Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Valov, I.; Luerssen, B.; Gregoratti, L.; deSouza, R.A.; Martin, M.; Bredow, T.; Günther, S.; Dudin, P.; Mutoro, E.; Barinov, A.; Janek, J.

doi:10.1039/c0cp01024c

Journal Article

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Valov, I.FZJ* ; Luerssen, B. ; Mutoro, E. ; Gregoratti, L. ; deSouza, R. A.FZJ* ; Bredow, T.FZJ* ; Günther, S.FZJ* ; Barinov, A.FZJ* ; Dudin, P.FZJ* ; Martin, M.FZJ* ; Janek, J.

2011
RSC Publ. Cambridge

Physical Chemistry Chemical Physics 13, 3394 - 3410 (2011) [10.1039/c0cp01024c]

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Please use a persistent id in citations: http://hdl.handle.net/2128/7365 doi:10.1039/C0CP01024C

Abstract: Nitrogen is often used as an inert background atmosphere in solid state studies of electrode and reaction kinetics, of solid state studies of transport phenomena, and in applications e.g. solid oxide fuel cells (SOFC), sensors and membranes. Thus, chemical and electrochemical reactions of oxides related to or with dinitrogen are not supposed and in general not considered. We demonstrate by a steady state electrochemical polarisation experiments complemented with in situ photoelectron spectroscopy (XPS) that at a temperature of 450 °C dinitrogen can be electrochemically activated at the three phase boundary between N(2), a metal microelectrode and one of the most widely used solid oxide electrolytes--yttria stabilized zirconia (YSZ)--at potentials more negative than E = -1.25 V. The process is neither related to a reduction of the electrolyte nor to an adsorption process or a purely chemical reaction but is electrochemical in nature. Only at potentials more negative than E = -2 V did new components of Zr 3d and Y 3d signals with a lower formal charge appear, thus indicating electrochemical reduction of the electrolyte matrix. Theoretical model calculations suggest the presence of anionic intermediates with delocalized electrons at the electrode/electrolyte reaction interface. The ex situ SIMS analysis confirmed that nitrogen is incorporated and migrates into the electrolyte beneath the electrode.

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