Primary Oxide Latent Storage and Spillover for Reversible Electrocatalysis in Oxygen and Hydrogen Electrode Reactions

  • Milan M. Jaksic
  • Angeliki Siokou
  • Georgios D. Papakonstantinou
  • Jelena M. JaksicEmail author
Part of the Nanostructure Science and Technology book series (NST)


Ever since Sir William Grove invented gas fed fuel cells (FC), the main electrocatalytic challenge has been to establish the reversible oxygen electrode (ROE) to take advantage of the entire thermodynamically available current/voltage range between hydrogen and oxygen evolving limits. This challenge is the main subject of the present study.

Now, hypo-d-(f)-oxides of transition elements (d ≤ 5) have the pronounced effect of causing spontaneous adsorptive dissociation of water molecules, which is the main and initial thermodynamic precondition for the reversible latent storage and spillover properties of primary oxides (Pt-OH, Au-OH), indispensable ingredients in electrocatalysis for the oxygen electrode reactions. The higher the altervalent number (or capacity) of these oxides, given the proper valence in the hypo-d-(f)-oxide supports, the higher the overall (electro)catalytic yields for cathodic oxygen reduction (ORR) and anodic evolution (OER). In fact, cyclic voltammetry reveals the interrelated redox properties of the primary (Pt-OH) and surface (Pt=O) oxides in between the cathodic hydrogen and anodic oxygen evolving limits. Of course, the existence of the primary oxides has long been known as the intermediate state between hydrogen oxidation in heterogeneous Doeberriner reaction on Pt catalyst, and self-catalyzation by water molecules (Ertel). Such interfering interrelated and auto-catalytic species substantially define and restrict electrocatalytic properties of plain (Pt, Au), or non-interactive supported noble metals (Pt/C, Au/C), along the potential axis, and within some positive range even make them highly polarizable. Meanwhile, the latter can be continuously electrocatalytically depolarized and reactivated. For more than a century, such spontaneously renewable activation and maintenance of the reversible electrocatalytic state for the oxygen electrode reactions all along cyclic voltammograms has been the main electrocatalytic challenge. So, continuously and spontaneously renewable dissociative adsorption of water molecules upon hypo-d-(f)-oxide supports enables the latent storage and electrocatalytic spillover properties of the primary oxide(s) for the reversible oxygen electrode (ROE) behavior, and Pt-OH and Au-O have been identified and substantiated all along the potential axis between the hydrogen and oxygen evolving limits. Meanwhile, on plain individual transition metals, under such conditions there usually occurs a surface oxide (Pt=O) reaction polarization within a broader positive potential range because of the absence of primary oxide spillover. Such advanced latent storage and spillover of the primary oxide electrocatalytic properties suggests interactive (SMSI—Strong Metal-Support Interaction) nanostructured hyper-d-Pt (Au, RuPt) clusters, which become selectively grafted on individual or composite mixed valence hypo-d-(f)-oxide supports. The latter then feature the extra high stability, pronounced electronic conductivity and many other d-electronic based metal properties mostly arising from the hypo-hyper-d-d-(f)-interelectronic bonding effect, along with spontaneous dissociative water molecules adsorption upon exposed oxide support surfaces, thereby yielding renewable primary oxide latent storage by simple continuous water vapor supply, and characteristic membrane-type hydroxide ions surface migration. Migrating hydroxide, as an individual species, under imposed polarization partially transfers its prevailing electron to the metallic electrocatalyst, thence resulting in a Pt-OH (Au-OH) dipole, and by the surface repulsion obeys reversible spillover distribution and imposes electrocatalytic ROE properties all over the catalyst surface and DL pseudo-capacitance charging and discharging, as well. The strong adsorptive surface oxide (Pt=O → 1) deposition out of the primary oxide (Pt-OH → 0) irreversible disproportionation, thereby imposes unusually high reaction polarization of Pt, Au, Pd and all other noble and transition d-metals within a very broad (600 mV, and even broader) potential range, and thereby, in general, mostly pronounced polarizable non-catalytic properties for oxygen electrode (ORR, OER) reactions. Thus, the strong interactive and selective hypo-hyper-d-d-interelectronic grafting bonded of nanostructured individual (Pt), or prevailing hyper-d-intermetallic phase (MoPt3; HfPd3) cluster catalysts on altervalent and mixed-valence hypo-d-(f)-oxide supports, make possibly primary oxide latent storage and enhanced spillover, and thus enable approaching their reversible (electro)catalytic properties and optimization for the ROE. The reversible alterpolar bronze behaves (Pt/HxNbO5 ⇔ Pt/Nb(OH)5, x ≈ 0.3), as the thermodynamic equilibrium alterpolar state, thereby substantially advanced electrocatalytic properties of these composite interactive electrocatalysts for both oxygen (ORR, OER) and hydrogen (HOR, HER) electrode reactions, and consequently, have been inferred as spontaneously altering, and strong spillover features, in particular unique and superior for the revertible ((PEMFC versus WE) = Water Electrolysis) cells.


Oxygen Reduction Reaction Electrocatalytic Activity Hydrogen Evolution Reaction Oxygen Evolution Reaction Mixed Valence 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The present chapter has been conceived and carried out at the Institute of Chemical Engineering Sciences, ICEHT/FORTH, Patras, Greece.


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Copyright information

© Springer International Publishing Switzerland 2016

Authors and Affiliations

  • Milan M. Jaksic
    • 1
    • 2
  • Angeliki Siokou
    • 1
  • Georgios D. Papakonstantinou
    • 1
  • Jelena M. Jaksic
    • 1
    Email author
  1. 1.Institute of Chemical Engineering Sciences, CEHT/FORTHPatrasGreece
  2. 2.Faculty of Agriculture, University of BelgradeBelgradeSerbia

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