Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

Valov, Ilia; Janek, Jürgen

doi:10.1016/j.ssi.2005.11.021

Cited by 16 publications

(16 citation statements)

References 12 publications

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“…The special aspects of interfacial reactions including relevance for heterogeneous catalysis are considered for example, in references [6,7]. Recently, substantial progress was achieved in several respects, for example: 1) in the understanding of elementary chemical reaction steps at gassolid interfaces; [8][9][10][11][12] 2) in connecting elementary rate constants with effective parameters measured in relaxation kinetics; [13][14][15][16][17] 3) in including space charges into chemical diffusion; [18][19][20] 4) in taking into account coupling diffusion with internal reactions; [21,22] 5) in the study of complex and nonlinear processes. [23][24][25][26][27][28][29][30][31][32][33] On the experimental front, the development of specific in situ techniques has contributed to the in-depth understanding of defect chemistry and transport (see, for example, references [23,[34][35][36][37]).…”

Section: Introductionmentioning

confidence: 99%

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material

2008

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The kinetics of stoichiometry change of an oxide--a prototype of a simple solid-state reaction and a process of substantial technological relevance--is studied and analyzed in great detail. Oxygen incorporation into strontium titanate was chosen as a model process. The complete reaction can be phenomenologically and mechanistically understood beginning with the surface reaction and ending with the transport in the perovskite. Key elements are a detailed knowledge of the defect chemistry of the perovskite as well as the application of a variety of experimental and theoretical tools, many of them evolving from this study. The importance of the reaction and transport steps for (electro)chemical applications is emphasized.

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Section: Introductionmentioning

confidence: 99%

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material

2008

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“…Different approaches have been applied to incorporate nitrogen into oxide materials: (i) a thermochemical approach (in the temperature range 1473 o T/K o 2673), 18 (ii) pulsed laser deposition (PLD), 19 and (iii) an electrochemical approach. 20,21 The difference between these three methods can be illustrated by decomposing eqn (1) into two reactions: In approach (i) the electrons required for reaction (4) to proceed are generated by reaction (3) proceeding towards the left (i.e. low oxygen activities).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Valov

Luerßen

Mutoro

et al. 2011

Phys. Chem. Chem. Phys.

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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 1C 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 = À1.25 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 = À2 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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“…Keeping in mind the mechanistic studies carried out by Valov and Janek [13], showing unambiguously that nitrogen diffusion is by far not the slowest step of the whole incorporation process, this is not surprising. Furthermore, it should be mentioned that the maximum amount of incorporated nitrogen depends also on the cationic dopant concentration.…”

Section: Resultsmentioning

confidence: 91%

Nitrogen‐doped zirconia single crystals

Rödel¹,

Wang

Lerch

et al. 2006

Cryst. Res. Technol.

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The aim of this work is the preparation of nitrogen-doped single crystals of cation-stabilized zirconia. Thin plates of these crystals were nitrided in a graphite heated resistance furnace with nitrogen as reaction gas. Several dwell times and reaction temperatures were tested and their effect on the amount of incorporated nitrogen is investigated. During nitridation at high temperatures a rock salt-type 'ZrN' layer grows on the surface, leading to the destruction of the crystal. In contrast to the fluorite-type bulk material, which can be described as a fast anion conductor, the surface layer shows electronic conductivity. For possible applications of the bulk material (solid electrolyte) the formation of the surface layer must be avoided. Therefore, the interface between surface epilayer and bulk material was investigated in detail by electron microscopy methods.

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Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

Cited by 16 publications

References 12 publications

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Nitrogen‐doped zirconia single crystals

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Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

Cited by 16 publications

References 12 publications

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO3 as a Model Material

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO3 as a Model Material

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Nitrogen‐doped zirconia single crystals

Contact Info

Product

Resources

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How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO₃ as a Model Material