Improved Electrochemical Phase Diagrams from Theory and Experiment: The Ni-Water System and Its Complex Compounds

L. F. Huang, M. J. Hutchison, R. J. Santucci, J. R. Scully, J. M. Rondinelli*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

119 Scopus citations


Electrode potential-pH (Pourbaix) diagrams provide a phase map of the most stable compounds of a metal, its corrosion products, and associated ions in solution. The utility of these phase diagrams is that they enable the assessment of electrochemical stabilities, for example, of Ni metal and its derived oxides, hydroxides, and oxyhydroxides, against corrosion in aqueous environments. Remarkably, the Ni Pourbaix diagrams reported over the last 50 years are largely inconsistent with various electrochemical observations, which may be attributed to inaccurate experimental free energies of formation (ΔfG) for the complex Ni-based compounds used in producing the available diagrams. Here we show that state-of-the-art density-functional theory (DFT) can be used to obtain accurate ΔfG values, which lead to Ni Pourbaix diagrams that are more consistent with direct electrochemical experiments: Electrochemical impedance spectroscopy and surface-enhanced Raman spectroscopy are used to characterize the electrochemical stabilities of NiO and Ni(OH)2 formed on Ni, demonstrating the reliability in correction-free first-principles based Pourbaix diagrams. Our results show the importance in applying modern density functionals in combination with experimental advances in aqueous environment compound identification for assessing electrochemical phase stability of materials, which will be useful for the design, synthesis, and selection of corrosion-resistant metals, photoabsorbers, and photocatalytic materials.

Original languageEnglish (US)
Pages (from-to)9782-9789
Number of pages8
JournalJournal of Physical Chemistry C
Issue number18
StatePublished - May 11 2017

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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