Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution

By A. Bergmann, E. Martínez-Moreno, D. Teschner, P. Chernev, Manuel Gliech, Jorge Ferreira de Araújo, T. Reier, Holger Dau, P. Strasser. Nature Communications, 2015

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Water splitting catalysed by earth-abundant materials is pivotal for global-scale production of non-fossil fuels, yet our understanding of the active catalyst structure and reactivity is still insufficient. Here we report on the structurally reversible evolution of crystalline Co3O4 electrocatalysts during oxygen evolution reaction identified using advanced in situ X-ray techniques. At electrode potentials facilitating oxygen evolution, a sub-nanometre shell of the Co3O4 is transformed into an X-ray amorphous CoOx(OH)y which comprises di-μ-oxo-bridged Co3+/4+ ions. Unlike irreversible amorphizations, here, the formation of the catalytically-active layer is reversed by re-crystallization upon return to non-catalytic electrode conditions. The Co3O4 material thus combines the stability advantages of a controlled, stable crystalline material with high catalytic activity, thanks to the structural flexibility of its active amorphous oxides. We propose that crystalline oxides may be tailored for generating reactive amorphous surface layers at catalytic potentials, just to return to their stable crystalline state under rest conditions. Understanding of catalyst structure and reactivity is important for the development of water splitting catalysts. Here, the authors report reversible structural transformation of the near-surface of crystalline Co3O4 electrocatalysts to an amorphous CoOx(OH)yduring oxygen evolution.

Subfields: Electrical and Electronic Engineering, Electrochemistry, Renewable Energy, Sustainability and the Environment

View Paper: https://www.semanticscholar.org/paper/bbc8331f5a2b97193c5403353c711de4b8661bd0