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


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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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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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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The authors declare no competing financial interests.

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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).

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