 1565–1575 (2010).

  11. 11

    Yamanaka, I., Hashimoto, T., Ichihashi, R. & Otsuka, K. Direct synthesis of H2O2 acid solutions on carbon cathode prepared from activated carbon and vapor-growing-carbon-fiber by a H2/O2 fuel cell. Electrochim. Acta 53, 4824–4832 (2008).

  12. 12

    Lobyntseva, E., Kallio, T., Alexeyeva, N., Tammeveski, K. & Kontturi, K. Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies. Electrochim. Acta 52, 7262–7269 (2007).

  13. 13

    Jirkovský, J. S. et al. Single atom hot-spots at Au–Pd nanoalloys for electrocatalytic H2O2 Production. J. Am. Chem. Soc. 133, 19432–19441 (2011).

  14. 14

    Fellinger, T-P., Hasché, F., Strasser, P. & Antonietti, M. Mesoporous nitrogen-doped carbon for the electrocatalytic synthesis of hydrogen peroxide. J. Am. Chem. Soc. 134, 4072–4075 (2012).

  15. 15

    Gouérec, P. & Savy, M. Oxygen reduction electrocatalysis: Ageing of pyrolyzed cobalt macrocycles dispersed on an active carbon. Electrochim. Acta 44, 2653–2661 (1999).

  16. 16

    Bezerra, C. W. B. et al. A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction. Electrochim. Acta 53, 4937–4951 (2008).

  17. 17

    Schulenburg, H. et al. Catalysts for the oxygen reduction from heat-treated iron(III) tetramethoxyphenylporphyrin chloride: Structure and stability of active sites. J. Phys. Chem. B 107, 9034–9041 (2003).

  18. 18

    Sheng, W., Gasteiger, H. A. & Shao-Horn, Y. Hydrogen oxidation and evolution reaction kinetics on platinum: Acid vs alkaline electrolytes. J. Electrochem. Soc. 157, B1529–B1536 (2010).

  19. 19

    Ayers, K. E., Dalton, L. T. & Anderson, E. B. Efficient generation of high energy density fuel from water. ECS Trans. 41, 27–38 (2012).

  20. 20

    Viswanathan, V., Hansen, H. A., Rossmeisl, J. & Nørskov, J. K. Unifying the 2e– and 4e– reduction of oxygen on metal surfaces. J. Phys. Chem. Lett. 3, 2948–2951 (2012).

  21. 21

    Norskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nature Chem. 1, 37–46 (2009).

  22. 22

    Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chem. 1, 552–556 (2009).

  23. 23

    Koper, M. T. M. Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis. J. Electroanal. Chem. 660, 254–260 (2011).

  24. 24

    Janik, M. J., Taylor, C. D. & Neurock, M. First-principles analysis of the initial electroreduction steps of oxygen over Pt(111). J. Electrochem. Soc. 156, B126–B135 (2009) doi:10.1149/1.3008005.

  25. 25

    Tripković, V., Skúlason, E., Siahrostami, S., Nørskov, J. K. & Rossmeisl, J. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations. Electrochim. Acta 55, 7975–7981 (2010).

  26. 26

    Stephens, I. E. L., Bondarenko, A. S., Gronbjerg, U., Rossmeisl, J. & Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ. Sci. 5, 6744–6762 (2012).

  27. 27

    Rossmeisl, J., Karlberg, G. S., Jaramillo, T. & Norskov, J. K. Steady state oxygen reduction and cyclic voltammetry. Faraday Discuss. 140, 337–346 (2009).

  28. 28

    Peterson, A. A. & Nørskov, J. K. Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts. J. Phys. Chem. Lett. 3, 251–258 (2012).

  29. 29

    Skulason, E. et al. A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. Phys. Chem. Chem. Phys. 14, 1235–1245 (2012).

  30. 30

    Hansen, H. A. et al. Electrochemical chlorine evolution at rutile oxide (110) surfaces. Phys. Chem. Chem. Phys. 12, 283–290 (2010).

  31. 31

    Maroun, F., Ozanam, F., Magnussen, O. M. & Behm, R. J. The role of atomic ensembles in the reactivity of bimetallic electrocatalysts. Science 293, 1811–1814 (2001).

  32. 32

    Strmcnik, D. et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. Nature Chem. 2, 880–885 (2010).

  33. 33

    Viswanathan, V. et al. Simulating linear sweep voltammetry from first-principles: Application to electrochemical oxidation of water on Pt(111) and Pt3Ni(111). J. Phys. Chem. C 116, 4698–4704 (2012).

  34. 34

    Siahrostami, S., Bjorketun, M. E., Strasser, P., Greeley, J. & Rossmeisl, J. Tandem cathode for proton exchange membrane fuel cells. Phys. Chem. Chem. Phys. 15, 9326–9334 (2013).

  35. 35

    Wu, H. L., Yau, S. & Zei, M. S. Crystalline alloys produced by mercury electrodeposition on Pt(111) electrode at room temperature. Electrochim. Acta 53, 5961–5967 (2008).

  36. 36

    Angerstein-Kozlowska, H., MacDougall, B. & Conway, B. E. Origin of activation effects of acetonitrile and mercury in electrocatalytic oxidation of formic acid. J. Electrochem. Soc. 120, 756–766 (1973).

  37. 37

    Skuílason, E. et al. Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations. J. Phys. Chem. C 114, 18182–18197 (2010).

  38. 38

    Paulus, U. A., Schmidt, T. J., Gasteiger, H. A. & Behm, R. J. Oxygen reduction on a high-surface area Pt/Vulcan carbon catalyst: A thin-film rotating ring-disk electrode study. J. Electroanal. Chem. 495, 134–145 (2001).

  39. 39

    Van der Vliet, D. F. et al. Mesostructured thin films as electrocatalysts with tunable composition and surface morphology. Nature Mater. 11, 1051–1058 (2012).

  40. 40

    Perez-Alonso, F. J. et al. The effect of size on the oxygen electroreduction activity of mass-selected platinum nanoparticles. Angew. Chem. Intl Ed. 51, 4641–4643 (2012).

  41. 41

    Wesselmark, M., Wickman, B., Lagergren, C. & Lindbergh, G. Hydrogen oxidation reaction on thin platinum electrodes in the polymer electrolyte fuel cell. Electrochem. Commun. 12, 1585–1588 (2010).

  42. 42

    Wolfschmidt, H., Weingarth, D. & Stimming, U. Enhanced reactivity for hydrogen reactions at Pt nanoislands on Au(111). ChemPhysChem 11, 1533–1541 (2010).

  43. 43

    Mortensen, J. J., Hansen, L. B. & Jacobsen, K. W. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B 71, 035109 (2005).

  44. 44

    Atomic Simulation Environment (ASE), available at https://wiki.fysik.dtu.dk/ase, Center for Atomic Scale Material Design (CAMD), Technical University of Denmark, Lyngby.

  45. 45

    Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

  46. 46

    Verdaguer-Casadevall, A., Hernandez-Fernandez, P., Stephens, I. E. L., Chorkendorff, I. & Dahl, S. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum. J. Power Sources 220, 205–210 (2012).

  47. 47

    Alvarez-Rizatti, M. & Jüttner, K. Electrocatalysis of oxygen reduction by UPD of lead on gold single-crystal surfaces. J. Electroanal. Chem. Interfacial Electrochem. 144, 351–363 (1983).

  48. 48

    Jirkovsky, J. S., Halasa, M. & Schiffrin, D. J. Kinetics of electrocatalytic reduction of oxygen and hydrogen peroxide on dispersed gold nanoparticles. Phys. Chem. Chem. Phys. 12, 8042–8053 (2010).

  49. 49

    Blizanac, B. B., Ross, P. N. & Markovic, N. M. Oxygen electroreduction on Ag(111): The pH effect. Electrochim. Acta 52, 2264–2271 (2007).

  50. 50

    CRC Handbook of Chemistry and Physics (CRC Press, 1996).

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Acknowledgements

The authors gratefully acknowledge financial support from the Danish Ministry of Science’s UNIK initiative, Catalysis for Sustainable Energy and The Danish Council for Strategic Research’s project NACORR (12-132695). M.E-E. acknowledges financial support from EU PF7’s initiative Fuel Cell and Hydrogen Joint Undertaking’s project CathCat (GA 303492). B.W. thanks Formas (project number 219-2011-959) for financial support. The Center for Individual Nanoparticle Functionality is supported by the Danish National Research Foundation (DNRF54).

Author information

J.R. and S.S. conceived the DFT calculations. S.S. and M.K. performed the DFT calculations. A.V. and I.E.L.S. designed the experiments. A.V. performed the electrochemical experiments, D.D. the TEM, P.M. the XPS and B.W. the EQCM and SEM-EDS. E.A.P. and R.F. prepared the Ag3Pt sample and performed its XRD. S.S., A.V. and I.E.L.S. co-wrote the first draft of the paper. A.V. designed the figures. All authors discussed the results and commented on the manuscript.

Correspondence to Ifan E. L. Stephens or Jan Rossmeisl.

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Patent application EP 13165265.3 ‘Alloy catalyst material’ has been filed.

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Siahrostami, S., Verdaguer-Casadevall, A., Karamad, M. et al. Enabling direct H2O2 production through rational electrocatalyst design. Nature Mater 12, 1137–1143 (2013) doi:10.1038/nmat3795

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