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Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

Nature Energy volume 2, Article number: 17070 (2017) Cite this article

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Abstract

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolysers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using density functional theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. The results suggest design principles for this class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

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Figure 1: Moiré patterns of monolayer NiOH films on Pt(111) substrates.
Figure 2: Energetics of monolayer NiOH films with various moiré patterns on Pt(111) substrates.
Figure 3: Electrochemical phase diagrams for bulk Ni and Ni films at pH 13.
Figure 4: Born–Haber analysis of the interface formation energies of monolayer Ni films on Pt(111) and Au(111) substrates.
Figure 5: In situ synchrotron measurements of Ni (hydroxy)oxide films on Pt(111).
Figure 6: Water dissociation at Pt–NiOH–water three-phase boundaries.
Figure 7: Electrochemical phase diagram for Mn and Co monolayer films at pH 13.

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References

  1. Stamenkovic, V. R., Strmcnik, D., Lopes, P. P. & Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 16, 57–69 (2017).

    Google Scholar 

  2. Kodama, K., Jinnouchi, R., Takahashi, N., Murata, H. & Morimoto, Y. Activities and stabilities of Au-modified stepped-Pt single-crystal electrodes as model cathode catalysts in polymer electrolyte fuel cells. J. Am. Chem. Soc. 138, 4194–4200 (2016).

    Google Scholar 

  3. Frydendal, R., Paoli, E. A., Chorkendorff, I., Rossmeisl, J. & Stephens, I. E. L. Toward an active and stable catalyst for oxygen evolution in acidic media: Ti-stabilized MnO2 . Adv. Energy Mater. 5, 1500991 (2015).

    Google Scholar 

  4. Kibsgaard, J., Gorlin, Y., Chen, Z. & Jaramillo, T. F. Meso-structured platinum thin films: active and stable electrocatalysts for the oxygen reduction reaction. J. Am. Chem. Soc. 134, 7758–7765 (2012).

    Google Scholar 

  5. Greeley, J. & Markovic, N. M. The road from animal electricity to green energy: combining experiment and theory in electrocatalysis. Energy Environ. Sci. 5, 9246–9256 (2012).

    Google Scholar 

  6. Paoli, E. A. et al. Oxygen evolution on well-characterized mass-selected Ru and RuO2 nanoparticles. Chem. Sci. 6, 190–196 (2015).

    Google Scholar 

  7. Reier, T., Oezaslan, M. & Strasser, P. Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and Pt catalysts: a comparative study of nanoparticles and bulk materials. ACS Catal. 2, 1765–1772 (2012).

    Google Scholar 

  8. Danilovic, N. et al. Using surface segregation to design stable Ru–Ir oxides for the oxygen evolution reaction in acidic environments. Angew. Chem. Int. Ed. 53, 14016–14021 (2014).

    Google Scholar 

  9. Escudero-Escribano, M. et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 352, 73–76 (2016).

    Google Scholar 

  10. Chang, S. H. et al. Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution. Nat. Commun. 5, 4191 (2014).

    Google Scholar 

  11. Cui, C., Gan, L., Heggen, M., Rudi, S. & Strasser, P. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat. Mater. 12, 765–771 (2013).

    Google Scholar 

  12. Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous Solutions 2nd edn 644 (National Association of Corrosion Engineers, 1974).

    Google Scholar 

  13. Sheng, W. et al. Non-precious metal electrocatalysts with high activity for hydrogen oxidation reaction in alkaline electrolytes. Energy Environ. Sci. 7, 1719–1724 (2014).

    Google Scholar 

  14. Cui, X., Ren, P., Deng, D., Deng, J. & Bao, X. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ. Sci. 9, 123–129 (2016).

    Google Scholar 

  15. Sheng, W. et al. Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy. Nat. Commun. 6, 5848 (2015).

    Google Scholar 

  16. Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).

    Google Scholar 

  17. Rizo, R., Herrero, E. & Feliu, J. M. Oxygen reduction reaction on stepped platinum surfaces in alkaline media. Phys. Chem. Chem. Phys. 15, 15416–15425 (2013).

    Google Scholar 

  18. Lee, Y., Suntivich, J., May, K. J., Perry, E. E. & Shao-Horn, Y. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 3, 399–404 (2012).

    Google Scholar 

  19. Subbaraman, R. et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 334, 1256–1260 (2011).

    Google Scholar 

  20. Strmcnik, D. et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat. Chem. 5, 300–306 (2013).

    Google Scholar 

  21. Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).

    Google Scholar 

  22. Danilovic, N. et al. Enhancing the alkaline hydrogen evolution reaction activity through the bifunctionality of Ni(OH)2/metal catalysts. Angew. Chem. Int. Ed. 51, 12495–12498 (2012).

    Google Scholar 

  23. Strmcnik, D., Lopes, P. P., Genorio, B., Stamenkovic, V. R. & Markovic, N. M. Design principles for hydrogen evolution reaction catalyst materials. Nano Energy 29, 29–36 (2016).

    Google Scholar 

  24. Ng, J. W. D. et al. Gold-supported cerium-doped NiOx catalysts for water oxidation. Nat. Energy 1, 16053 (2016).

    Google Scholar 

  25. Görlin, M. et al. Oxygen evolution reaction dynamics, Faradaic charge efficiency, and the active metal redox states of Ni–Fe oxide water splitting electrocatalysts. J. Am. Chem. Soc. 138, 5603–5614 (2016).

    Google Scholar 

  26. Tang, R. et al. Oxygen evolution reaction electrocatalysis on SrIrO3 grown using molecular beam epitaxy. J. Mater. Chem. A 4, 6831–6836 (2016).

    Google Scholar 

  27. Skúlason, E. et al. Catalytic activity of Pt nano-particles for H2 formation. Top. Catal. 57, 273–281 (2014).

    Google Scholar 

  28. Busch, M. et al. Beyond the top of the volcano? —A unified approach to electrocatalytic oxygen reduction and oxygen evolution. Nano Energy 29, 126–135 (2016).

    Google Scholar 

  29. McCrum, I. T. & Janik, M. J. pH and alkali cation effects on the Pt cyclic voltammogram explained using density functional theory. J. Phys. Chem. C 120, 457–471 (2016).

    Google Scholar 

  30. Hörmann, N. G. et al. Some challenges in the first-principles modeling of structures and processes in electrochemical energy storage and transfer. J. Power Sources 275, 531–538 (2015).

    Google Scholar 

  31. Clayborne, A., Chun, H.-J., Rankin, R. B. & Greeley, J. Elucidation of pathways for NO electroreduction on Pt(111) from first principles. Angew. Chem. Int. Ed. 54, 8255–8258 (2015).

    Google Scholar 

  32. Chan, K. & Nørskov, J. K. Potential dependence of electrochemical barriers from ab initio calculations. J. Phys. Chem. Lett. 7, 1686–1690 (2016).

    Google Scholar 

  33. Shaikhutdinov, S. & Freund, H.-J. Ultrathin oxide films on metal supports: structure–reactivity relations. Annu. Rev. Phys. Chem. 63, 619–633 (2012).

    Google Scholar 

  34. Surnev, S., Fortunelli, A. & Netzer, F. P. Structure–property relationship and chemical aspects of oxide–metal hybrid nanostructures. Chem. Rev. 113, 4314–4372 (2013).

    Google Scholar 

  35. Fu, Q., Yang, F. & Bao, X. Interface-confined oxide nanostructures for catalytic oxidation reactions. Acc. Chem. Res. 46, 1692–1701 (2013).

    Google Scholar 

  36. Fu, Q. et al. Interface-confined ferrous centers for catalytic oxidation. Science 328, 1141–1144 (2010).

    Google Scholar 

  37. Merte, L. R. et al. Water-mediated proton hopping on an iron oxide surface. Science 336, 889–893 (2012).

    Google Scholar 

  38. Sun, D. et al. Theoretical study of the role of a metal–cation ensemble at the oxide–metal boundary on CO oxidation. J. Phys. Chem. C 116, 7491–7498 (2012).

    Google Scholar 

  39. Kudernatsch, W. et al. Direct visualization of catalytically active sites at the FeO–Pt(111) interface. ACS Nano 9, 7804–7814 (2015).

    Google Scholar 

  40. Walton, A. S. et al. Interface controlled oxidation states in layered cobalt oxide nanoislands on gold. ACS Nano 9, 2445–2453 (2015).

    Google Scholar 

  41. Merte, L. R. et al. Tuning the reactivity of ultrathin oxides: NO adsorption on monolayer FeO(111). Angew. Chem. Int. Ed. 55, 9267–9271 (2016).

    Google Scholar 

  42. Chen, G. X. et al. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation. Science 344, 495–499 (2014).

    Google Scholar 

  43. Yin, H. J. et al. Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity. Nat. Commun. 6, 6430 (2015).

    Google Scholar 

  44. Wang, L. et al. Optimizing the volmer step by single-layer nickel hydroxide nanosheets in hydrogen evolution reaction of platinum. ACS Catal. 5, 3801–3806 (2015).

    Google Scholar 

  45. Wang, L. et al. Platinum-nickel hydroxide nanocomposites for electrocatalytic reduction of water. Nano Energy 31, 456–461 (2017).

    Google Scholar 

  46. Mansour, A. N. & Melendres, C. A. Analysis of X-ray absorption spectra of some nickel oxycompounds using theoretical standards. J. Phys. Chem. A 102, 65–81 (1998).

    Google Scholar 

  47. Skúlason, 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).

    Google Scholar 

  48. Zeng, Z. & Greeley, J. Characterization of oxygenated species at water/Pt(111) interfaces from DFT energetics and XPS simulations. Nano Energy 29, 369–377 (2016).

    Google Scholar 

  49. Rossmeisl, J., Chan, K., Skúlason, E., Björketun, M. E. & Tripkovic, V. On the pH dependence of electrochemical proton transfer barriers. Catal. Today 262, 36–40 (2016).

    Google Scholar 

  50. Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Google Scholar 

  51. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Google Scholar 

  52. Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Google Scholar 

  53. Zeng, Z. et al. Towards first principles-based prediction of highly accurate electrochemical Pourbaix diagrams. J. Phys. Chem. C 119, 18177–18187 (2015).

    Google Scholar 

  54. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505–1509 (1998).

    Google Scholar 

  55. Klimes, J., Bowler, D. R. & Michaelides, A. Van der Waals density functionals applied to solids. Phys. Rev. B 83, 195131 (2011).

    Google Scholar 

  56. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Google Scholar 

  57. Hansen, H. A., Rossmeisl, J. & Norskov, J. K. Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT. Phys. Chem. Chem. Phys. 10, 3722–3730 (2008).

    Google Scholar 

  58. Zeng, Z., Calle-Vallejo, F., Mogensen, M. B. & Rossmeisl, J. Generalized trends in the formation energies of perovskite oxides. Phys. Chem. Chem. Phys. 15, 7526–7533 (2013).

    Google Scholar 

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Acknowledgements

This work was supported through a Department of Energy Early Career award through the Office of Science, Office of Basic Energy Sciences, Chemical, Biological, and Geosciences Division under DE-SC0010379. Use of the Center for Nanoscale Materials and the Advanced Photon Source were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract E-AC02-06CH11357. N.M.M. acknowledges support from the US Department of Energy Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering. We acknowledge the computing resources provided on Blues and Fusion, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory, and the National Energy Research Scientific Computing Center (NERSC).

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Authors and Affiliations

  1. Davidson School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, USA

    Zhenhua Zeng, Joseph Kubal & Jeffrey Greeley

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

    Kee-Chul Chang & Nenad M. Markovic

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  1. Zhenhua Zeng
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Contributions

Z.Z. and J.G. proposed the research direction, designed computations and guided the project. Z.Z. and J.K. performed the computations. K.-C.C. and N.M.M. designed, performed and analysed the experiments. Z.Z. and J.G. analysed the results and drafted the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Jeffrey Greeley.

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Supplementary Methods, Supplementary Discussion, Supplementary Tables 1–8, Supplementary Figures 1–31, Supplementary References. (PDF 2148 kb)

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Zeng, Z., Chang, KC., Kubal, J. et al. Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion. Nat Energy 2, 17070 (2017). https://doi.org/10.1038/nenergy.2017.70

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